CN107248569B - Antimony/nitrogen-doped carbon composite prepared by taking 1-ethyl-3-methylimidazol dicyandiamide as carbon source and preparation method and application thereof - Google Patents

Antimony/nitrogen-doped carbon composite prepared by taking 1-ethyl-3-methylimidazol dicyandiamide as carbon source and preparation method and application thereof Download PDF

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CN107248569B
CN107248569B CN201710298922.9A CN201710298922A CN107248569B CN 107248569 B CN107248569 B CN 107248569B CN 201710298922 A CN201710298922 A CN 201710298922A CN 107248569 B CN107248569 B CN 107248569B
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antimony
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doped carbon
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CN107248569A (en
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周小四
许欣
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Nanjing Normal University
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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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a method for preparing an antimony/nitrogen-doped carbon composite by using 1-ethyl-3-methylimidazolium dicyandiamide as a carbon source, which comprises the following steps: dissolving antimony trichloride and 1-ethyl-3-methylimidazol dicyandiamide in methanol respectively, mixing under vigorous stirring, mixing the two solutions fully, standing, centrifuging to collect a gelatinous white solid, and centrifuging and washing with methanol; subjecting the resulting product to hydrogenation in H2Carbonizing in an Ar atmosphere to obtain the antimony/nitrogen doped carbon composite. The invention also provides the antimony/nitrogen-doped carbon composite prepared by the method and application of the composite as a negative electrode material of a sodium-ion battery. The method takes the antimony trichloride and the ionic liquid 1-ethyl-3-methylimidazol dicyanamide as raw materials, has simple process, green and environment-friendly raw materials and is suitable for batch production, and the prepared antimony/nitrogen-doped carbon composite has excellent electrochemical performance and can be used as an ideal cathode material of a sodium ion battery to replace hard carbon with low reversible capacity to be applied to the sodium ion battery.

Description

Antimony/nitrogen-doped carbon composite prepared by taking 1-ethyl-3-methylimidazol dicyandiamide as carbon source and preparation method and application thereof
Technical Field
The invention relates to an electrode material, in particular to an antimony/nitrogen-doped carbon composite prepared by taking 1-ethyl-3-methylimidazol dicyandiamide as a carbon source, a preparation method thereof and application of the antimony/nitrogen-doped carbon composite as a sodium ion battery cathode material.
Background
Common chemical power sources today include lead-acid batteries, nickel metal hydride batteries, nickel cadmium batteries, and lithium ion batteries. These chemical sources of electricity play a significant role in today's human life and the development of the national economy. Among them, the lead-acid battery has low material price and mature technology development, so the lead-acid battery is most widely applied. However, lead-acid batteries have low energy density and contain heavy metal element lead, which causes serious pollution to the environment. These limitations of lead-acid batteries limit further expansion of their range of applications. The rapid development of society puts higher demands on battery technology, and the development of novel environment-friendly batteries has become a trend. Lithium ion batteries are widely used in the fields of portable electronic devices, hybrid vehicles and pure electric vehicles due to their high energy density and long cycle life. However, lithium batteries have low crust content (0.0065%), uneven geographical distribution, and high cost, which makes lithium batteries unable to meet the increasing large-scale energy storage requirements. In recent years, sodium ion batteries have attracted attention as a substitute for lithium ion batteries, mainly because they have advantages of inexpensive raw materials, abundant resources, environmental friendliness, and the like.
To date, a variety of positive electrode materials for sodium ion batteries have been prepared, while the development of negative electrode materials for sodium ion batteries is relatively slow. Therefore, designing and preparing high-performance cathode materials are urgent matters for the development of sodium ion batteries. Antimony has a high theoretical capacity (660 mAh. g)-1) And the conductivity is good, so that the material becomes a promising negative electrode material of the sodium ion battery. However, antimony has serious volume change in the process of sodium intercalation, which easily causes antimony particles to be pulverized and electric contact to be lost, and finally, the cycle stability is poor.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for preparing an antimony/nitrogen-doped carbon composite, which is green and environment-friendly and has a simple process, and provides a sodium ion battery cathode material with excellent electrochemical performance.
