CN110380038B - Pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and preparation method thereof - Google Patents

Pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and preparation method thereof Download PDF

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CN110380038B
CN110380038B CN201910670928.3A CN201910670928A CN110380038B CN 110380038 B CN110380038 B CN 110380038B CN 201910670928 A CN201910670928 A CN 201910670928A CN 110380038 B CN110380038 B CN 110380038B
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antimony
composite material
antimony oxide
shell
pyrolytic carbon
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CN110380038A (en
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王志远
董康泽
罗绍华
刘延国
王庆
张亚辉
郝爱民
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Northeastern University Qinhuangdao Branch
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    • 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
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • Y02E60/10—Energy storage using batteries

Abstract

A pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and a preparation method thereof belong to the technical field of battery cathode materials; the composite material is formed by compounding carbon-coated nano-scale antimony oxide-antimony alloy particles and pyrolytic carbon, wherein the carbon-coated nano-scale antimony oxide-antimony alloy particles are uniformly embedded in the pyrolytic carbon; the preparation method comprises the following steps: 1) NaCl: carbon source: mixing tin sources, dissolving with deionized water, stirring by magnetic force, completely freezing, and freeze-drying under vacuum; 2) carrying out primary heat treatment, and cooling to room temperature; 3) washing, filtering and drying; 4) and (3) after drying, carrying out secondary heat treatment, and cooling to room temperature to obtain the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy. The composite material is used as a battery cathode, and in a potassium ion half-battery test, under a specific current density, the first charge reversible capacity is 300-650 mAh g‑1After 25-100 cycles, the capacity is 150-490 mAh g‑1。

Description

Pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and preparation method thereof
Technical Field
The invention belongs to the technical field of battery cathode materials, relates to a potassium ion battery cathode material technology, and particularly relates to a pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and a preparation method thereof.
Background
Due to the continuous exhaustion of the conventional fossil energy and the aggravation of global environmental problems, the development of sustainable and clean energy is more and more focused. Secondary batteries have become one of the most promising energy storage devices due to their high energy conversion efficiency and portability. Due to the chemical nature, abundant natural resources and low cost of lithium ions, there is a great interest in potassium ion batteries.
In recent years, research on potassium ion batteries has mainly focused on carbon-based materials, but the theoretical specific capacity of the potassium ion batteries is only 280mA · h/g, and the potassium ion batteries cannot meet the current requirements for development of high-energy density potassium ion batteries. Metallic antimony has attracted wide attention in recent years due to the theoretical specific capacity as high as 660 mA.h/g, but in the process of potassium ion deintercalation, the structural stability of elemental antimony is easily damaged due to huge volume expansion, so that the material is cracked and pulverized, and the cycle performance is seriously influenced. Meanwhile, the simple substance antimony material has the problems of high irreversible capacity of first charge and discharge, poor conductivity during complete potassium alloying, influence on rate performance and the like. The modification method for the antimony negative electrode mainly comprises the following aspects: firstly, compounding metal antimony and carbon, and relieving volume expansion by using a basic skeleton stabilized by carbon so as to enable the metal antimony to have excellent cycle performance of carbon and high theoretical capacity of antimony; and secondly, preparing the nano-antimony, shortening the diffusion path of potassium ions and simultaneously weakening the volume change of the material in the potassium-removing process to a certain extent. And thirdly, preparing a multi-shell structure, so that each layer of the multi-shell structure has a synergistic effect in the potassium process. The three modification methods have certain effect on improving the performance of the antimony oxide-antimony negative electrode, but the key problem of the antimony oxide-antimony alloy composite material cannot be completely solved by a single method.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and a preparation method thereof. The material is formed by compounding carbon-coated nano-scale antimony oxide-antimony alloy particles and pyrolytic carbon, wherein the carbon-coated nano-scale antimony oxide-antimony alloy particles are uniformly embedded in the pyrolytic carbon, and the pyrolytic carbon is amorphous carbon formed by pyrolyzing a carbon source at 400-800 ℃; the multi-shell layer is composed of outermost carbon, middle antimony oxide and antimony elementary substance in the middle; the composite material is used as a potassium ion battery cathode and has the characteristics of high capacity, good cycling stability, excellent rate capability and the like.
The pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy is formed by compounding carbon-coated nano antimony oxide-antimony alloy particles and pyrolytic carbon, and the multi-shell structure is adjusted by controlling the heat treatment time and temperature; the diameter of the antimony oxide-antimony alloy particles is 5-30 nm, and the thickness of the carbon coating layer is 1-5 nm.
The battery cathode material is tested in a potassium ion half-battery at 100-5000 mA g-1The first charge reversible capacity is 300-650 mAh g at the current density of-1After 25-100 cycles, the capacity is 150-490 mAh g-1. Exhibits excellent electrochemical performance.
The preparation method of the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy comprises the following steps:
step 1, preparing a precursor:
(1) mixing a template agent NaCl, an antimony source and a carbon source, dissolving in deionized water, and magnetically stirring for 3-12 hours to prepare a mixed solution; wherein the molar ratio of antimony ions contained in the antimony source to carbon atoms in the carbon source is 1 (10-500), and the molar ratio of antimony ions contained in the antimony source to NaCl is 1 (100-500);
(2) pre-freezing the prepared mixed solution at-40 to-10 ℃, freezing and vacuum-drying after completely freezing, removing water by vacuum drying at-70 to-10 ℃, and collecting the dried substance to obtain a precursor;
step 2, primary heat treatment:
putting the precursor into a crucible, placing the crucible in a tubular furnace for heat treatment in an inert atmosphere, heating to 550-750 ℃, preserving heat for 2-5 hours, and naturally cooling to room temperature to obtain an intermediate product, wherein inert gas is introduced into the tubular furnace at a flow rate of 50-500 mL/min to remove air, and then inert gas is continuously introduced at a flow rate of 50-200 mL/min;
and step 3, washing and drying:
taking the intermediate product out of the tube furnace, repeatedly washing and filtering the intermediate product by using deionized water until NaCl is completely removed; drying the washed mixture at the temperature of 60-80 ℃ to obtain powder;
and 4, secondary heat treatment:
and carrying out secondary heat treatment on the powder, keeping the temperature at 200-340 ℃ for 1-24 h, and cooling to room temperature in an air atmosphere to obtain the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy.
In the step 1, the carbon source is one or more of citric acid, sucrose, glucose, starch and vitamin C; the antimony source is one of antimony trichloride, antimony acetate, antimony tartrate or antimony nitrate.
In the step 1, the dosage of the deionized water is more than or equal to the solubility of NaCl, namely the NaCl is completely dissolved.
In the step 1, a refrigerator is adopted for pre-freezing.
In the step 1, the pressure of freeze drying is less than or equal to-50 pa.
In the step 2, the heating conditions are as follows: one or more of argon or helium is used as an inert gas source.
In the step 2, the heating rate of the heat treatment is 5-10 ℃/min.
And in the step 3, drying by using an oven.
In the step 4, the heating conditions are as follows: and under the air atmosphere, the heating rate is 1-10 ℃/min.
Vacuum drying to remove water so as to maintain the cubic structure of NaCl; the carbon source is carbonized into a simple substance in the heat treatment process, the metal ions are reduced into a simple substance, and the simple substance is aggregated to form an alloy.
The invention has the beneficial effects that:
(1) the volume change of the antimony cathode material in the process of inserting and removing potassium is buffered by the structure of the carbon-coated antimony oxide-antimony multi-shell layer prepared by the method. The introduction of the antimony oxide layer enables the antimony oxide-antimony electrode material to form K through conversion reaction during the first discharge process2O and antimony metal, K2The O layer can be used as a protective layer to further relieve the volume expansion of the metal antimony in the charging and discharging processes; the uniformly coated carbon layer can not only inhibit the alloy particles from growing up in the heat treatment process, but also inhibit the volume change of the metal antimony in the potassium removal processCan play a role of buffering. In addition, the carbon material has excellent conductivity and potassium storage function, and the flexibility of the carbon material also effectively buffers the volume change of the alloy on the substrate.
