CN114068904B - Carbon-coated tin-based chalcogenide composite material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a carbon-coated tin-based chalcogenide composite material and a preparation method and application thereof, which are mainly realized by the following steps: firstly, hydrolyzing stannic acid salt into a nano spherical tin dioxide precursor; coating a layer of polydopamine on the surface of the film; and finally, carrying out heat treatment on the carbon-coated tin-based chalcogenide composite material and selenium powder or sulfur powder to obtain the carbon-coated tin-based chalcogenide (SnSe or SnS) composite material. The material is in a typical core-shell structure, and nitrogen selenium or nitrogen sulfur co-doped carbon can relieve volume expansion of tin-based chalcogenide and can provide more active sites. When the target product is used for a negative electrode material of a sodium-ion battery, excellent rate performance and cycle stability are shown, and especially ultrahigh first-turn coulombic efficiency is shown.
Description
Technical Field
The invention relates to the technical field of negative electrode materials of sodium ion batteries, in particular to a carbon-coated tin-based chalcogenide composite material and a preparation method and application thereof.
Background
With the increasing development of human society, the conventional fossil energy is exhausted, and the problems of energy shortage and environmental pollution are more and more severe. Therefore, the demand of human beings for clean and efficient energy is more urgent, and the development of clean and renewable energy is a hot problem in the current society. The clean renewable energy needs to be converted into electric energy and stored for effective utilization. The lithium ion battery widely used at present is restricted by the exhaustion of lithium resources in the future, and the sodium ion battery is more and more favored by researchers due to the abundant and cheaper reserve of sodium. However, since the radius of sodium ions is larger than that of lithium ions, the electrode material originally used for a lithium ion battery cannot be directly used for a sodium ion battery. Therefore, the search for electrode materials suitable for sodium ion batteries is a primary task of current researchers.
The tin-based negative electrode material has wide attention due to rich raw materials, low price and high theoretical specific capacity. The chalcogen compounds (stannous sulfide and stannous selenide) are representative cathode materials, and have two-dimensional layered structures, and Na is added in the sodium storage process + Firstly, sodium tin sulfide (selenide) is formed by intercalation between layers, and then conversion reaction and alloying reaction are carried out to convert into Na 2 S(Na 2 Se) and Na x Sn. The combination of multi-step sodium storage reactions allows tin-based chalcogenides to have a higher theoretical specific capacity, however its lower conductivity and greater volume expansion during sodium storage remain two key issues to be addressed.
In contrast, researchers often modify tin-based chalcogenides by using two ways of material nanocrystallization design (e.g., quantum dots, nanowires, nanosheets, etc.) and compounding with carbon materials with good conductivity (e.g., graphene, carbon nanotubes, etc.). Although major advances have been made in modification work, the synthesis process of most of the work is complex and time-consuming. In addition, the weak interfacial coupling between the tin-based chalcogenide and the carbon material allows the active material to be easily exfoliated from the carbon material, eventually resulting in a rapid decay in capacity.
Disclosure of Invention
The invention aims to provide a carbon-coated tin-based chalcogenide composite material and a preparation method and application thereof, aiming at the problems that the conventional tin-based chalcogenide preparation process is complex and time-consuming, and the volume expansion is serious and the conductivity is poor when the tin-based chalcogenide composite material is used as a sodium ion battery cathode material. The raw materials and the generated solution in the preparation process of the material are easy to process and have no pollution, the preparation cost is low, the operation process is simple, and the repeatability is high. Meanwhile, compared with a pure carbon layer, the unique double-heteroatom doped carbon layer has more defects and active sites, the conductivity is improved, and the adsorption capacity to sodium ions is also greatly improved. When the electrode material is used as a sodium ion battery cathode material, the electrode material has high rate performance, high cycle stability and ultrahigh first-turn coulombic efficiency.
The invention prepares uniform stannic oxide nano-particles by a simple method, takes the stannic oxide nano-particles as a precursor, coats polydopamine with a certain thickness on the surface, and then carries out heat treatment with selenium powder or sulfur powder under the protection of inert gas to obtain the carbon-coated tin-based chalcogenide composite material with a typical core-shell structure.