The technical scheme is as follows: a method for preparing an antimony/nitrogen-doped carbon composite by using 1-ethyl-3-methylimidazolium dicyandiamide as a carbon source, which comprises the following steps:
1) dissolving antimony trichloride in methanol to form a clear solution, and obtaining a solution A;
2) dissolving 1-ethyl-3-methylimidazol dicyanamide in methanol to obtain a solution B;
3) pouring the solution B into the solution A under the condition of vigorous stirring, fully mixing the two solutions, standing, centrifuging to collect a gelatinous white solid, and centrifuging and washing by using methanol;
4) subjecting the product obtained in step 3) to reaction in H2And carbonizing in an/Ar mixed atmosphere to obtain the antimony/nitrogen-doped carbon composite.
In the method, the mass ratio of the added antimony trichloride to the 1-ethyl-3-methylimidazole dicyandiamide is 7: 10-9: 10.
In the step 3), standing for 10-20 hours; the number of times of centrifugal washing with methanol is 3 to 6.
In the step 4), the carbonization is to place the product obtained in the step 3) into a tubular furnace, and the temperature of the tubular furnace is 4-10 ℃ per minute-1Heating to 550-650 ℃ at the rate of (1) and keeping for 2-4 h; h2In a mixed atmosphere of/Ar, H2The volume percentage of (A) is 5-10%.
The method takes non-volatile and non-flammable ionic liquid 1-ethyl-3-methylimidazol dicyanamide as a carbon source, and antimony and the ionic liquid are mixed, dissolved, centrifuged, carbonized and the like to obtain the antimony/nitrogen-doped carbon composite. Accordingly, in another aspect, the present invention provides an antimony/nitrogen-doped carbon composite prepared by the above method. Testing the components of the obtained antimony/nitrogen-doped carbon composite by using an X-ray powder diffractometer (XRD) and an X-ray photoelectron spectroscopy (XPS); the size, morphology, microstructure, and the like of the obtained antimony/nitrogen-doped carbon composite were analyzed using a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM), selective electron diffraction (SAED), and a high-resolution transmission electron microscope (HRTEM). The result shows that the surface of the antimony/nitrogen-doped carbon composite is smooth, nano-sized antimony is uniformly distributed in an amorphous carbon substrate, nitrogen is doped in the carbon substrate, and antimony nano crystal grains are uniformly coated by the nitrogen-doped carbon.
The antimony/nitrogen-doped carbon composite is used as a sodium ion battery cathode material to test the electrochemical performance of the sodium ion battery cathode material, and the result shows that the antimony/nitrogen-doped carbon composite has excellent electrochemical performance, and the charge/discharge specific capacity of the first ring is 440/720mAhg-1After circulating for 150 circles, the specific charge/discharge capacity can still be 385.4/395mAh g-1The capacity retention rate reaches 87.5%/54.8%, and the rate capability is excellent. Therefore, the invention also provides the application of the antimony/nitrogen-doped carbon composite as a negative electrode material of a sodium ion battery, and provides a negative electrode material of the sodium ion battery, wherein the negative electrode material of the sodium ion battery comprises the antimony/nitrogen-doped carbon composite.
Has the advantages that: the method for preparing the antimony/nitrogen-doped carbon compound takes antimony trichloride and ionic liquid 1-ethyl-3-methylimidazol dicyanamide ionic liquid as raw materials, and the antimony/nitrogen-doped carbon compound is obtained by mixing, centrifuging and pyrolyzing the raw materials. The method has simple process, the used raw materials are green and environment-friendly, the method is suitable for batch production, and the prepared antimony/nitrogen-doped carbon composite has excellent electrochemical performance, can be used as an ideal sodium ion battery cathode material to replace hard carbon with low reversible capacity to be applied to a sodium ion battery, and is a sodium ion battery cathode material with a prospect.
Drawings
FIG. 1a is a Scanning Electron Microscope (SEM) image of an antimony/nitrogen-doped carbon composite showing the smooth surface of the composite resulting from pyrolysis, indicating that the antimony is coated with nitrogen-doped carbon; FIG. 1b is a Transmission Electron Microscope (TEM) image of an antimony/nitrogen-doped carbon composite showing that antimony has an average size of about 15nm in the composite and is uniformly distributed in the carbon substrate; FIG. 1c is a Selected Area Electron Diffraction (SAED) diagram of an antimony/nitrogen-doped carbon composite showing the formation of hexagonal antimony nanocrystals in an amorphous carbon substrate; FIG. 1d is a High Resolution Transmission Electron Microscopy (HRTEM) image of an antimony/nitrogen doped carbon composite showing 0.31nm interplanar spacing in the antimony grains, with the antimony nanocrystals uniformly coated with nitrogen doped carbon.
