CN112397699B - Transition metal chalcogenide/carbon composite material rich in anion vacancies and preparation method and application thereof - Google Patents

Transition metal chalcogenide/carbon composite material rich in anion vacancies and preparation method and application thereof Download PDF

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CN112397699B
CN112397699B CN202011282462.9A CN202011282462A CN112397699B CN 112397699 B CN112397699 B CN 112397699B CN 202011282462 A CN202011282462 A CN 202011282462A CN 112397699 B CN112397699 B CN 112397699B
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transition metal
metal chalcogenide
carbon composite
composite material
anion
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CN112397699A (en
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王贝贝
王刚
马生华
焦筱娟
王惠
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Northwestern University
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Abstract

A transition metal chalcogenide/carbon composite material rich in anion vacancy as well as a preparation method and application thereof relate to a metal chalcogenide composite material as well as a preparation method and application thereof. The invention aims to solve the defects of low conductivity, large volume effect and poor mechanical strength of the conventional transition metal chalcogenide, and the problems of low specific capacity and low rate capability when the transition metal chalcogenide is used as a negative electrode material of a potassium ion battery. The transition metal chalcogenide/carbon composite material rich in anion vacancies is prepared by a method of hydrothermal synthesis and high-temperature calcination in-situ anion introduction, and has the chemical formula of WMxN2‑xAnd M and N are different elements. The method comprises the following steps: firstly, preparing a network carbon skeleton; secondly, compounding the transition metal chalcogenide with the network carbon skeleton; a transition metal chalcogenide/carbon composite material rich in anion vacancy is used as a negative electrode material of a potassium ion battery.

Description

Transition metal chalcogenide/carbon composite material rich in anion vacancies and preparation method and application thereof
Technical Field
The invention relates to a metal chalcogenide composite material and a preparation method and application thereof.
Background
Currently, lithium ion batteries have been widely used in the fields of portable devices and electric vehicles. However, the lithium ion battery has limited application in large-scale energy storage systems due to the low lithium resource reserves (abundance of only 17 ppm). Therefore, the development of other types of metal-ion batteries is becoming more urgent. Sodium and potassium are elements of the same main group of lithium, and have attracted considerable attention because they have physical and chemical properties similar to those of lithium. But compared with a sodium ion battery, the potassium ion battery has higher energy density and faster migration speed, and the potassium resource is abundant in the earth crust (the abundance is about 2.09%), is cheap and easy to obtain, effectively ensures the supply of the resource, and makes the potassium ion battery become the research and development focus in the electrochemical energy storage field. At present, the negative electrode material of the potassium ion battery mainly comprises four types, namely a carbon material, a metal and an alloy, an organic material and various metal compounds, wherein the metal compound has higher theoretical specific capacity compared with the carbon material, has smaller volume effect in the charging and discharging processes compared with the metal and the alloy material, has the characteristic of difficult dissolution in electrolyte compared with the organic negative electrode material, and has great research interest in the field of electrochemical energy storage. Among various metal compounds, the transition metal chalcogenide has a typical layered structure, and K ions are rapidly deintercalated between layers to provide a large specific capacity and excellent rate performance, and thus has received much attention. However, the defects of low conductivity, large volume effect, poor mechanical strength and the like still exist, so that the advantages of the transition metal chalcogenide are not fully exerted, and the poor specific capacity and rate capability are displayed. In order to improve the specific capacity, the cycle and the rate capability of the transition metal chalcogenide electrode material, the development and the design of a novel electrode material become the key of the current research field of the potassium ion battery.
Disclosure of Invention
The invention aims to solve the problems of low electrical conductivity, large volume effect and poor mechanical strength of the existing transition metal chalcogenide, and the problems of low specific capacity and rate capability when the transition metal chalcogenide is used as a negative electrode material of a potassium ion battery, and provides a transition metal chalcogenide/carbon composite material rich in anion vacancies and a preparation method and application thereof.