(2) The pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy is prepared by a salt dissolving template method, the thicknesses of antimony oxide and antimony shells can be adjusted through heat treatment at different temperatures and time, the preparation process is simple and safe, the production cost is low, the formed structure is stable, and the pyrolytic carbon composite material has excellent performance when being used as a potassium ion battery cathode material.
(3) Meanwhile, the secondary heat treatment process has wide expansibility, is simple and easy to implement, is not limited to the antimony metal material embedded in the reticular carbon structure, and is suitable for various forms of pyrolytic carbon-coated antimony metal materials. The multi-shell antimony oxide-antimony composite material prepared by the method has the advantages of uniform particles, good dispersibility, large specific surface area, stable structure, high specific capacity, good cycle performance and excellent rate capability.
Drawings
FIG. 1 is an SEM image of an antimony oxide-antimony alloy composite material according to embodiments 1-5 of the present invention before secondary heat treatment;
FIG. 2 is an XRD spectrum of an antimony oxide-antimony alloy composite material of examples 1 to 5 of the present invention before secondary heat treatment;
FIG. 3 is a graph showing the charge-discharge cycle performance of the lithium ion battery negative electrode made of the alloy composite material before the secondary heat treatment in examples 1 to 5 of the present invention;
FIG. 4 is an SEM image of the antimony oxide-antimony alloy composite material of example 1 of the present invention after a secondary heat treatment at 240 ℃ for 4 hours;
FIG. 5 is an XRD pattern of the antimony oxide-antimony alloy composite material of example 1 of the present invention after a secondary heat treatment at 240 ℃ for 4 hours;
FIG. 6 is a graph showing the charge-discharge cycle characteristics of the negative electrode of a potassium ion battery produced from the alloy composite material of example 1 of the present invention after the secondary heat treatment;
FIG. 7 is an SEM image of the antimony oxide-antimony alloy composite material of example 2 of the present invention after a secondary heat treatment at 240 ℃ for 12 hours;
FIG. 8 is an XRD pattern of the antimony oxide-antimony alloy composite material of example 2 of the present invention after a secondary heat treatment at 240 ℃ for 12 hours;
FIG. 9 is a graph showing the charge-discharge cycle characteristics of the negative electrode of the potassium ion battery obtained from the alloy composite material of example 2 of the present invention after the secondary heat treatment;
FIG. 10 is an XRD pattern of the antimony oxide-antimony alloy composite material of example 3 of the present invention after secondary heat treatment at 280 ℃ for 4 hours;
FIG. 11 is a secondary heat treatment at 300 ℃ for 4 hours of an XRD pattern of an antimony oxide-antimony alloy composite material of example 4 of the present invention;
FIG. 12 is a secondary heat treatment at 340 ℃ for 4h of an XRD pattern of the antimony oxide-antimony alloy composite material of example 5 of the present invention;
Detailed Description
In the embodiments 1 to 5, SEM and XRD of the antimony oxide-antimony alloy composite material after the first heat treatment and the charge-discharge cycle performance diagrams of the lithium ion battery negative electrode prepared from the alloy composite material before the second heat treatment are the same.
Example 1
A pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy is formed by uniformly embedding carbon-coated nano antimony oxide-antimony alloy particles on a pyrolytic carbon structure, wherein the multi-shell structure is adjusted by controlling heat treatment time and temperature; the diameter of the antimony oxide-antimony alloy particles is 5-30 nm, and the thickness of the carbon coating layer is 1-5 nm.