FIG. 2a is an X-ray diffraction (XRD) pattern of an antimony/nitrogen doped carbon composite (Sb @ NC) showing that the characteristic peak (012) of antimony appears at 28.7 deg., corresponding to a interplanar spacing of 0.31nm, consistent with results observed with HRTEM; FIG. 2b is an XPS plot of antimony/nitrogen doped carbon composite (Sb @ NC) and ionic liquid derived nitrogen doped carbon (NC) showing that the signal for N is clearly visible, and that the high resolution N1s XPS spectrum shows a new peak at 399.1eV, which is likely to be comparable to SbCl3Emim-dca in a reducing atmosphere (H)2Ar) during pyrolysis to produce Sb-N-C bonds.
FIG. 3a is a graph of the charge/discharge curves for an antimony/nitrogen doped carbon composite (Sb @ NC) showing first cycle charge and discharge capacities of 440 and 720mAh g-1The coulomb efficiency is about 61%; the large irreversible capacity loss (39%) of the first turn is usually due to the first turn discharge processThe electrolyte is decomposed and a solid electrolyte membrane is formed on the surface of the composite; FIG. 3b is a graph of the cycle performance of antimony/nitrogen-doped carbon composite (Sb @ NC), nitrogen-doped carbon (NC) and antimony nanocrystals (Sb), FIG. 3c is a graph of the cycle performance of high-content-antimony/nitrogen-doped carbon composite (H-Sb @ NC) and low-content-antimony/nitrogen-doped carbon composite (L-Sb @ NC) (based on the TGA results, the obtained Sb content is named as high-content and low-content antimony/nitrogen-doped carbon composite), antimony/sucrose pyrolytic carbon composite (Sb @ SC), and antimony/polyacrylonitrile pyrolytic carbon composite (Sb @ PNC), and the cycle performance graphs (FIGS. 3b and 3c) are graphs of the cycle performance of Na/Na in the voltage range of 0.01 to 2Vvs Na/Na+Current density of 100mAg-1Under the conditions of (1), the cycle performance of 7 materials and the first-circle discharge capacity of the antimony/nitrogen-doped carbon compound are 720 mAh.g-1The reversible capacity after 100 cycles is 395mAh g-1Higher than the capacity of other six materials; FIG. 3d is a graph of the rate capability of antimony/nitrogen doped carbon composites (Sb @ NC), antimony/sucrose pyrolytic carbon composites (Sb @ SC), antimony/polyacrylonitrile pyrolytic carbon composites (Sb @ PNC), the graph of the rate capability (FIG. 3d) showing that the antimony/nitrogen doped carbon composites (Sb @ NC) are at 2 or 5A g even at high current densities, e.g., 2 or 5A g-1The capacity retention rate can still be maintained at 63.9 or 53.1%, corresponding to 285 or 237mAh g-1The capacity of (c).
Detailed Description
Example 1
(1) Preparation of antimony/nitrogen doped carbon composites
400mg of antimony trichloride was weighed and dissolved in 5mL of methanol to form a clear solution, which was designated as solution A. 500mg of 1-ethyl-3-methylimidazolium dicyanamide ionic liquid was dissolved in 5mL of methanol to obtain a solution B. Solution B was poured into solution a under vigorous stirring to obtain a homogeneous solution and stirring was terminated. After standing for 12h, the white solid was collected by centrifugation, washed with methanol and centrifuged 5 times. Subsequently, the product obtained is placed in a porcelain boat and transferred into a tube furnace, in H2The temperature was raised to 600 ℃ at a rate of 5 ℃/min under an/Ar (5: 95v/v) atmosphere and then maintained at 600 ℃ for 2h to give a black antimony/nitrogen doped carbon composite (Sb @ NC).
(2) Characterization of antimony/nitrogen-doped carbon composites
The size, morphology and microstructure of the resulting antimony/nitrogen doped carbon composite were analyzed using SEM, TEM, SAED and HRTEM images. FIG. 1a is a Scanning Electron Microscope (SEM) image of an antimony/nitrogen-doped carbon composite showing that the composite obtained by pyrolysis has a smooth surface, indicating that antimony is coated with nitrogen-doped carbon. FIG. 1b is a Transmission Electron Micrograph (TEM) of the antimony/nitrogen-doped carbon composite, from which it can be seen that antimony has an average size of about 15nm in the composite and is uniformly distributed in the carbon matrix. FIG. 1c is a Selected Area Electron Diffraction (SAED) plot of an antimony/nitrogen doped carbon composite, demonstrating the formation of hexagonal antimony nanocrystals with some of the amorphous carbon substrate. FIG. 1d is a High Resolution Transmission Electron Microscopy (HRTEM) image of an antimony/nitrogen-doped carbon composite showing that the interplanar spacing in the antimony grains is 0.31nm, with the larger interplanar spacing favoring Na+Intercalation and alloying.