The transition metal chalcogenide/carbon composite material rich in anion vacancy is synthesized by hydrothermal methodAnd high-temperature calcination and in-situ anion introduction method, wherein the chemical formula is WMxN2-x/C, wherein M is S, Se or Te, N is S, Se or Te, and M and N are different elements; the value range of x is 0<x<2。
A preparation method of a transition metal chalcogenide/carbon composite material rich in anion vacancies is completed by the following steps:
firstly, preparing a network carbon skeleton:
putting methylcellulose and an activating agent into a mortar for grinding to obtain a mixture;
the mass ratio of the methyl cellulose to the activating agent in the first step is (0.05-1) to (0.05-1);
placing the mixture in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 150-300 ℃ under the atmosphere of argon, calcining for 1-3 h at 150-300 ℃, heating the tubular furnace to 600-900 ℃, calcining for 2-6 h at 600-900 ℃, and finally cooling to room temperature to obtain a gray black product;
thirdly, immersing the gray black product into hydrochloric acid, washing under stirring, taking out, washing with absolute ethyl alcohol, washing with deionized water to neutrality, and drying to obtain a three-dimensional network carbon skeleton;
secondly, compounding the transition metal chalcogenide with the network carbon skeleton:
adding a three-dimensional network carbon skeleton into N, N-dimethyl pyrrolidone, and performing ultrasonic dispersion to obtain a solution A;
the ratio of the mass of the three-dimensional network carbon skeleton to the volume of the N, N-dimethyl pyrrolidone in the second step is (5 mg-20 mg): 5 mL-20 mL);
the power of ultrasonic dispersion in the second step is 10-50W, and the time of ultrasonic dispersion is 0.5-2 h;
② reducing agent and Na2WO4·2H2Adding O and N sources into N, N-dimethyl pyrrolidone, and stirring to obtain a solution B;
the N source in the second step is thiourea, selenium powder or tellurium powder;
the mass ratio of the reducing agent to the volume of the N, N-dimethyl pyrrolidone in the second step is (50 mg-150 mg): 10 mL-50 mL;
na in step two2WO4·2H2The volume ratio of the mass of O to the volume of N, N-dimethyl pyrrolidone is (500 mg-700 mg) to (10 mL-50 mL);
the mass ratio of the N source to the volume of the N, N-dimethyl pyrrolidone in the second step is (200 mg-400 mg): 10 mL-50 mL;
thirdly, adding the solution A into the solution B, and stirring for reaction to obtain a mixed solution; transferring the mixed solution into a polytetrafluoroethylene hydrothermal kettle, heating the polytetrafluoroethylene hydrothermal kettle to 160-200 ℃, carrying out hydrothermal reaction for 12-36 h at 160-200 ℃, and cooling to room temperature to obtain a reaction product; firstly, washing a reaction product by using absolute ethyl alcohol, then washing the reaction product by using deionized water, and finally drying the reaction product in a blast drying oven to obtain a transition metal chalcogenide/network carbon skeleton with a chemical formula of WN2/C, wherein N is S, Se or Te;
the volume ratio of the solution A to the solution B in the second step is (1-2) to (1-10);
fourthly, WN2Placing the/C and M powder in a mortar for grinding to obtain a mixture; placing the mixture in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 500-800 ℃ under the argon atmosphere, calcining the mixture for 1-3 h at 500-800 ℃, and cooling the calcined mixture to room temperature to obtain the transition metal chalcogenide/carbon composite material rich in anion vacancy, wherein the chemical formula is WMxN2-x/C, wherein M is S, Se or Te, N is S, Se or Te, and M and N are different elements; the value range of x is 0<x<2；
In the second step, the M powder is S, Se or Te, and the M powder and WN2N in the/C is different elements;
WN described in the second step2The mass ratio of the/C powder to the M powder is (0.05-1) to (0.05-1).
A transition metal chalcogenide/carbon composite material rich in anion vacancy is used as a negative electrode material of a potassium ion battery.
The principle and the advantages of the invention are as follows:
firstly, synthesizing a three-dimensional network carbon skeleton through one-step calcination and subsequent etching, and then obtaining a transition metal chalcogenide/carbon composite material (WM) rich in anion vacancies by adopting a method of hydrothermal synthesis and high-temperature calcination in-situ anion introductionxN2-xThe preparation process is simple, the requirement on equipment is low, and the method has guiding significance on the electron and defect regulation of other transition metal chalcogenide-based materials;
secondly, the theoretical specific capacity of the metal chalcogenide in the transition metal chalcogenide/carbon composite material rich in anion vacancies prepared by the invention is higher, and the larger interlayer spacing is beneficial to K+The diffusion and migration of the electrode material are carried out to promote potassium storage active sites, the three-dimensional network carbon skeleton has the characteristics of large specific surface area and high conductivity, and the coulomb efficiency and the cycle stability of the electrode material are improved;
in the process of preparing the transition metal chalcogenide/carbon composite material rich in anion vacancy, N atoms are used for partially replacing M atoms, anion vacancy is generated in situ in a crystal structure, the existence of the anion vacancy can weaken the splitting of a W4d crystal field, the band gap is reduced, the electronic conductivity of the transition metal chalcogenide is greatly improved, more active sites are induced, the change of a composite structure in the potassium storage process is reduced, and the K is accelerated+Diffusion dynamics, and rate performance enhancement;
fourthly, when the transition metal chalcogenide/carbon composite material rich in anion vacancy is prepared to be used as the negative electrode material of the potassium ion battery, the temperature is 0.1A g-1The specific capacity of potassium storage is still higher than 485mAh g when the current density is circulated for five circles-1At 1.6Ag-1The specific capacity of potassium storage of the 45 th circle circulating under the current density is still higher than 240mAh g-1The result shows that the transition metal chalcogenide/carbon composite material rich in anion vacancies has better rate performance.
A transition metal chalcogenide/carbon composite material rich in anion vacancy is used as a negative electrode material of a potassium ion battery.
