CN111799458B - Tin elemental composite tungsten disulfide/reduced graphene oxide composite electrode material and preparation method and application thereof - Google Patents
Tin elemental composite tungsten disulfide/reduced graphene oxide composite electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a tin elemental substance composite tungsten disulfide/reduced graphene oxide composite electrode material and a preparation method and application thereof, and belongs to the field of tungsten disulfide nano material preparation. The invention provides a simple and controllable method for preparing a simple substance tin composite tungsten disulfide/reduced graphene oxide composite electrode material, which comprises the following steps: by utilizing a solvothermal and normal-temperature liquid-phase reduction process and under the auxiliary action of a template agent, tin nanoparticles are reduced and grown on the tungsten disulfide nanosheets of the tungsten disulfide/reduced graphene oxide composite material, and the conductivity of the finally obtained tin elemental composite tungsten disulfide/reduced graphene oxide composite electrode material is effectively enhanced by utilizing a tin elemental substance, so that the electrochemical performance of the material is improved. The tin elemental substance composite tungsten disulfide/reduced graphene oxide composite electrode material prepared by the invention has good dispersibility, uniform size and uniform appearance, and is 200 mA.g‑1After the current density of (3) is cycled for 200 cycles, the capacity retention rate is 92%, so that the lithium ion battery anode material can be applied to a battery anode material.
Description
Technical Field
The invention belongs to the field of preparation of tungsten disulfide nano materials, and relates to a tin elemental substance composite tungsten disulfide/reduced graphene oxide composite electrode material, and a preparation method and application thereof.
Background
The sodium ion battery has the characteristics of high energy density, long cycle life, green cleanness and the like, and is one of the most important energy storage devices in the current energy field. In recent decades, scientists have continuously developed research on the improvement of the performance of the sodium-ion battery, and the performance of the sodium-ion battery is more and more excellent through continuous experimental adjustment and improvement. Transition metal sulfides are gradually the focus of attention in the field of electrochemical research by virtue of their high theoretical capacity and their excellent cycling characteristics and rate capability. Compared with the traditional embedded sodium ion battery active material, the embedded sodium ion battery active material usually exists in the form of a block, but the block is stacked by a nano-layered structure, tungsten disulfide (WS2) is used as a transition metal chalcogenide, has sufficient resources, higher theoretical capacity and high electrode potential, is a layered compound with a graphene-like structure, and the unique layered structure and the larger interlayer spacing (6.12nm) thereof are beneficial to the deintercalation of sodium ions in the charging and discharging processes. However, tungsten disulfide is greatly deformed in the charging and discharging processes, and the cycle performance is not ideal enough. As a semiconductor material, the material has the defect of poor conductivity, so that the electron transmission is slow and the rate capability is poor.
According to the literature report, the carbon material is used as the matrix, which is beneficial to the transmission of electrons and can effectively improve the electrochemical stability of the composite material. For example, jin Ren et al uses tungsten disulfide and three-dimensional single-walled carbon nanotube composite material as the negative electrode material of lithium ion battery (Ren J, Wang Z, Yang F, et al free and 3D single-walled carbon nanotubes/WS)2,nanosheets foams as ultra-long-life anodes for rechargeable lithium ion batteries[J]Electrochimica Acta,2018.), greatly improves the cycling stability of the material, the material circulates for 1000 circles under the current density of 1A/g, and the capacity is stabilized at 688.9 mAh/g. However, tungsten disulfide itself has poor conductivity, resulting in poor rate capability.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a simple tin substance composite tungsten disulfide/reduced graphene oxide composite electrode material, and a preparation method and application thereof. According to the invention, the simple substance tin composite tungsten disulfide/reduced graphene oxide composite electrode material is prepared by a simple preparation method. The tin elemental compound tungsten disulfide/reduced graphene oxide composite electrode material prepared by the invention has better capacity retention rate and has greater potential in battery cathode application.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a tin simple substance composite tungsten disulfide/reduced graphene oxide composite electrode material, which comprises the following steps:
1) uniformly dispersing reduced graphene oxide, tungsten hexachloride and thioacetamide in water to obtain a reaction solution; cooling the reaction solution after hydrothermal reaction to obtain a product, centrifugally washing the product, and collecting powder through freeze drying to obtain the tungsten disulfide/reduced graphene oxide composite material;
2) adding polyvinylpyrrolidone, stannous chloride dihydrate, tungsten disulfide/reduced graphene oxide composite material and sodium borohydride into water, and uniformly dispersing to obtain precursor liquid; centrifugally washing the precursor solution, and then freeze-drying and collecting powder to obtain the elemental tin composite tungsten disulfide/reduced graphene oxide composite material;
3) and calcining and annealing the elemental tin composite tungsten disulfide/reduced graphene oxide composite material to obtain the elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material.
Preferably, in the step 1), the reaction charge ratio of the reduced graphene oxide, water, tungsten hexachloride and thioacetamide is (30-60) mg, (30-60) mL, (0.295-0.59) g, (0.5625-1.125) g.