The preparation method of the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy comprises the following steps:
step 1, preparing a precursor:
(1) template NaCl (20.64g) and antimony source (SbCl)30.423g) and a carbon source (citric acid, 2.5g) are dissolved in deionized water (75ml), and the mixture is magnetically stirred for 3 hours to prepare a mixed clear mixed solution;
(2) pre-freezing the prepared mixed solution in a refrigerator at the temperature of-10 ℃, putting the mixed solution into a freeze dryer after completely freezing, removing water by vacuum drying at the temperature of-40 ℃ to keep the cubic structure of NaCl, and collecting the dried substance to obtain a precursor;
step 2, primary heat treatment:
putting the precursor into a crucible, firstly introducing argon into a tubular furnace at the flow rate of 200mL/min to remove air, then continuously introducing inert gas at the flow rate of 200mL/min, heating to 600 ℃, preserving heat for 2h, and naturally cooling to room temperature to obtain an intermediate product A;
and step 3, washing and drying:
taking the intermediate product out of the tube furnace, repeatedly washing and filtering the intermediate product by using deionized water until NaCl is completely removed; drying the washed mixture in an oven at 60 ℃ to obtain powder;
and 4, secondary heat treatment:
and (3) carrying out secondary heat treatment on the powder, heating to 240 ℃ at the heating rate of 1 ℃/min, preserving the heat for 4h, and cooling to room temperature in the air atmosphere to obtain the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy.
As shown in the SEM image before the secondary heat treatment of the antimony oxide-antimony alloy composite material shown in FIG. 1, the carbon structure and the uniformly embedded nano-scale alloy particles can be seen from the SEM image; the XRD pattern of the antimony oxide-antimony alloy composite material before secondary heat treatment is shown in figure 2. The obtained alloy is known as antimony oxide and antimony; in addition, antimony oxide has a weak peak intensity, indicating its small thickness; FIG. 3 is a graph showing the charge-discharge cycle characteristics of the negative electrode for a lithium ion battery made of the alloy composite material before the secondary heat treatment, and it can be seen that the charge-discharge cycle characteristics are 0.1A g-1The reversible capacity of 250mAh g at 100 times of current density-1。
The secondary heat treatment of the antimony oxide-antimony alloy composite material shown in FIG. 4 is carried out at 240 ℃ for 4h, and an SEM image shows a carbon structure and uniformly embedded nanoscale alloy particles; the XRD pattern of the antimony oxide-antimony alloy composite material shown in figure 5 is obtained by secondary heat treatment at 240 ℃ for 4 hours. The resulting alloy is known as an antimony oxide-antimony alloy, and in addition, an increase in peak intensity of antimony oxide indicates an increase in thickness thereof; FIG. 6 is a graph showing the charge-discharge cycle characteristics of the negative electrode of a potassium ion battery obtained from the alloy composite material after the secondary heat treatment, and it can be seen that the charge-discharge cycle characteristics are 0.1A g-1Has a 100-time reversible capacity of 480mAh g at a current density-1。
Example 2
A pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy is formed by uniformly embedding carbon-coated nano antimony oxide-antimony alloy particles on a pyrolytic carbon structure, wherein the multi-shell structure is adjusted by controlling heat treatment time and temperature; the diameter of the antimony oxide-antimony alloy particles is 5-30 nm, and the thickness of the carbon coating layer is 1-5 nm.