Drawings
FIG. 1 is an SEM image of a three-dimensional network carbon skeleton prepared in one step I of an example;
FIG. 2 is an SEM image of an anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared according to one step two (4) of the example;
FIG. 3 is an XPS plot of an anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared according to one step two (r) of the example;
FIG. 4 is an EPR diagram, in which "■" is an EPR curve of the anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared in EXAMPLE one step two (r) and "●" is a transition metal chalcogenide/carbon network skeleton WSe prepared in EXAMPLE one step two (r)2EPR curve of/C;
FIG. 5 is a charge and discharge curve, in which 1 is a charge and discharge curve of a potassium ion battery prepared by using the anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared in example III, and 2 is a transition metal chalcogenide/carbon network skeleton WSe prepared by using example III2Charge-discharge curve of the potassium ion battery prepared by the method;
FIG. 6 is a graph of rate performance, in which 1 is a graph of rate performance of a potassium ion battery prepared in example III using the anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared in example III, and 2 is a graph of rate performance of a transition metal chalcogenide/carbon network skeleton WSe prepared in example IV using example III2Charge and discharge curves of the prepared potassium ion battery.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: this embodiment is a transition metal chalcogenide/carbon rich in anion vacanciesThe composite material is prepared by a method of hydrothermal synthesis and high-temperature calcination in-situ anion introduction, and has a chemical formula of WMxN2-x/C, wherein M is S, Se or Te, N is S, Se or Te, and M and N are different elements; the value range of x is 0<x<2。
The second embodiment is as follows: the embodiment is a preparation method of a transition metal chalcogenide/carbon composite material rich in anion vacancies, which is completed by the following steps:
firstly, preparing a network carbon skeleton:
putting methylcellulose and an activating agent into a mortar for grinding to obtain a mixture;
the mass ratio of the methyl cellulose to the activating agent in the first step is (0.05-1) to (0.05-1);
placing the mixture in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 150-300 ℃ under the atmosphere of argon, calcining for 1-3 h at 150-300 ℃, heating the tubular furnace to 600-900 ℃, calcining for 2-6 h at 600-900 ℃, and finally cooling to room temperature to obtain a gray black product;
thirdly, immersing the gray black product into hydrochloric acid, washing under stirring, taking out, washing with absolute ethyl alcohol, washing with deionized water to neutrality, and drying to obtain a three-dimensional network carbon skeleton;
secondly, compounding the transition metal chalcogenide with the network carbon skeleton:
adding a three-dimensional network carbon skeleton into N, N-dimethyl pyrrolidone, and performing ultrasonic dispersion to obtain a solution A;
the ratio of the mass of the three-dimensional network carbon skeleton to the volume of the N, N-dimethyl pyrrolidone in the second step is (5 mg-20 mg): 5 mL-20 mL);
the power of ultrasonic dispersion in the second step is 10-50W, and the time of ultrasonic dispersion is 0.5-2 h;
② reducing agent and Na2WO4·2H2Adding O and N sources into N, N-dimethyl pyrrolidone, and stirring to obtain a solution B;
the N source in the second step is thiourea, selenium powder or tellurium powder;
the mass ratio of the reducing agent to the volume of the N, N-dimethyl pyrrolidone in the second step is (50 mg-150 mg): 10 mL-50 mL;
na in step two2WO4·2H2The volume ratio of the mass of O to the volume of N, N-dimethyl pyrrolidone is (500 mg-700 mg) to (10 mL-50 mL);
the mass ratio of the N source to the volume of the N, N-dimethyl pyrrolidone in the second step is (200 mg-400 mg): 10 mL-50 mL;
thirdly, adding the solution A into the solution B, and stirring for reaction to obtain a mixed solution; transferring the mixed solution into a polytetrafluoroethylene hydrothermal kettle, heating the polytetrafluoroethylene hydrothermal kettle to 160-200 ℃, carrying out hydrothermal reaction for 12-36 h at 160-200 ℃, and cooling to room temperature to obtain a reaction product; firstly, washing a reaction product by using absolute ethyl alcohol, then washing the reaction product by using deionized water, and finally drying the reaction product in a blast drying oven to obtain a transition metal chalcogenide/network carbon skeleton with a chemical formula of WN2/C, wherein N is S, Se or Te;
the volume ratio of the solution A to the solution B in the second step is (1-2) to (1-10);
fourthly, WN2Placing the/C and M powder in a mortar for grinding to obtain a mixture; placing the mixture in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 500-800 ℃ under the argon atmosphere, calcining the mixture for 1-3 h at 500-800 ℃, and cooling the calcined mixture to room temperature to obtain the transition metal chalcogenide/carbon composite material rich in anion vacancy, wherein the chemical formula is WMxN2-x/C, wherein M is S, Se or Te, N is S, Se or Te, and M and N are different elements; the value range of x is 0<x<2；
In the second step, the M powder is S, Se or Te, and the M powder and WN2N in the/C is different elements;
WN described in the second step2The mass ratio of the/C powder to the M powder is (0.05-1) to (0.05-1).