Preferably, in the step 1), the hydrothermal reaction temperature is 200-240 ℃, and the reaction time is 12-48 h.
Preferably, in the step 2), the reaction charge ratio of the polyvinylpyrrolidone, the stannous chloride dihydrate, the tungsten disulfide/reduced graphene oxide composite material, the sodium borohydride and the water is (1-4) mg, (0.2-1) mg, (10-30) mL.
Preferably, in the step 1) and the step 2), the temperature of freeze drying is-40 to-70 ℃, the time is 8 to 12 hours, and the vacuum degree of a freeze drying environment is 10 to 40 Pa.
Preferably, the calcination annealing treatment in step 3) specifically includes: under the protection of inert atmosphere, the calcining temperature is 400-600 ℃, the heating rate is 5-20 ℃/min, and the heat preservation time is 1-3 h.
The invention also discloses the elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material prepared by the preparation method.
Preferably, the elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material is 200 mA-g-1After the current density of (1) is cycled for 200 circles, the capacity retention rate is 92%.
The invention also discloses an application of the tin elemental substance composite tungsten disulfide/reduced graphene oxide composite electrode material as a battery cathode material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a tin simple substance composite tungsten disulfide/reduced graphene oxide composite electrode material, which utilizes a solvothermal method and a normal-temperature liquid-phase reduction process to prepare the tin simple substance composite tungsten disulfide/reduced graphene oxide (Sn @ WS) under the auxiliary action of taking thioacetamide as a template agent2The composite material is calcined and annealed to successfully prepare the tin elemental composite tungsten disulfide/reduced graphene oxide (Sn @ WS)2/rGO) composite electrode material. In the preparation method, tungsten disulfide nanosheets are grown on reduced oxidized stones by a solvothermal method which is simple to operateOn the graphene structure, a method with easily controlled parameters and mild process is used for reducing tungsten disulfide/reduced graphene oxide (WS) by adopting a normal-temperature liquid-phase reduction process and the assistance of a template agent2The tin elementary substance nano particles are reduced and grown on the tungsten disulfide nano sheet of the/rGO) composite material, the composite material has higher theoretical capacity by utilizing the stronger conductivity of the tin metal elementary substance, and the conductivity of the finally obtained composite electrode material can be effectively enhanced, so that the electrochemical performance is improved. The preparation method has simple process and high repeatability, and is favorable for popularization and application of the preparation method.
The invention also discloses the elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material prepared by the preparation method. In the material, elemental tin nanoparticles are reduced and grown on tungsten disulfide nano-sheets, and scanning electron microscope tests show that the elemental tin nanoparticles can be uniformly dispersed in WS2The surface of the/rGO composite material can utilize a tin simple substance with excellent conductivity in the material, so that the overall electrochemical performance of the tin simple substance composite tungsten disulfide/reduced graphene oxide composite electrode material is improved.
Furthermore, the cycle performance test proves that the elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material prepared by the invention has the working pressure of 200 mA.g-1After the current density of (2) is cycled for 200 circles, the capacity retention rate is 92%, so that the current density has excellent cycling stability.
The invention also discloses an application of the elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material as a battery cathode material. Sn @ WS prepared by using method2the/rGO composite electrode material has wide research value and application value in the electrochemical field.
Drawings
FIG. 1 is a schematic representation of Sn @ WS prepared in example 3 of the present invention2An X-ray diffraction (XRD) pattern of the/rGO composite electrode material;
FIG. 2 is a diagram of Sn @ WS prepared in example 3 of the present invention2Scanning Electron Microscope (SEM) pictures of/rGO composite electrode materials; wherein, (a) is a low-power graph and (b) is a high-power graph;
FIG. 3 is Sn @ WS prepared in example 3 of the present invention2A cycle performance profile for/rGO composite electrode materials;
FIG. 4 is Sn @ WS prepared in example 3 of the present invention2Rate performance graph of/rGO composite electrode material.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The specific technical scheme is as follows: preparation of elemental tin composite tungsten disulfide/reduced graphene oxide (Sn @ WS)2Method for the production of/rGO) composite products, comprising the following steps:
the method comprises the following steps: under the condition of room temperature, 30-60 mg of rGO is added into 30-60 mL of deionized water and subjected to ultrasonic treatment for 2-6 hours to form a uniform solution A, and the concentration of the uniform solution A is controlled to be 0.5-2 mol/L. The ultrasonic power is 300-1000W;
step two: adding 0.295-0.59 g of tungsten hexachloride and 0.5625-1.125 g of thioacetamide into the solution A, stirring at the speed of 500-800 r/min for 0.5-3 h to obtain a solution B.