A preparation method of a carbon-coated tin-based chalcogenide composite material comprises the following steps:
(1) Dissolving stannate in deionized water to prepare stannate solution with a certain concentration, and continuously stirring;
(2) Slowly adding a certain amount of alcohol solvent into the stannate solution obtained in the step (1), stirring for a certain time at room temperature of 25 ℃, then carrying out centrifugal separation, washing and drying to obtain a white precursor product A;
(3) Dispersing the white precursor product A obtained in the step (2) in deionized water, performing ultrasonic dispersion, adding Tris (hydroxymethyl) aminomethane (Tris) to adjust the pH value of the solution, adding dopamine hydrochloride, continuously stirring for a certain time at room temperature, performing centrifugal separation, washing and drying to obtain a black product B;
(4) And (4) placing selenium powder or sulfur powder and the black product B in the step (3) in a tube furnace, and carrying out heat treatment under the protection of inert gas to obtain the nitrogen-selenium-codoped carbon-coated stannous selenide composite material or the nitrogen-sulfur-codoped carbon-coated stannous sulfide composite material.
The following are preferred technical schemes of the invention:
in the step (1), the stannate is sodium stannate trihydrate (Na) 2 SnO 3 ·3H 2 O) or potassium stannate trihydrate (K) 2 SnO 3 ·3H 2 O), stannate concentration of 0.01-0.03mol L -1 。
In the step (2), the alcohol solvent is any one of monohydric alcohols such as absolute methanol, absolute ethanol and isopropanol, the volume ratio of the alcohol solvent to the deionized water in the step (1-2) is 1, the stirring time is 6-48h, and the drying condition is as follows: placing in a vacuum oven at 50-80 deg.C for 12-24h.
In the step (3), the ratio of the white precursor product A to the deionized water is 50-150 mg:80mL, preferably 100mg:80mL, every 100mg of white precursor product A corresponds to 80mL of deionized water, the pH value of the solution is 8.0-9.0, the mass of the dopamine hydrochloride is 0.5-3 times of the mass of the used white precursor product A, the stirring time is 12-48h, and the drying condition is as follows: placing in a vacuum oven at 50-80 deg.C for 12-24h.
In the step (4), the mass of the selenium powder or the sulfur powder is 1-3 times of that of the black product B, the inert gas is one of nitrogen or argon, the heat treatment temperature is 500-700 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 2-4h.
The carbon-coated tin-based chalcogenide composite material is of a typical core-shell structure, the particle diameter of the carbon-coated tin-based chalcogenide composite material is about 110-150nm, the thickness of a surface carbon layer is about 10-30nm, and the middle part of the carbon-coated tin-based chalcogenide composite material is SnSe or SnS.
Mixing the obtained carbon-coated tin-based chalcogenide composite material serving as a negative electrode material of a sodium ion battery with conductive carbon black (Super P) and a binding agent (CMC) to obtain slurry, coating the slurry on a metal copper foil current collector to obtain a negative electrode, taking glass fibers as a diaphragm, taking metal sodium as a counter electrode, and using 1mol L of electrolyte -1 NaClO 4 In a glove box filled with argon, the assembly of the cell was completed. And (3) standing the assembled sodium-ion battery for 24 hours, then carrying out constant-current charge-discharge test, wherein the voltage window is 0.01-3.0V, and testing the specific capacity, the rate capability and the long cycle performance of the battery cathode in a constant temperature environment of 25 +/-1 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) The tin dioxide is synthesized by a simple and easy-to-operate room temperature precipitation method, and compared with the existing tin dioxide synthesized by urea and hydrothermal conditions, the tin dioxide has smaller and uniform particle size and larger and stable yield. Meanwhile, the reaction conditions are simple, and the energy consumption is reduced.
(2) In the synthesis of the carbon-coated tin-based chalcogenide composite material, the tin dioxide is used as a precursor, and the one-step heat treatment method is adopted, so that compared with the existing method of firstly carbonizing and then selenizing (or vulcanizing), the method does not need argon-hydrogen mixed gas, can be realized only by common inert atmosphere, and has the advantages of safe operation, simple condition and energy conservation.
(3) The prepared carbon-coated tin-based chalcogenide composite material has a stable structure, and the surface double-hetero atom doped carbon layer has more defects and active sites compared with a pure carbon layer, so that the overall conductivity of the material and the adsorption capacity of the material on sodium ions are greatly improved. Meanwhile, the carbon layer can also buffer the stress change of the internal SnSe or SnS in the process of sodium deintercalation, relieve the volume expansion, ensure that the material has better electrochemical performance and cycling stability, and has excellent application prospect in the field of energy storage.