The composition of the resulting antimony/nitrogen-doped carbon composite was tested by XRD (JCPDS card No. 35-0732). Figure 2a is an X-ray diffraction (XRD) pattern of an antimony/nitrogen doped carbon composite (Sb @ NC) showing that the characteristic peak (012) of antimony appears at 28.7 deg., corresponding to a interplanar spacing of 0.31nm, consistent with results observed with HRTEM, demonstrating that the antimony in the composite obtained by pyrolysis is nanocrystalline. FIG. 2b is an XPS plot of antimony/nitrogen doped carbon composite (Sb @ NC) and ionic liquid derived nitrogen doped carbon (NC) showing that the signal for N is clearly visible, and that the high resolution N1s XPS spectrum shows a new peak at 399.1eV, which is likely to be comparable to SbCl3Emim-dca in a reducing atmosphere (H)2/Ar), analysis of XPS plots (fig. 2b) indicates that Sb-N-C bonds may form in the antimony/nitrogen doped carbon composite, contributing to improved sodium storage performance.
(3) Electrochemical performance test
Using deionized water as a solvent, grinding and uniformly mixing the antimony/nitrogen-doped carbon composite (Sb @ NC) prepared in the embodiment, carbon black and sodium carboxymethylcellulose in a mass ratio of 7: 2: 1, coating the obtained uniform slurry on a Cu foil, and drying the Cu foil in vacuum at40 ℃ for 12 hours to obtain the loading capacity of 0.8-1.2mg em-2The electrode sheet of (1). Using 1mol of L-1NaClO4The ethylene carbonate/propylene carbonate/fluorinated ethylene carbonate (volume ratio is 1: 0.1) solution is used as the electrolyte of the sodium ion battery, and the glass fiber and the pure sodium metal foil are respectively used as the diaphragm and the 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.
Constant current charge and discharge test of the cell at room temperature, using a blue CT2001A multichannel cell test system at 0.01-2V vs Na/Na+Within a fixed voltage range. Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) were tested using the parsta 4000 electrochemical workstation. CV at 0.1mV s-1At a sweep rate of (2), EIS is performed at a sine wave frequency in the range of 100kHz to 10mHz with an amplitude of 10.0 mV. The specific performance is shown in fig. 3a, 3b, 3 d. FIG. 3a is a graph of the charge/discharge curves for an antimony/nitrogen doped carbon composite (Sb @ NC) showing first cycle charge and discharge capacities of 440 and 720mAh g-1The coulomb efficiency is about 61%; the large irreversible capacity loss (39%) of the first cycle is due to the electrolyte decomposing during the first cycle of discharge and forming a solid electrolyte membrane on the composite surface. FIG. 3b is a graph showing the cycle performance of an antimony/nitrogen-doped carbon composite (Sb @ NC) having a first discharge capacity of 720mAh · g-1The reversible capacity after 100 cycles is 395mAh g-1. FIG. 3d is a graph of the rate capability of antimony/nitrogen doped carbon composites (Sb @ NC), antimony/sucrose pyrolytic carbon composites (Sb @ SC), antimony/polyacrylonitrile pyrolytic carbon composites (Sb @ PNC), the rate capability graph (FIG. 3d) showing that the antimony/nitrogen doped carbon composites (Sb @ NC) are at even high current densities, e.g., 2 or 5A · g ·-1The capacity retention rate can still be maintained at 63.9 or 53.1%, corresponding to 285 or 237mAh g-1The capacity of (c).