The preparation method of the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy comprises the following steps:
step 1, preparing a precursor:
(1) template NaCl (60.34g) antimony source (SbCl)30.423g) and a carbon source (citric acid, 2.5g) were dissolved in deionized water (75ml), and stirred magnetically for 2 hours to prepare a clear mixed solution;
(2) pre-freezing the prepared mixed solution in a refrigerator at the temperature of-15 ℃, putting the mixed solution into a freeze dryer after completely freezing, removing water by vacuum drying at the temperature of-45 ℃ to keep the cubic structure of NaCl, and collecting the dried substance to obtain a precursor;
step 2, primary heat treatment:
putting the precursor into a crucible, firstly introducing argon into a tubular furnace at the flow rate of 200mL/min to remove air, then continuously introducing inert gas at the flow rate of 200mL/min, heating to 600 ℃, preserving heat for 2h, and naturally cooling to room temperature to obtain an intermediate product;
and step 3, washing and drying:
taking the intermediate product out of the tube furnace, repeatedly washing and filtering the intermediate product by using deionized water until NaCl is completely removed; drying the washed mixture in an oven at 60 ℃ to obtain powder;
and 4, secondary heat treatment:
and carrying out secondary heat treatment on the obtained powder, heating to 240 ℃ at a heating rate of 1 ℃/min, preserving the heat for 12h, and cooling to room temperature in an air atmosphere to obtain the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy.
As shown in FIG. 7, SEM image of 12h at 240 ℃ of the secondary heat treatment of the antimony oxide-antimony alloy composite material shows, and carbon structure can be seen from the SEM imageAnd uniformly embedded nano-scale alloy particles; as shown in figure 8, the XRD pattern of the antimony oxide-antimony alloy composite material is obtained by secondary heat treatment at 240 ℃ for 12 hours. The obtained alloy is antimony oxide-antimony alloy, and the peak intensity of antimony oxide is equal to that of metal antimony; FIG. 9 is a graph showing the charge-discharge cycle characteristics of the negative electrode of a potassium ion battery obtained from the alloy composite material after the secondary heat treatment, and it can be seen that the charge-discharge cycle characteristics are 0.1A g-1The reversible capacity of 450mAh g at 100 times of current density-1。
Example 3
A pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy is formed by uniformly embedding carbon-coated nano antimony oxide-antimony alloy particles on a pyrolytic carbon structure, wherein the multi-shell structure is adjusted by controlling heat treatment time and temperature; the diameter of the antimony oxide-antimony alloy particles is 5-30 nm, and the thickness of the carbon coating layer is 1-5 nm.
The preparation method of the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy comprises the following steps:
step 1, preparing a precursor:
(1) template NaCl (20.85g) and antimony source (SbCl)30.423g) and a carbon source (citric acid, 2.5g) are dissolved in deionized water (75ml), and the mixture is magnetically stirred for 4 hours to prepare a mixed solution;
(2) pre-freezing the prepared mixed solution in a refrigerator at the temperature of-10 ℃, putting the mixed solution into a freeze dryer after completely freezing, removing water by vacuum drying at the temperature of-45 ℃ to keep the cubic structure of NaCl, and collecting the dried substance to obtain a precursor;
step 2, heat treatment:
putting the precursor into a crucible, firstly introducing argon into a tubular furnace at the flow rate of 100mL/min to remove air, then continuously introducing inert gas at the flow rate of 50mL/min, heating to 600 ℃, preserving heat for 2h, and naturally cooling to room temperature to obtain an intermediate product;
and step 3, washing and drying:
taking the intermediate product out of the tube furnace, repeatedly washing and filtering the intermediate product by using deionized water until NaCl is completely removed; drying the washed mixture in an oven at 70 ℃ to obtain powder;
and 4, secondary heat treatment:
and carrying out secondary heat treatment on the obtained powder, heating to 280 ℃ at the heating rate of 1 ℃/min, preserving the heat for 4h, and cooling to room temperature in the air atmosphere to obtain the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy. As shown in figure 10, the antimony oxide-antimony alloy composite material is subjected to secondary heat treatment at 280 ℃ and an XRD pattern for 4 h. The resulting alloys are known as antimony oxide and antimony.
Example 4
A pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy is formed by uniformly embedding carbon-coated nano antimony oxide-antimony alloy particles on a pyrolytic carbon structure, wherein the multi-shell structure is adjusted by controlling heat treatment time and temperature; the diameter of the antimony oxide-antimony alloy particles is 5-30 nm, and the thickness of the carbon coating layer is 1-5 nm.