Drawings
Fig. 1 is a scanning electron microscope picture of the nitrogen-selenium co-doped carbon-coated stannous selenide composite material prepared in example 1;
fig. 2 is a transmission electron microscope picture of the nitrogen-selenium co-doped carbon-coated stannous selenide composite material prepared in example 1;
fig. 3 is an X-ray diffraction pattern of the nitrogen-selenium co-doped carbon-coated stannous selenide composite material prepared in example 1.
Fig. 4 is a graph of the rate capability of the sodium ion battery of the nitrogen-selenium co-doped carbon-coated stannous selenide composite material prepared in example 1.
Fig. 5 is a constant current charge and discharge diagram of the sodium ion battery made of the nitrogen-selenium co-doped carbon-coated stannous selenide composite material prepared in example 1.
Fig. 6 is a graph of the cycle performance of the sodium ion battery made of the nitrogen-selenium co-doped carbon-coated stannous selenide composite material prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following detailed description. It should be noted that the specific implementation examples are not intended to limit the scope of the present invention, and that conventional modifications by those skilled in the art are also considered as the implementable scope of the present invention without substantial technical contribution, and all are within the protection scope of the present invention.
Example 1
(1) 2mmol of sodium stannate trihydrate (Na) are weighed 2 SnO 3 ·3H 2 O) is dissolved in 100mL of deionized water, stirred until the solution is clear, then 150mL of absolute ethyl alcohol is slowly added, the solution is cloudy, and the stirring is continued for 24 hours; at 6000r min -1 The white product is obtained by centrifugal separation at the rotating speed of the microwave, and is respectively washed three times by deionized water and absolute ethyl alcohol, and is dried for 12 hours in a vacuum oven at the temperature of 60 ℃ to obtain the tin dioxide (SnO) 2 ) A nanoparticle;
(2) Weighing 100mg of the SnO 2 Dissolving in 80mL deionized water, performing ultrasonic dispersion for 15min, adding 100mg Tris buffer substance to adjust the pH value of the solution to 8.5, and performing ultrasonic dispersionAdding 200mg of dopamine hydrochloride, and stirring for 24 hours; at 10000r min -1 The black product is obtained by centrifugal separation at the rotating speed of the raw material, and is respectively washed three times by deionized water and absolute ethyl alcohol, and is dried for 12 hours in a vacuum oven at the temperature of 60 ℃ to obtain the poly-dopamine-coated tin dioxide (SnO) 2 @PDA)；
(3) 50mg SnO was weighed 2 @ PDA and 100mg selenium powder, respectively placed at the downstream and upstream of the tube furnace, and passed through nitrogen gas at 2 deg.C for min -1 The temperature is raised to 600 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally cooled to 25 ℃ at room temperature to obtain the nitrogen-selenium co-doped carbon-coated stannous selenide composite material.
Example 2
(1) Weighing 2mmol potassium stannate trihydrate (K) 2 SnO 3 ·3H 2 O) is dissolved in 100mL of deionized water, stirred until the solution is clear, then 150mL of absolute ethyl alcohol is slowly added, the solution is cloudy, and the stirring is continued for 24 hours; at 6000r min -1 Centrifugally separating at the rotating speed of (1) to obtain a white product, respectively cleaning with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain SnO 2 A nanoparticle;
(2) Weighing 100mg of the SnO 2 Dissolving in 80mL deionized water, performing ultrasonic dispersion for 15min, adding 100mg of Tris buffer substance to adjust the pH value of the solution to 8.5, adding 200mg of dopamine hydrochloride, and stirring for 24h; at 10000r min -1 Centrifugally separating at the rotating speed of (1) to obtain a black product, respectively cleaning with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain SnO 2 @PDA；
(3) 50mg SnO was weighed 2 @ PDA and 100mg selenium powder, respectively placed at the downstream and upstream of the tube furnace, and passed through nitrogen gas at 2 deg.C for min -1 The temperature is raised to 600 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally cooled to 25 ℃ at room temperature to obtain the nitrogen-selenium co-doped carbon-coated stannous selenide composite material.