Comparative example 1
(1) Preparation of high-content-antimony/nitrogen-doped carbon composite (H-Sb @ NC)
500mg of antimony trichloride was weighed out and dissolved in 5mL of methanol to form a clear solution, designated as solution A. 500mg of 1-ethyl-3-methylimidazolium dicyanamide ionic liquid was dissolved in 5mL of methanol to obtain a solution B. Pour solution B under vigorous stirringAdding the mixture into the solution A to obtain a uniform solution, and stopping stirring. After standing for 12h, the white solid was collected by centrifugation, washed with methanol and centrifuged 5 times. Subsequently, the product obtained is transferred into a porcelain boat and transferred into a tube furnace, in H2Heating to 600 ℃ at a heating rate of 5 ℃/min under an/Ar (5: 95v/v) atmosphere, and then keeping at 600 ℃ for 2H to obtain the black high-content-antimony/nitrogen-doped carbon composite (H-Sb @ NC).
(2) Electrochemical performance test
Grinding and uniformly mixing the high-content-antimony/nitrogen-doped carbon composite (H-Sb @ NC) prepared in the step (1), carbon black and sodium carboxymethylcellulose in a mass ratio of 7: 2: 1 by taking deionized water as a solvent, coating the obtained uniform slurry on a Cu foil, and drying the Cu foil in vacuum at40 ℃ for 12 hours to obtain the material with the loading capacity of 0.8-1.2mg cm-2The electrode sheet of (1). Using 1mol of L- 1NaClO4The ethylene carbonate/propylene carbonate/fluorinated ethylene carbonate (volume ratio is 1: 0.1) solution is used as the electrolyte of the sodium ion battery, and the glass fiber and the pure sodium metal foil are respectively used as the diaphragm and the 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 obtained high-content-antimony/nitrogen-doped carbon composite (H-Sb @ NC) was subjected to sodium ion battery performance tests, the specific process and condition parameters were the same as those of example 1, and the specific test results are shown in FIG. 3 c. As shown in FIG. 3c, the cycle performance diagram (FIG. 3c) shows the first cycle charge/discharge capacity of 407/624mAh g of the material-1(ii) a The charging/discharging capacity is reduced to 285/292mAh g after 100 cycles of circulation-1The capacity retention rate is 70.0%/46.8%, which is obviously lower than the cycle performance of the antimony/nitrogen-doped carbon composite (Sb @ NC).
Comparative example 2
(1) Preparation of Low-content-Black antimony/Nitrogen-doped carbon composite (L-Sb @ NC)
320mg of antimony trichloride was weighed and dissolved in 5mL of methanol to form a clear solution, designated as solution A. 500mg of 1-ethyl-3-methylimidazolium dicyanamide ionic liquid was dissolved in 5mL of methanol to obtain solution B. Pour solution B under vigorous stirringThe mixture was added to solution A to obtain a uniform dispersion, and the stirring was stopped. After standing for 12h, the white solid was collected by centrifugation, washed with methanol and centrifuged 5 times. Subsequently, the product obtained is placed in a porcelain boat and transferred into a tube furnace, in H2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere of/Ar (5: 95v/v), and then keeping at 600 ℃ for 2h to obtain the low-content-black antimony/nitrogen-doped carbon composite (L-Sb @ NC).
(2) Electrochemical performance test
Grinding and uniformly mixing the low-content-black antimony/nitrogen-doped carbon composite (L-Sb @ NC) prepared in the step (1), carbon black and sodium carboxymethylcellulose in a mass ratio of 7: 2: 1 by taking deionized water as a solvent, coating the obtained uniform slurry on a Cu foil, and drying the Cu foil in vacuum at40 ℃ for 12 hours to obtain the low-content-black antimony/nitrogen-doped carbon composite (L-Sb @ NC) with a loading amount of 0.8-1.2mg cm-2The electrode sheet of (1). Using 1mol L-1NaClO4The ethylene carbonate/propylene carbonate/fluorinated ethylene carbonate (volume ratio is 1: 0.1) solution is used as the electrolyte of the sodium ion battery, and the glass fiber and the pure sodium metal foil are respectively used as the diaphragm and the 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.
As shown in FIG. 3c, the cycle performance diagram (FIG. 3c) shows the first cycle charge/discharge capacity of 374/584mAh g of the material-1(ii) a After 100 cycles, the capacity is reduced to 314/319mAh g-1The capacity retention rate was 91.5%/54.6%, and the capacity retention rate was not low, but was significantly lower than the cycle performance of the antimony/nitrogen-doped carbon composite (Sb @ NC).