The preparation method of the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy comprises the following steps:
step 1, preparing a precursor:
(1) template NaCl (20.65g) and antimony source (SbCl)30.423g) and a carbon source (citric acid, 2.5g) are dissolved in deionized water (75ml), and the mixture is magnetically stirred for 6 hours to prepare a mixed solution;
(2) pre-freezing the prepared mixed solution in a refrigerator at the temperature of-10 ℃, putting the mixed solution into a freeze dryer after completely freezing, removing water by vacuum drying at the temperature of-50 ℃ to keep the cubic structure of NaCl, and collecting the dried substance to obtain a precursor;
step 2, heat treatment:
putting the precursor into a crucible, firstly introducing argon into a tubular furnace at the flow rate of 100mL/min to remove air, then continuously introducing inert gas at the flow rate of 120mL/min, heating to 600 ℃, preserving heat for 2h, and naturally cooling to room temperature to obtain an intermediate product;
step 3, washing and drying
Taking the intermediate product out of the tube furnace, repeatedly washing and filtering the intermediate product by using deionized water until NaCl is completely removed; drying the washed mixture in an oven at 60 ℃ to obtain powder;
step 4, secondary heat treatment
And carrying out secondary heat treatment on the obtained powder, heating to 300 ℃ at the heating rate of 1 ℃/min, preserving the heat for 4h, and cooling to room temperature in the air atmosphere to obtain the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy. As shown in figure 11, the antimony oxide-antimony alloy composite material is subjected to secondary heat treatment at 300 ℃ for 4 h. The alloys obtained were found to be antimony oxide and antimony.
Example 5
A pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy is formed by uniformly embedding carbon-coated nano antimony oxide-antimony alloy particles on a pyrolytic carbon structure, wherein the multi-shell structure is adjusted by controlling heat treatment time and temperature; the diameter of the antimony oxide-antimony alloy particles is 5-30 nm, and the thickness of the carbon coating layer is 1-5 nm.
The preparation method of the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy comprises the following steps:
step 1, preparing a precursor:
(1) template NaCl (22.44g) and antimony source (SbCl)30.423g) and a carbon source (citric acid, 2.5g) are dissolved in deionized water (75ml), and the mixture is magnetically stirred for 8 hours to prepare a mixed solution;
(2) pre-freezing the prepared mixed solution in a refrigerator at the temperature of-10 ℃, putting the mixed solution into a freeze dryer after completely freezing, removing water by vacuum drying at the temperature of-46 ℃ to keep the cubic structure of NaCl, and collecting the dried substance to obtain a precursor;
step 2, heat treatment:
putting the precursor into a crucible, firstly introducing argon into a tubular furnace at a flow rate of 130mL/min to remove air, then continuously introducing inert gas at a flow rate of 130mL/min, heating to 600 ℃, preserving heat for 2h, and naturally cooling to room temperature to obtain an intermediate product;
and step 3, washing and drying:
taking the intermediate product out of the tube furnace, repeatedly washing and filtering the intermediate product by using deionized water until NaCl is completely removed; drying the washed mixture in an oven at 70 ℃ to obtain powder;
and 4, secondary heat treatment:
and carrying out secondary heat treatment on the obtained powder, heating to 340 ℃ at a heating rate of 1 ℃/min, preserving heat for 4h, and cooling to room temperature in an air atmosphere to obtain the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy. As shown in figure 12, the antimony oxide-antimony alloy composite material is subjected to secondary heat treatment at 340 ℃ and an XRD pattern for 4 h. The obtained alloy was found to be an amorphous antimony oxide.
Example 6
A pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy is formed by uniformly embedding carbon-coated nano antimony oxide-antimony alloy particles on a pyrolytic carbon structure, wherein the multi-shell structure is adjusted by controlling heat treatment time and temperature; the diameter of the antimony oxide-antimony alloy particles is 5-30 nm, and the thickness of the carbon coating layer is 1-5 nm.