Example 3
(1) Weighing 2mmol of Na 2 SnO 3 ·3H 2 Dissolving O in 100mL of deionized water, stirring until the solution is clear, slowly adding 150mL of isopropanol until white turbidity appears in the solution, and continuously stirring for 24 hours; at 6000r min -1 Centrifugally separating at the rotating speed of a clock to obtain a white product, respectively cleaning with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain SnO 2 A nanoparticle;
(2) Weighing 100mg of the SnO 2 Dissolving in 80mL deionized water, performing ultrasonic dispersion for 15min, adding 100mg of Tris buffer substance to adjust the pH value of the solution to 8.5, adding 200mg of dopamine hydrochloride, and stirring for 24h; at 10000r min -1 Centrifugally separating at the rotating speed of (2) to obtain a black product, respectively cleaning the black product with deionized water and absolute ethyl alcohol for three times, and drying the black product in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain SnO 2 @PDA；
(3) 50mg SnO was weighed 2 @ PDA and 100mg selenium powder, respectively placed at the downstream and upstream of the tube furnace, and introduced with nitrogen gas at 2 deg.C for min -1 The temperature is raised to 600 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally cooled to 25 ℃ at room temperature to obtain the nitrogen-selenium co-doped carbon-coated stannous selenide composite material.
Example 4
(1) Weighing 2mmol of Na 2 SnO 3 ·3H 2 Dissolving O in 100mL of deionized water, stirring until the solution is clear, slowly adding 150mL of anhydrous ethanol until the solution is cloudy, and continuously stirring for 24 hours; at 6000r min -1 Centrifugally separating at the rotating speed of (1) to obtain a white product, respectively cleaning with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain SnO 2 A nanoparticle;
(2) Weighing 100mg of the SnO 2 Dissolving in 80mL deionized water, performing ultrasonic dispersion for 15min, adding 100mg of Tris buffer substance to adjust the pH value of the solution to 8.5, adding 300mg of dopamine hydrochloride, and stirring for 24h; at 10000r min -1 Centrifugally separating at the rotating speed of (2) to obtain a black product, respectively cleaning the black product with deionized water and absolute ethyl alcohol for three times, and drying the black product in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain SnO 2 @PDA；
(3) 50mg SnO was weighed 2 @ PDA and 100mg selenium powder, respectively placed at the downstream and upstream of the tube furnace, and introduced with nitrogen gas at 2 deg.C for min -1 Heating to 600 ℃ at a heating rate, keeping the temperature for 2 hours, then naturally cooling to 25 ℃ at room temperature to obtain the nitrogen-selenium co-doped carbon-coated stannous selenideAnd (5) synthesizing the materials.
Example 5
(1) Weighing 2mmol of Na 2 SnO 3 ·3H 2 Dissolving O in 100mL of deionized water, stirring until the solution is clear, slowly adding 150mL of anhydrous ethanol until the solution is cloudy, and continuously stirring for 24 hours; at 6000r min -1 Centrifugally separating at the rotating speed of (2) to obtain a white product, respectively cleaning with deionized water and absolute ethyl alcohol for three times, and drying in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain SnO 2 A nanoparticle;
(2) Weighing 100mg of the SnO 2 Dissolving in 80mL of deionized water, performing ultrasonic dispersion for 15 hours, adding 100mg of Tris buffer substance to ensure that the pH value of the solution is 8.5, adding 200mg of dopamine hydrochloride, and stirring for 24 hours; at 10000r min -1 Centrifugally separating at the rotating speed of (2) to obtain a black product, respectively cleaning the black product with deionized water and absolute ethyl alcohol for three times, and drying the black product in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain SnO 2 @PDA；
(3) 50mg SnO was weighed 2 @ PDA and 100mg sulfur powder, respectively placed at the downstream and upstream of the tube furnace, and introduced with nitrogen gas at 2 deg.C for min -1 The temperature is raised to 600 ℃ at the temperature raising rate, the temperature is kept for 2 hours, and then the temperature is naturally cooled to 25 ℃ at room temperature to obtain the nitrogen-sulfur co-doped carbon-coated stannous sulfide composite material.
Performance testing
The carbon-coated tin-based chalcogenide composite materials prepared in the above examples 1 to 5 were used as negative electrode materials of sodium ion batteries, and assembled into sodium ion batteries for constant current charge and discharge tests. FIG. 4 shows the results of the rate capability test of example 1, and it can be seen that the sodium ion battery is at 0.1 ag -1 、0.2A g -1 、0.5Ag -1 、1A g -1 、2A g -1 、5A g -1 And 10A g -1 Respectively has a capacity of 562.6mA h g -1 、503.9mA h g -1 、421.6mA h g -1 、390.9mA h g -1 、352.2mA h g -1 、301.0mA h g -1 And 285.3mA h g -1 And excellent rate capability is shown. FIG. 5 shows the electrodes at 0.1 ag -1 The coulombic efficiency of the first loop of the constant-current charge-discharge curve under the current density is up to 89.9 percent. From the cycle of FIG. 6As can be seen from the ring performance diagram, the sodium ion battery is 1 Ag -1 The capacity retention rate of 83.8% under the current density after 100 cycles, and the excellent cycle stability is shown.