Comparative example 3
(1) Preparation of antimony/sucrose pyrolytic carbon composite (Sb @ SC)
400mg of antimony trichloride was weighed and dissolved in 5mL of methanol to form a clear solution, designated as solution A. 500mg of sucrose was dissolved in 5mL of methanol to obtain solution B. The solution B was poured into the solution A under vigorous stirring to obtain a uniform dispersion, and then the stirring was terminated. After standing for 12h, the white solid was collected by centrifugation, washed with methanol and centrifuged 5 times. Subsequently, the product obtained is placed in a porcelain boat and transferred toIn a tube furnace, in H2Heating to 600 ℃ at a heating rate of 5 ℃/min under an atmosphere of/Ar (5: 95v/v), and then keeping at 600 ℃ for 2 hours to obtain a black antimony/sucrose pyrolytic carbon composite (Sb @ SC).
(2) Electrochemical performance test
Grinding and uniformly mixing the antimony/sucrose pyrolytic carbon composite (Sb @ SC) prepared in the step (1), carbon black and sodium carboxymethylcellulose in a mass ratio of 7: 2: 1 by taking deionized water as a solvent, coating the obtained uniform slurry on a Cu foil, and drying the Cu foil in vacuum at40 ℃ for 12 hours to obtain the product with the loading capacity of 0.8-1.2mg cm-2The electrode sheet of (1). Using 1mol of L-1NaClO4The ethylene carbonate/propylene carbonate/fluorinated ethylene carbonate (volume ratio is 1: 0.1) solution is used as the electrolyte of the sodium ion battery, and the glass fiber and the pure sodium metal foil are respectively used as the diaphragm and the 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.
As shown in FIGS. 3c and 3d, the cycle performance diagram (FIG. 3c) shows that the first-turn specific charge/discharge capacity of the material is 281/501 mAh g-1(ii) a After 100 cycles, the specific charge/discharge capacity is 215/219mAh g-1The capacity retention rate is 76.8%/43.6%, which is lower than the cycle performance of the antimony/nitrogen-doped carbon composite. The rate capability graph (FIG. 3d) shows that the material is at 5Ag-1Capacity of 200mAhg at current density-1The rate capability is obviously lower than that of the antimony/nitrogen-doped carbon composite (Sb @ NC).
Comparative example 4
(1) Preparation of antimony/polyacrylonitrile pyrolytic carbon composite (Sb @ PNC)
400mg of antimony trichloride was weighed and dissolved in 5mL of N, N-dimethylformamide to form a clear solution, designated as solution A. 500mg of polyacrylonitrile was dissolved in 5mL of N, N-dimethylformamide to obtain a solution B. The solution B was poured into the solution A under vigorous stirring to obtain a uniform dispersion, and then the stirring was terminated. After 12 hours, a white solid was collected by centrifugation. The white solid was washed with methanol and centrifuged 5 times. Subsequently, the product obtained is placed in a porcelain boat and transferred into a tube furnace, in H2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere of/Ar (5: 95v/v), and then keeping at 600 ℃ for 2 hours to obtain the black antimony/polyacrylonitrile pyrolytic carbon composite.
(2) Electrochemical performance test
Grinding and uniformly mixing the antimony/polyacrylonitrile pyrolytic carbon composite (Sb @ PNC) prepared in the step (1), carbon black and sodium carboxymethylcellulose in a mass ratio of 7: 2: 1 by taking deionized water as a solvent, coating the obtained uniform slurry on a Cu foil, and drying the Cu foil in vacuum at40 ℃ for 12 hours to obtain the product with the loading capacity of 0.8-1.2mg cm-2The electrode sheet of (1). Using 1mol of L-1NaClO4The ethylene carbonate/propylene carbonate/fluorinated ethylene carbonate (volume ratio is 1: 0.1) solution is used as the electrolyte of the sodium ion battery, and the glass fiber and the pure sodium metal foil are respectively used as the diaphragm and the 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.
As shown in FIGS. 3c and 3d, the cycle performance diagram (FIG. 3c) shows that the first-turn specific charge/discharge capacity of the material is 217/376 mAh g-1(ii) a After 100 cycles, the specific charge/discharge capacity is 167/168mAh g-1The capacity retention rate is 76.7%/44.5%, which is lower than the cycle performance of the antimony/nitrogen-doped carbon composite. The rate capability plot (FIG. 3d) shows that the material is at 5A g-1At a current density, the capacity is 110mAh g-1The rate capability is obviously lower than that of the antimony/nitrogen-doped carbon composite (Sb @ NC).