The principle and advantages of the embodiment are as follows:
firstly, the three-dimensional network carbon skeleton is synthesized by one-step calcination and subsequent etching, and then the transition metal chalcogenide/carbon composite material (WM) rich in anion vacancy is obtained by adopting the method of hydrothermal synthesis and high-temperature calcination in-situ anion introductionxN2-xThe preparation process is simple, the requirement on equipment is low, and the method has guiding significance on the electron and defect regulation of other transition metal chalcogenide-based materials;
secondly, the theoretical specific capacity of the metal chalcogenide in the transition metal chalcogenide/carbon composite material rich in anion vacancies prepared by the embodiment is higher, and the larger interlayer spacing is favorable for K+The diffusion and migration of the electrode material are carried out to promote potassium storage active sites, the three-dimensional network carbon skeleton has the characteristics of large specific surface area and high conductivity, and the coulomb efficiency and the cycle stability of the electrode material are improved;
thirdly, in the process of preparing the transition metal chalcogenide/carbon composite material rich in anion vacancy, the N atom is used for partially replacing the M atom, the anion vacancy is generated in situ in the crystal structure, the existence of the anion vacancy can weaken the splitting of the W4d crystal field, the band gap is reduced, the electronic conductivity of the transition metal chalcogenide is greatly improved, more active sites are induced, the change of the composite structure in the potassium storage process is reduced, and the K is accelerated+Diffusion dynamics, and rate performance enhancement;
fourthly, when the transition metal chalcogenide/carbon composite material rich in anion vacancy is prepared to be used as the negative electrode material of the potassium ion battery, the concentration of the transition metal chalcogenide/carbon composite material is 0.1A g-1The specific capacity of potassium storage is still higher than 485mAh g when the current density is circulated for five circles-1At 1.6Ag-1The specific capacity of potassium storage of the 45 th circle circulating under the current density is still higher than 240mAh g-1The result shows that the transition metal chalcogenide/carbon composite material rich in anion vacancies has better rate performance.
A transition metal chalcogenide/carbon composite material rich in anion vacancy is used as a negative electrode material of a potassium ion battery.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that: the activating agent in the first step is potassium carbonate, sodium bicarbonate, potassium hydroxide or sodium hydroxide; the grinding time in the first step is 0.5-3 h. The other steps are the same as those in the second embodiment.
The fourth concrete implementation mode: the present embodiment differs from the second to third embodiments in that: step one, heating the tubular furnace to 150-300 ℃ at a heating rate of 3-8 ℃/min; step one, heating the tubular furnace to 600-900 ℃ at a heating rate of 1-5 ℃/min. The other steps are the same as those in the second to third embodiments.
The fifth concrete implementation mode: the second to fourth embodiments are different from the first to fourth embodiments in that: the mass fraction of the hydrochloric acid in the step one is 7-38%; the drying temperature in the third step is 50-90 ℃; washing for 12-24 h under stirring at 100-1200 r/min, and washing for 3-5 times with absolute alcohol. The other steps are the same as those in the second to fourth embodiments.
The sixth specific implementation mode: the second to fifth embodiments are different from the first to fifth embodiments in that: the reducing agent in the second step is NaBH4Or N2H4·H2O; the stirring speed in the second step is 200 r/min-1000 r/min, and the stirring time is 0.5 h-2 h. The other steps are the same as those in the second to fifth embodiments.
The seventh embodiment: the present embodiment differs from one of the second to sixth embodiments in that: heating the polytetrafluoroethylene hydrothermal kettle to 160-200 ℃ at a heating rate of 1-5 ℃/min; in the second step, the reaction product is firstly cleaned for 3 to 6 times by using absolute ethyl alcohol, then cleaned for 3 to 6 times by using deionized water, and finally dried for 6 to 12 hours in a blast drying oven with the temperature of 50 to 90 ℃. The other steps are the same as in embodiments two to six.
The specific implementation mode is eight: the second embodiment differs from the first embodiment in that: the grinding time in the second step is 0.5 to 3 hours; in the second step, the tubular furnace is heated to 500-800 ℃ under the argon atmosphere, and the heating rate is 2-6 ℃/min. The other steps are the same as those in the second to seventh embodiments.