The discharge capacities at different current densities of the carbon-coated tin-based chalcogenide composite materials of examples 1 to 5 assembled into a sodium ion battery as a negative electrode material of the sodium ion battery are shown in table 1:
TABLE 1
As can be seen from the table, changing the type of stannate (example 2), alcohol solvent (example 3) has no significant effect on the electrochemical performance of the final product compared to the control (example 1). Increasing the amount of dopamine hydrochloride (example 4) slightly decreased the capacity of the final product due to the increased carbon content in the material resulting in a decrease in the high capacity SnSe content. After the last step of selenization is changed into sulfurization (example 5), the capacity of the material is obviously improved, mainly because although SnS and SnSe are layered materials, the mechanism of sodium storage is similar, but the relative atomic mass of S is smaller than that of Se, so the theoretical sodium storage capacity of SnS is higher than that of SnSe.
Claims (10)
1. A preparation method of a carbon-coated tin-based chalcogenide composite material is characterized by comprising the following steps of:
step 1: dissolving stannate in deionized water to prepare stannate solution, and continuously stirring;
step 2: adding an alcohol solvent into the stannate solution obtained in the step (1), stirring, performing centrifugal separation, washing and drying to obtain a white precursor product A;
and 3, step 3: dispersing the white precursor product A obtained in the step 2 in deionized water, performing ultrasonic dispersion, adding tris (hydroxymethyl) aminomethane, adjusting the pH value of the solution, adding dopamine hydrochloride, stirring, performing centrifugal separation, washing and drying to obtain a black product B;
and 4, step 4: and (4) placing selenium powder or sulfur powder and the black product B in the step (3) in a tube furnace, and carrying out heat treatment under the protection of inert gas to obtain the nitrogen-selenium co-doped carbon-coated stannous selenide composite material or the nitrogen-sulfur co-doped carbon-coated stannous sulfide composite material.
2. The method according to claim 1, wherein in step 1, the stannate is sodium stannate trihydrate or potassium stannate trihydrate, and the concentration of stannate in the stannate solution is 0.01-0.03mol L -1 。
3. The preparation method according to claim 1, wherein in the step 2, the alcohol solvent is any one of absolute methanol, absolute ethanol and isopropanol monohydric alcohol;
the volume ratio of the alcohol solvent to the deionized water in the step 1 is (1-2) to 1.
4. The method according to claim 1, wherein the stirring time in step 2 is 6 to 48 hours.
5. The method according to claim 1, wherein in the step 2, the drying conditions are as follows: placing in a vacuum oven at 50-80 deg.C for 12-24h.
6. The preparation method according to claim 1, wherein in the step 3, the ratio of the amount of the white precursor product A to the amount of deionized water is 50 to 150mg:80 mL;
adjusting the pH value of the solution to 8.0-9.0;
the mass of the dopamine hydrochloride is 0.5 to 3 times of that of the white precursor product A.
7. The preparation method according to claim 1, wherein in the step 3, the stirring time is 12-48 h;
the drying conditions were: placing in a vacuum oven at 50-80 deg.C for 12-24h.
8. The preparation method according to claim 1, wherein in step 4, the mass of the selenium powder or sulfur powder is 1 to 3 times that of the black product B used;
the inert gas is one of nitrogen or argon;
the temperature of the heat treatment is 500-700 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 2-4h.
9. The nitrogen-selenium co-doped carbon-coated stannous selenide composite or the nitrogen-sulfur co-doped carbon-coated stannous sulfide composite prepared by the preparation method according to any one of claims 1 to 8.
10. The application of the nitrogen-selenium co-doped carbon-coated stannous selenide composite material or the nitrogen-sulfur co-doped carbon-coated stannous sulfide composite material as a sodium ion battery electrode material according to claim 9.
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| WO2019204135A1 (en) * | 2018-04-16 | 2019-10-24 | Nanotek Instruments, Inc. | Alkali metal-selenium secondary battery containing a cathode of encapsulated selenium particles |
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| CN109873149A (en) * | 2019-03-13 | 2019-06-11 | 中国石油大学(华东) | Molybdenum disulfide and the co-modified stannous sulfide nanosphere and preparation method thereof of double carbon-coatings |
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