Comparative example 5
(1) Preparation of Nitrogen-doped carbon Compounds (NC)
1.0mL of 1-ethyl-3-methylimidazolium dicyanamide was placed in a porcelain boat and transferred into a tube furnace in H2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere of/Ar (5: 95v/v), and then keeping at 600 ℃ for 2h to obtain the black nitrogen-doped carbon compound (NC).
(2) Electrochemical performance test
Deionized water is used as a solvent, and the nitrogen-doped carbon compound (NC) prepared in the step (1) is ground with carbon black and sodium carboxymethylcellulose in a mass ratio of 7: 2: 1Grinding and mixing uniformly, coating the obtained uniform slurry on a Cu foil, and vacuum drying at40 ℃ for 12h to obtain the slurry with the loading capacity of 0.8-1.2mg cm-2The electrode sheet of (1). Using 1mol of L-1NaClO4The ethylene carbonate/propylene carbonate/fluorinated ethylene carbonate (volume ratio is 1: 0.1) solution is used as the electrolyte of the sodium ion battery, and the glass fiber and the pure sodium metal foil are respectively used as the diaphragm and the 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.
As shown in FIG. 3b, the cycle performance diagram (FIG. 3b) shows that the first-turn specific charge/discharge capacity of the material is 90/302 mAhg-1(ii) a After 100 cycles, the specific charge/discharge capacity is 116/117mAh g-1The capacity retention rate is 77.3%/38.8%, which is lower than the cycle performance of antimony/nitrogen doped carbon composite (Sb @ NC).
Comparative example 6
(1) Preparation of antimony nanocrystals (Sb)
Under the protection of argon, 0.45g of NaBH4Dissolved in a single-neck flask containing 13ml of N-dimethylformamide and heated to 60 ℃. Subsequently, the single-neck flask was immediately charged with 0.68 g of SbCl by a syringe32ml of N-dimethylformamide. The reaction in the single-neck flask quickly darkened and rapidly cooled using an ice-water bath. After cooling to room temperature, the resultant antimony nanocrystals (Sb) were collected by centrifugation, washed several times with deionized water, and dried overnight at40 ℃.
(2) Electrochemical performance test
Grinding and uniformly mixing the antimony nanocrystals (Sb) prepared in the step (1), carbon black and sodium carboxymethylcellulose in a mass ratio of 7: 2: 1 by taking deionized water as a solvent, coating the obtained uniform slurry on a Cu foil, and drying the Cu foil in vacuum at40 ℃ for 12 hours to obtain the product with the loading capacity of 0.8-1.2mg cm-2The electrode sheet of (1). Using 1mol of L-1NaClO4The ethylene carbonate/propylene carbonate/fluorinated ethylene carbonate (volume ratio is 1: 0.1) solution is used as the electrolyte of the sodium ion battery, the glass fiber and the pure sodium metal foil are respectively used as the diaphragm of the sodium ion battery anda counter electrode. 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.
As shown in FIG. 3b, the cycle performance diagram (FIG. 3b) shows that the first-turn specific charge/discharge capacity of the material is 390/592 mAhg-1(ii) a After 100 cycles, the specific charge/discharge capacity is 40/42mAh g-1The capacity retention rate is 10.3%/7.0%, which is lower than the cycle performance of antimony/nitrogen-doped carbon composite (Sb @ NC).
Example 2
400mg of antimony trichloride was weighed and dissolved in 5mL of methanol to form a clear solution, designated as solution A. 500mg of 1-ethyl-3-methylimidazolium dicyanamide ionic liquid was dissolved in 5mL of methanol to obtain a solution B. The solution B was poured into the solution A under vigorous stirring to obtain a uniform dispersion, and then the stirring was terminated. After standing for 12h, the white solid was collected by centrifugation, washed with methanol and centrifuged 5 times. Subsequently, the product obtained is transferred into a porcelain boat and transferred into a tube furnace, in H2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere of/Ar (10: 90v/v), and then keeping at 600 ℃ for 4h to obtain the black antimony/nitrogen-doped carbon composite.
The structural characterization and electrochemical performance test of the prepared antimony/nitrogen-doped carbon composite were performed in the same manner as in example 1, and the results were substantially the same as in example 1.