The preparation method of the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy comprises the following steps:
step 1, preparing a precursor:
(1) template NaCl (42.24g) and antimony source (SbCl)30.32g) and a carbon source (citric acid, 5g) are dissolved in deionized water (150ml), and the mixture is magnetically stirred for 5 hours to prepare a mixed clear solution;
(2) pre-freezing the prepared mixed solution in a refrigerator at the temperature of-10 ℃, putting the mixed solution into a freeze dryer after completely freezing, removing water by vacuum drying at the temperature of-32 ℃ to keep the cubic structure of NaCl, and collecting the dried substance to obtain a precursor;
step 2, heat treatment:
putting the precursor into a crucible, firstly introducing argon into a tubular furnace at the flow rate of 100mL/min to remove air, then continuously introducing inert gas at the flow rate of 120mL/min, heating to 750 ℃, preserving heat for 3h, and naturally cooling to room temperature to obtain an intermediate product;
and step 3, washing and drying:
taking the intermediate product out of the tube furnace, repeatedly washing and filtering the intermediate product by using deionized water until NaCl is completely removed; drying the washed mixture in an oven at 60 ℃ to obtain powder;
and 4, secondary heat treatment:
and carrying out secondary heat treatment on the obtained powder, heating to 260 ℃ at a heating rate of 2 ℃/min, preserving heat for 4h, and cooling to room temperature in an air atmosphere to obtain the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy.
Example 7
A pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy is formed by uniformly embedding carbon-coated nano antimony oxide-antimony alloy particles on a pyrolytic carbon structure, wherein the multi-shell structure is adjusted by controlling heat treatment time and temperature; the diameter of the antimony oxide-antimony alloy particles is 5-30 nm, and the thickness of the carbon coating layer is 1-5 nm.
The preparation method of the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy comprises the following steps:
step 1, preparing a precursor:
(1) template NaCl (20.64g) and antimony source (SbCl)30.84g) and a carbon source (citric acid, 2.6g) are dissolved in deionized water (80ml), and the mixture is magnetically stirred for 8 hours to prepare a mixed solution;
(2) pre-freezing the mixed solution in a refrigerator at the temperature of-5 ℃, putting the mixed solution into a freeze dryer after completely freezing, removing water by vacuum drying at the temperature of-26 ℃ to keep the cubic structure of NaCl, and collecting the dried substance to obtain a precursor;
step 2, heat treatment:
putting the precursor into a crucible, firstly introducing argon into a tubular furnace at the flow rate of 200mL/min to remove air, then continuously introducing inert gas at the flow rate of 100mL/min, heating to 550 ℃, preserving heat for 3h, and naturally cooling to room temperature to obtain an intermediate product;
and step 3, washing and drying:
taking the intermediate product out of the tube furnace, repeatedly washing and filtering the intermediate product by using deionized water until NaCl is completely removed; drying the washed mixture in an oven at 50 ℃ to obtain powder;
step 4, secondary heat treatment
And carrying out secondary heat treatment on the obtained powder, heating to 270 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and cooling to room temperature in an air atmosphere to obtain the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy.
From the relative strength of the peak positions of the antimony oxide and the antimony by XRD, it can be judged that at 240 ℃, the peak strength of the antimony oxide gradually becomes stronger along with the extension of the secondary heat treatment time, the peak strength of the antimony becomes weaker, and finally the antimony tends to be relatively consistent in height. This indicates that the thickness of antimony oxide at the outer layer of antimony gradually increases with the time of heat treatment, but antimony is not completely oxidized to antimony oxide state at 240 ℃. With the rise of the temperature of the secondary heat treatment, the peak intensity of the antimony oxide is found to be stronger than that of the antimony, and finally, the antimony oxide can be completely oxidized at 340 ℃ and simultaneously becomes an amorphous state, namely, the antimony is completely oxidized into amorphous antimony oxide. When the prepared material is used as a negative electrode material of a potassium ion battery, the electrochemical performance of secondary heat treatment for 4 hours at 240 ℃ is found to be optimal.