The specific implementation method nine: the second to eighth differences from the first embodiment are as follows: a transition metal chalcogenide/carbon composite material rich in anion vacancy is used as a negative electrode material of a potassium ion battery. The other steps are the same as those in the second to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from the second to ninth embodiments in that: the potassium ion battery is prepared by the following steps:
firstly, mixing a transition metal chalcogenide/carbon composite material rich in anion vacancies, acetylene black and polyvinylidene fluoride according to a mass ratio of 8:1:1 to obtain a mixture; adding N-methyl pyrrolidone into the mixture, and stirring at room temperature for 24h to obtain slurry;
the ratio of the mass of the mixture in the step one to the volume of the N-methylpyrrolidone is (10 mg-20 mg): 1 mL-2 mL;
coating the slurry on a foamed nickel wafer with the diameter of 14mm, drying for 12 hours in a vacuum drying oven at the temperature of 80 ℃, cooling to room temperature, and pressing by using a powder tablet press with the pressing pressure of 15MPa to obtain an electrode slice; the mass of the transition metal chalcogenide/carbon composite material rich in anion vacancies on the electrode sheet is 2 mg-cm-2；
Thirdly, assembling:
sequentially placing the electrode plate, the diaphragm, the electrolyte, the potassium metal sheet and the gasket prepared in the second step in the center of the negative electrode shell, covering the negative electrode shell with the positive electrode shell, and sealing the negative electrode shell by using a sealing machine, wherein the working electrode is the electrode plate prepared in the second step, the counter electrode and the reference electrode are the potassium metal sheets, the diaphragm is a glass fiber diaphragm, and the electrolyte is KPF6A solution; obtaining a potassium ion battery;
KPF described in step three6The solution is KPF6Dissolving into a mixed solution of diethyl carbonate and ethylene carbonateIn the agent, the volume ratio of diethyl carbonate to ethylene carbonate is 1:1, KPF6The volume ratio of the amount of the substance (2) to the mixed solvent of diethyl carbonate and ethylene carbonate was 0.8mol: 1L. The other steps are the same as in the second to ninth embodiments.
The present invention will be described in detail with reference to the accompanying drawings 1 to 6 and examples.
The first embodiment is as follows: a preparation method of a transition metal chalcogenide/carbon composite material rich in anion vacancies is completed by the following steps:
firstly, preparing a network carbon skeleton:
putting methylcellulose and an activating agent into a mortar for grinding to obtain a mixture;
the mass ratio of the methyl cellulose to the activating agent in the first step is 1: 6;
the activating agent in the first step is sodium bicarbonate;
the grinding time in the first step is 1 h;
secondly, placing the mixture in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 200 ℃ under the atmosphere of argon, calcining the mixture for 2 hours at 200 ℃, heating the tubular furnace to 800 ℃, calcining the mixture for 4 hours at 800 ℃, and finally cooling the mixture to room temperature to obtain a gray black product;
step one, heating the tubular furnace to 200 ℃ at a heating rate of 3 ℃/min;
step one, heating the tubular furnace to 800 ℃ at a heating rate of 1 ℃/min;
thirdly, immersing the gray black product into hydrochloric acid, washing under stirring, taking out, washing with absolute ethyl alcohol, washing with deionized water to neutrality, and drying to obtain a three-dimensional network carbon skeleton;
the mass fraction of the hydrochloric acid in the step one is 10 percent;
the drying temperature in the third step is 70 ℃;
washing for 24 hours under the stirring condition in the step one, taking out and washing for 5 times by using absolute ethyl alcohol, wherein the stirring speed is 600 r/min;
secondly, compounding the transition metal chalcogenide with the network carbon skeleton:
adding a three-dimensional network carbon skeleton into N, N-dimethyl pyrrolidone, and performing ultrasonic dispersion to obtain a solution A;
the volume ratio of the mass of the three-dimensional network carbon skeleton to the N, N-dimethyl pyrrolidone in the second step is 10mg:10 mL;
the power of ultrasonic dispersion in the second step is 35W, and the time of ultrasonic dispersion is 0.5 h;
② reducing agent and Na2WO4·2H2Adding O and N sources into N, N-dimethyl pyrrolidone, and stirring to obtain a solution B;
the reducing agent in the second step is NaBH4；
The stirring speed in the second step is 800r/min, and the stirring time is 1 h;
the N source in the second step is selenium powder;
the mass ratio of the reducing agent to the volume of the N, N-dimethyl pyrrolidone in the second step is 100mg to 20 mL;
na in step two2WO4·2H2The volume ratio of the mass of O to the volume of N, N-dimethyl pyrrolidone is 660mg to 20 mL;
the mass ratio of the N source to the volume of the N, N-dimethyl pyrrolidone in the second step is 320mg:20 mL;
thirdly, adding the solution A into the solution B, and stirring for reaction to obtain a mixed solution; transferring the mixed solution into a polytetrafluoroethylene hydrothermal kettle, heating the polytetrafluoroethylene hydrothermal kettle to 200 ℃, carrying out hydrothermal reaction at 200 ℃ for 24h, and cooling to room temperature to obtain a reaction product; firstly, washing a reaction product by using absolute ethyl alcohol, then washing the reaction product by using deionized water, and finally, putting the reaction product into a blast drying oven for drying to obtain a transition metal chalcogenide/network carbon skeleton with a chemical formula of WSe2/C；
The volume ratio of the solution A to the solution B in the second step is 1: 2;
the heating rate of heating the polytetrafluoroethylene hydrothermal kettle to 200 ℃ is 2 ℃/min;
in the second step, firstly, the reaction product is washed for 5 times by using absolute ethyl alcohol, then the reaction product is washed for 5 times by using deionized water, and finally the reaction product is dried for 10 hours in a blast drying oven with the temperature of 60 ℃;
fourthly, the WSe2Placing the/C and sulfur powder in a mortar for grinding to obtain a mixture; placing the mixture in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 700 ℃ under the argon atmosphere, calcining the mixture for 2 hours at 700 ℃, and cooling the mixture to room temperature to obtain a transition metal chalcogenide/carbon composite material rich in anion vacancies, wherein the chemical formula is WSSe/C;
the grinding time in the second step is 0.5 h;
in the second step, the tubular furnace is heated to 700 ℃ under the argon atmosphere, and the heating rate is 2 ℃/min;
WSe described in step two2The mass ratio of the/C to the sulfur powder is 1: 1.