Example 3
450mg of antimony trichloride was weighed out and dissolved in 5mL of methanol to form a clear solution, designated as solution A. 500mg of 1-ethyl-3-methylimidazolium dicyanamide ionic liquid was dissolved in 5mL of methanol to obtain a solution B. The solution B was poured into the solution A under vigorous stirring to obtain a uniform dispersion, and then the stirring was terminated. After standing for 15h, the white solid was collected by centrifugation, washed with methanol and centrifuged 5 times. Subsequently, the product obtained is placed in a porcelain boat and transferred into a tube furnace, in H2Heating to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere of/Ar (5: 95v/v), and then keeping at 600 ℃ for 2h to obtain the black antimony/nitrogen-doped carbon composite.
The structural characterization and electrochemical performance test of the prepared antimony/nitrogen-doped carbon composite were performed in the same manner as in example 1, and the results were substantially the same as in example 1.
Example 4
350mg of antimony trichloride was weighed out and dissolved in 5mL of methanol to form a clear solution, designated as solution A. 500mg of 1-ethyl-3-methylimidazolium dicyanamide ionic liquid was dissolved in 5mL of methanol to obtain a solution B. The solution B was poured into the solution A under vigorous stirring to obtain a uniform dispersion, and then the stirring was terminated. After standing for 10h, the white solid was collected by centrifugation, washed with methanol and centrifuged 6 times. Subsequently, the product obtained is placed in a porcelain boat and transferred into a tube furnace, in H2Heating to 550 ℃ at a heating rate of 4 ℃/min under an/Ar (5: 95v/v) atmosphere, and then keeping at 550 ℃ for 4h to obtain the black antimony/nitrogen-doped carbon composite.
The structural characterization and electrochemical performance test of the prepared antimony/nitrogen-doped carbon composite were performed in the same manner as in example 1, and the results were substantially the same as in example 1.
Example 5
450mg of antimony trichloride was weighed out and dissolved in 5mL of methanol to form a clear solution, designated as solution A. 500mg of 1-ethyl-3-methylimidazolium dicyanamide ionic liquid was dissolved in 5mL of methanol to obtain a solution B. The solution B was poured into the solution A under vigorous stirring to obtain a uniform dispersion, and then the stirring was terminated. After standing for 20h, the white solid was collected by centrifugation, washed with methanol and centrifuged 3 times. Subsequently, the product obtained is placed in a porcelain boat and transferred into a tube furnace, in H2Heating to 650 ℃ at a heating rate of 10 ℃/min under an atmosphere of/Ar (5: 95v/v), and then keeping at 650 ℃ for 3h to obtain the black antimony/nitrogen-doped carbon composite.
The structural characterization and electrochemical performance test of the prepared antimony/nitrogen-doped carbon composite were performed in the same manner as in example 1, and the results were substantially the same as in example 1.

Claims (8)

1. A method for preparing an antimony/nitrogen-doped carbon composite by using 1-ethyl-3-methylimidazolium dicyandiamide as a carbon source is characterized by comprising the following steps of:
1) dissolving antimony trichloride in methanol to form a clear solution, and obtaining a solution A;
2) dissolving 1-ethyl-3-methylimidazol dicyanamide in methanol to obtain a solution B;
3) pouring the solution B into the solution A under the condition of vigorous stirring, fully mixing the two solutions, standing, centrifuging to collect a gelatinous white solid, and centrifuging and washing by using methanol;
4) subjecting the product obtained in step 3) to reaction in H2Carbonizing in an/Ar mixed atmosphere to obtain the antimony/nitrogen-doped carbon composite;
the mass ratio of the antimony trichloride and the 1-ethyl-3-methylimidazol dicyandiamide added in the method is 7: 10-9: 10.
2. The method according to claim 1, wherein in the step 3), the standing time is 10-20 h.
3. The method according to claim 1, wherein in the step 3), the number of the centrifugal washing with methanol is 3 to 6.
4. The method of claim 1, wherein in the step 4), the carbonization is performed by placing the product obtained in the step 3) into a tube furnace at a temperature of 4-10 ℃ min-1The temperature is raised to 550-650 ℃ at the rate of (A) and then kept for 2-4 h.
5. The method of claim 1, wherein in step 4), the H is2In a mixed atmosphere of/Ar, H2The volume percentage of (A) is 5-10%.
6. An antimony/nitrogen-doped carbon composite, wherein the antimony/nitrogen-doped carbon composite is prepared by the method of any one of claims 1 to 5.
7. Use of the antimony/nitrogen-doped carbon composite of claim 6 as a negative electrode material for sodium ion batteries.
8. A negative electrode material for a sodium ion battery, comprising the antimony/nitrogen-doped carbon composite according to claim 6.
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