Claims (7)

1. A preparation method of a pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy is characterized by comprising the following steps:
step 1, preparing a precursor:
(1) mixing a template agent NaCl, an antimony source and a carbon source, dissolving in deionized water, and magnetically stirring for 3-12 hours to prepare a mixed solution; wherein the molar ratio of antimony ions contained in the antimony source to carbon atoms in the carbon source is 1 (10-500), and the molar ratio of antimony ions contained in the antimony source to NaCl is 1 (100-500);
the carbon source is one or more of citric acid, sucrose, glucose, starch and vitamin C; the antimony source is one of antimony acetate, antimony tartrate or antimony nitrate;
(2) pre-freezing the prepared mixed solution at-40 to-10 ℃, completely freezing, then carrying out freeze vacuum drying at-70 to-10 ℃, and collecting the dried substance to obtain a precursor;
step 2, primary heat treatment:
putting the precursor into a crucible, placing the crucible in a tube furnace for heat treatment in an inert atmosphere, heating to 550-750 ℃, preserving heat for 2-5 hours, and naturally cooling to room temperature to obtain an intermediate product; wherein, inert gas is introduced into the tubular furnace at the flow rate of 50-500 mL/min to remove air, and then the inert gas is continuously introduced at the flow rate of 50-200 mL/min;
and step 3, washing and drying:
taking the intermediate product out of the tube furnace, repeatedly washing and filtering the intermediate product by using deionized water until NaCl is completely removed; drying the washed mixture at the temperature of 60-80 ℃ to obtain powder;
and 4, secondary heat treatment:
carrying out secondary heat treatment on the powder, keeping the temperature at 200-340 ℃ for 1-24 h, and cooling to room temperature in an air atmosphere to obtain a pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy;
the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy is formed by compounding carbon-coated nano antimony oxide-antimony alloy particles and pyrolytic carbon, wherein the carbon-coated nano antimony oxide-antimony alloy particles are uniformly embedded in the pyrolytic carbon, and the pyrolytic carbon is amorphous carbon formed by pyrolyzing a carbon source at 400-800 ℃; the multi-shell layer is composed of outermost carbon, middle antimony oxide and antimony elementary substance in the middle; the diameter of the antimony oxide-antimony alloy particles is 5-30 nm, and the thickness of the carbon coating layer is 1-5 nm; the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy is 100-5000 mA-g in a potassium ion half-cell test-1The first charge reversible capacity is 300 to 650 mAh.g at the current density of (1)-1After 25 to 100 cycles, the capacity is 450 to 490mAh g-1。
2. The method for preparing the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy according to claim 1, wherein in the step 1, the amount of deionized water is more than or equal to the solubility of NaCl, namely NaCl is completely dissolved.
3. The method for preparing the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy according to claim 1, wherein in the step 1, pre-freezing is performed by a refrigerator, and the pressure of freeze drying is less than or equal to-50 pa.
4. The method for preparing the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy according to claim 1, wherein in the step 2, heating conditions are as follows: one or more of argon or helium is used as an inert gas source.
5. The method for preparing the pyrolytic carbon composite material with the embedded multi-shell antimony oxide-antimony alloy, according to claim 1, wherein in the step 2, the heating rate of the heat treatment is 5-10 ℃/min.
6. The method for preparing the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy according to claim 1, wherein in the step 3, an oven is adopted for drying.
7. The method for preparing the pyrolytic carbon composite material embedded with the multi-shell antimony oxide-antimony alloy according to claim 1, wherein in the step 4, heating conditions are as follows: and under the air atmosphere, the heating rate is 1-10 ℃/min.
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