FIG. 1 is an SEM image of a three-dimensional network carbon skeleton prepared in one step I of an example;
as can be seen from fig. 1, the three-dimensional network carbon skeleton prepared in step one of the examples has a honeycomb structure and is composed of interconnected macroporous and meso/microporous carbon walls, and these cavities/channels provide abundant porosity and active sites, providing a microreactor for growing transition metal chalcogenides.
FIG. 2 is an SEM image of an anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared according to one step two (4) of the example;
as can be seen from FIG. 2, the WSSe/C rich in anion vacancies is obtained by hydrothermal synthesis and high-temperature calcination in-situ anion introduction, and the WSSe nanosheets uniformly grow and are distributed on the surface and in the cavities/channels of the prepared three-dimensional network carbon skeleton.
FIG. 3 is an XPS plot of an anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared according to one step two (r) of the example;
as can be seen from FIG. 3, WSSe/C mainly contains W, S, Se and C, which show that S atoms are successfully doped into composite material WSe2in/C, and replacing Se atom, further proves that the prepared composite material consists of a network carbon skeleton C and an anion vacancy-rich transition metal chalcogenide WSSe.
FIG. 4 is an EPR diagram, in which "■" is an EPR curve of the anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared in EXAMPLE one step two (r) and "●" is a transition metal chalcogenide/carbon network skeleton WSe prepared in EXAMPLE one step two (r)2EPR curve of/C;
as can be seen from fig. 4, WSSe/C of the transition metal chalcogenide/carbon composite material rich in anion vacancies prepared in the second step of the example has a significant EPR signal at a g value of 2.003, indicating that anion vacancies are successfully introduced after the substitution of Se atoms by S atoms incorporated in situ by high-temperature calcination.
Example three: the preparation of a potassium ion battery using the anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared in example step di (r) was carried out as follows:
firstly, mixing the transition metal chalcogenide/carbon composite material WSSe/C rich in anion vacancies prepared in the step two to the step four, acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1 to obtain a mixture; adding N-methyl pyrrolidone into the mixture, and stirring at room temperature for 24h to obtain slurry;
the volume ratio of the mass of the mixture in the step one to the volume of the N-methylpyrrolidone is 10mg:1 mL;
coating the slurry on a foamed nickel wafer with the diameter of 14mm, drying for 12 hours in a vacuum drying oven at the temperature of 80 ℃, cooling to room temperature, and pressing by using a powder tablet press with the pressing pressure of 15MPa to obtain an electrode slice; the mass of the transition metal chalcogenide/carbon composite material rich in anion vacancies on the electrode sheet is 2 mg-cm-2；
Thirdly, assembling:
sequentially placing the electrode plate, the diaphragm, the electrolyte, the potassium metal sheet and the gasket prepared in the second step in the center of the negative electrode shell, covering the negative electrode shell with the positive electrode shell, and finally sealing the negative electrode shell by using a sealing machine, wherein working electricity is usedThe electrode slice prepared in the second step comprises a counter electrode and a reference electrode which are potassium metal slices, a diaphragm which is a glass fiber diaphragm and electrolyte which is KPF6A solution; obtaining a potassium ion battery;
KPF described in step three6The solution is KPF6Dissolving into a mixed solvent of diethyl carbonate and ethylene carbonate, wherein the volume ratio of diethyl carbonate to ethylene carbonate is 1:1, KPF6The volume ratio of the amount of the substance (2) to the mixed solvent of diethyl carbonate and ethylene carbonate was 0.8mol: 1L.
Example four: the present embodiment is different from the third embodiment in that: example step two preparation of transition Metal chalcogenide/network carbon skeleton WSe2Mixing the/C, the acetylene black and the polyvinylidene fluoride according to the mass ratio of 8:1:1 to obtain a mixture; n-methylpyrrolidone was added to the mixture, and the mixture was further stirred at room temperature for 24 hours to obtain a slurry. The other steps and parameters are the same as those in the third embodiment.
FIG. 5 is a charge and discharge curve, in which 1 is a charge and discharge curve of a potassium ion battery prepared by using the anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared in example III, and 2 is a transition metal chalcogenide/carbon network skeleton WSe prepared by using example III2Charge-discharge curve of the potassium ion battery prepared by the method;
as can be seen from FIG. 5, the anion vacancy rich WSSe/C composite electrode showed a pair of distinct charge/discharge plateaus at 1.45/1.76V, WSe without S atom incorporation2the/C composite electrode has smaller polarization, which shows that the reversibility of the WSSe/C composite electrode rich in anion vacancy in the processes of potassium intercalation and potassium deintercalation is greatly improved.
FIG. 6 is a graph of rate performance, in which 1 is a graph of rate performance of a potassium ion battery prepared in example III using the anion vacancy rich transition metal chalcogenide/carbon composite WSSe/C prepared in example III, and 2 is a graph of rate performance of a transition metal chalcogenide/carbon network skeleton WSe prepared in example IV using example III2Charge and discharge curves of the prepared potassium ion battery.
As can be seen from FIG. 6, the reversible specific capacities (at 0.1, 0.2, 0.4, 0.8, and 1.6A g) of the anion vacancy rich WSSe/C composite electrode at the respective current densities-1Has specific capacities of 485, 372, 310, 276, and 235mAh g at current densities of-1) Are all much higher than WSe without S atoms incorporated2(at 0.1, 0.2, 0.4, 0.8, and 1.6 Ag/C) composite electrode-1Has specific capacities of 367, 238, 172, 139 and 108mAhg at current densities of-1). The result shows that the WSSe/C composite material rich in anion vacancy obtained after the S atom is introduced in situ through high-temperature calcination has better rate performance.

Claims (10)

1. The transition metal chalcogenide/carbon composite material rich in anion vacancies is characterized in that the transition metal chalcogenide/carbon composite material rich in anion vacancies is prepared by a method of hydrothermal synthesis and high-temperature calcination in-situ anion introduction, and has the chemical formula of WMxN2-x/C, wherein M is S, Se or Te, N is S, Se or Te, and M and N are different elements; the value range of x is 0<x<2。
2. The method of claim 1, wherein the method comprises the steps of:
firstly, preparing a network carbon skeleton:
putting methylcellulose and an activating agent into a mortar for grinding to obtain a mixture;
the mass ratio of the methyl cellulose to the activating agent in the first step is (0.05-1) to (0.05-1);
placing the mixture in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 150-300 ℃ under the atmosphere of argon, calcining for 1-3 h at 150-300 ℃, heating the tubular furnace to 600-900 ℃, calcining for 2-6 h at 600-900 ℃, and finally cooling to room temperature to obtain a gray black product;
thirdly, immersing the gray black product into hydrochloric acid, washing under stirring, taking out, washing with absolute ethyl alcohol, washing with deionized water to neutrality, and drying to obtain a three-dimensional network carbon skeleton;
secondly, compounding the transition metal chalcogenide with the network carbon skeleton:
adding a three-dimensional network carbon skeleton into N, N-dimethyl pyrrolidone, and performing ultrasonic dispersion to obtain a solution A;
the ratio of the mass of the three-dimensional network carbon skeleton to the volume of the N, N-dimethyl pyrrolidone in the second step is (5 mg-20 mg): 5 mL-20 mL);
the power of ultrasonic dispersion in the second step is 10-50W, and the time of ultrasonic dispersion is 0.5-2 h;
② reducing agent and Na2WO4·2H2Adding O and N sources into N, N-dimethyl pyrrolidone, and stirring to obtain a solution B;
the N source in the second step is thiourea, selenium powder or tellurium powder;
the mass ratio of the reducing agent to the volume of the N, N-dimethyl pyrrolidone in the second step is (50 mg-150 mg): 10 mL-50 mL;
na in step two2WO4·2H2The volume ratio of the mass of O to the volume of N, N-dimethyl pyrrolidone is (500 mg-700 mg) to (10 mL-50 mL);
the mass ratio of the N source to the volume of the N, N-dimethyl pyrrolidone in the second step is (200 mg-400 mg): 10 mL-50 mL;
thirdly, adding the solution A into the solution B, and stirring for reaction to obtain a mixed solution; transferring the mixed solution into a polytetrafluoroethylene hydrothermal kettle, heating the polytetrafluoroethylene hydrothermal kettle to 160-200 ℃, carrying out hydrothermal reaction for 12-36 h at 160-200 ℃, and cooling to room temperature to obtain a reaction product; firstly, washing a reaction product by using absolute ethyl alcohol, then washing the reaction product by using deionized water, and finally drying the reaction product in a blast drying oven to obtain a transition metal chalcogenide/network carbon skeleton with a chemical formula of WN2/C, wherein N is S, Se or Te;
the volume ratio of the solution A to the solution B in the second step is (1-2) to (1-10);
fourthly, WN2Placing the/C and M powder in a mortar for grinding to obtain a mixture; placing the mixture in a tubular furnace, introducing argon into the tubular furnace, heating the tubular furnace to 500-800 ℃ under the argon atmosphere, calcining the mixture for 1-3 h at 500-800 ℃, and cooling the calcined mixture to room temperature to obtain the transition metal chalcogenide/carbon composite material rich in anion vacancy, wherein the chemical formula is WMxN2-x/C, wherein M is S, Se or Te, N is S, Se or Te, and M and N are different elements; the value range of x is 0<x<2；
In the second step, the M powder is S, Se or Te, and the M powder and WN2N in the/C is different elements;
WN described in the second step2The mass ratio of the/C powder to the M powder is (0.05-1) to (0.05-1).
3. The method for preparing a transition metal chalcogenide/carbon composite material rich in anion vacancies according to claim 2, wherein the activating agent in the first step (r) is potassium carbonate, sodium bicarbonate, potassium hydroxide or sodium hydroxide; the grinding time in the first step is 0.5-3 h.
4. The method for preparing a transition metal chalcogenide/carbon composite material rich in anion vacancies according to claim 2, wherein the first step is a step of heating the tube furnace to 150-300 ℃ at a heating rate of 3-8 ℃/min; step one, heating the tubular furnace to 600-900 ℃ at a heating rate of 1-5 ℃/min.
5. The method for preparing a transition metal chalcogenide/carbon composite material rich in anion vacancies according to claim 2, wherein the mass fraction of the hydrochloric acid in the step one is 7 to 38 percent; the drying temperature in the third step is 50-90 ℃; washing for 12-24 h under stirring at 100-1200 r/min, and washing for 3-5 times with absolute alcohol.
6. The method of claim 2, wherein the reducing agent in step two is NaBH4Or N2H4·H2O; the stirring speed in the second step is 200 r/min-1000 r/min, and the stirring time is 0.5 h-2 h.
7. The method for preparing a transition metal chalcogenide/carbon composite material rich in anion vacancies according to claim 2, wherein the heating rate of heating the polytetrafluoroethylene hydrothermal kettle to 160-200 ℃ in the second step is 1-5 ℃/min; in the second step, the reaction product is firstly cleaned for 3 to 6 times by using absolute ethyl alcohol, then cleaned for 3 to 6 times by using deionized water, and finally dried for 6 to 12 hours in a blast drying oven with the temperature of 50 to 90 ℃.
8. The method for preparing a transition metal chalcogenide/carbon composite material rich in anion vacancies according to claim 2, wherein the grinding time in the second and fourth steps is 0.5 to 3 hours; in the second step, the tubular furnace is heated to 500-800 ℃ under the argon atmosphere, and the heating rate is 2-6 ℃/min.
9. The use of an anion vacancy rich transition metal chalcogenide/carbon composite as claimed in claim 1, wherein an anion vacancy rich transition metal chalcogenide/carbon composite is used as a negative electrode material for a potassium ion battery.
10. The use of an anion vacancy rich transition metal chalcogenide/carbon composite as claimed in claim 9, wherein the potassium ion battery is prepared by the steps of:
firstly, mixing a transition metal chalcogenide/carbon composite material rich in anion vacancies, acetylene black and polyvinylidene fluoride according to a mass ratio of 8:1:1 to obtain a mixture; adding N-methyl pyrrolidone into the mixture, and stirring at room temperature for 24h to obtain slurry;
the ratio of the mass of the mixture in the step one to the volume of the N-methylpyrrolidone is (10 mg-20 mg): 1 mL-2 mL;
coating the slurry on a foamed nickel wafer with the diameter of 14mm, drying for 12 hours in a vacuum drying oven at the temperature of 80 ℃, cooling to room temperature, and pressing by using a powder tablet press with the pressing pressure of 15MPa to obtain an electrode slice; the mass of the transition metal chalcogenide/carbon composite material rich in anion vacancies on the electrode sheet is 2 mg-cm-2；
Thirdly, assembling:
sequentially placing the electrode plate, the diaphragm, the electrolyte, the potassium metal sheet and the gasket prepared in the second step in the center of the negative electrode shell, covering the negative electrode shell with the positive electrode shell, and sealing the negative electrode shell by using a sealing machine, wherein the working electrode is the electrode plate prepared in the second step, the counter electrode and the reference electrode are the potassium metal sheets, the diaphragm is a glass fiber diaphragm, and the electrolyte is KPF6A solution; obtaining a potassium ion battery;
KPF described in step three6The solution is KPF6Dissolving into a mixed solvent of diethyl carbonate and ethylene carbonate, wherein the volume ratio of the diethyl carbonate to the ethylene carbonate is 1:1, KPF6The volume ratio of the amount of the substance (2) to the mixed solvent of diethyl carbonate and ethylene carbonate was 0.8mol: 1L.
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