Step three: and transferring the solution C into a hydrothermal kettle, controlling the filling ratio to be 30-60%, then sealing the hydrothermal kettle, controlling the hydrothermal temperature to be 200-240 ℃ in a homogeneous reaction instrument, reacting for 12-48 h, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4-6 times, placing the product in a freeze dryer with the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa for drying for 8-12 hours to obtain black WS2a/rGO composite material.
Step five: dissolving PVP and stannous chloride dihydrate into 10-30 mL of aqueous solution completely, and stirring for 10-60 min at the stirring speed of 500-800 r/min. Adding the above WS2And stirring the/rGO composite material for 0.5-2 h at a stirring speed of 500-800 r/min. After mixing evenly, sodium borohydride is added, m (PVP) m (stannous chloride dihydrate) m (WS)2(1-4): (0.2-1): (rGO): (sodium borohydride). Stirring for 0.5-1 h at a speed of 500-800 r/min.
Step six: washing the precursor solution with absolute ethyl alcohol and deionized water, performing centrifugal separation, repeatedly washing for 4-6 times, and drying in a freeze dryer at the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa for 8-12 h to obtain black Sn @ WS2a/rGO composite material.
Step seven: taking the Sn @ WS2Annealing the/rGO composite material in a low-temperature tubular furnace, calcining at 400-600 ℃ under the protection of argon atmosphere, raising the temperature at 5-20 ℃/min, and preserving the heat for 1-3 h to obtain a product Sn @ WS2a/rGO composite electrode material.
The present invention is described in further detail below with reference to specific examples:
example 1
The method comprises the following steps: under the condition of room temperature, 30mg of rGO is added into 60mL of deionized water and is subjected to ultrasonic treatment for 2 hours to form a uniform solution A, and the concentration of the uniform solution A is controlled to be 0.5 mol/L. The ultrasonic power is 1000W;
step two: 0.295g of tungsten hexachloride and 0.5625g of thioacetamide are added into the solution A, the stirring speed is 800r/min, the mixture is stirred for 3 hours, and the obtained solution is a solution B.
Step three: and transferring the solution C into a hydrothermal kettle, controlling the filling ratio to be 60%, then sealing the hydrothermal kettle, controlling the hydrothermal temperature to be 240 ℃ in a homogeneous reaction instrument, reacting for 12 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 40Pa for 8 hr to obtain black WS2a/rGO composite material.
Step five: PVP and stannous chloride dihydrate are completely dissolved in 15mL of aqueous solution and stirred for 20min at the stirring speed of 800 r/min. Adding the above WS2the/rGO composite material is stirred for 0.5h at the stirring speed of 800 r/min. After mixing evenly, sodium borohydride is added, m (PVP) m (stannous chloride dihydrate) m (WS)2(rGO): sodium borohydride — 4:4: 1. Stirring for 1h at a stirring speed of 800 r/min.
Step six: washing the precursor solution with anhydrous ethanol and deionized water, centrifuging, washing for 4 times, drying in a freeze dryer at-40 deg.C and vacuum degree of 10Pa for 8 hr to obtain black Sn @ WS2a/rGO composite material.
Step seven: taking the Sn @ WS2Annealing the/rGO composite material in a low-temperature tubular furnace, calcining at 600 ℃ under the protection of argon atmosphere, raising the temperature at a rate of 20 ℃/min, and preserving the heat for 1h to obtain a product Sn @ WS2a/rGO composite electrode material.
Example 2
The method comprises the following steps: under the condition of room temperature, 50mg of rGO is added into 60mL of deionized water and is subjected to ultrasonic treatment for 5 hours to form a uniform solution A, and the concentration of the uniform solution A is controlled to be 1.2 g/L. The ultrasonic power is 800W;
step two: 0.59g of tungsten hexachloride and 1.125g of thioacetamide are added into the solution A, the stirring speed is 600r/min, and the solution is stirred for 3 hours, so that the solution B is obtained.
Step three: and transferring the solution C into a hydrothermal kettle, controlling the filling ratio to be 60%, then sealing the hydrothermal kettle, controlling the hydrothermal temperature to be 240 ℃ in a homogeneous reaction instrument, reacting for 48 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 10Pa for 10 hr to obtain black WS2a/rGO composite material.
Step five: PVP and stannous chloride dihydrate are completely dissolved in 25mL of aqueous solution and stirred for 60min at the stirring speed of 500 r/min. Adding the above WS2the/rGO composite material is stirred for 0.5h at the stirring speed of 500 r/min. After mixing evenly, sodium borohydride is added, m (PVP) m (stannous chloride dihydrate) m (WS)2(rGO): sodium borohydride ═ 3:2:1: 0.5. Stirring for 1h at a stirring speed of 800 r/min.
Step six: washing the precursor solution with anhydrous ethanol and deionized water, centrifuging, washing for 5 times, drying in a freeze dryer at-40 deg.C and vacuum degree of 10Pa for 12 hr to obtain black Sn @ WS2a/rGO composite material.
Step seven: taking the Sn @ WS2Annealing the/rGO composite material in a low-temperature tubular furnace, calcining at 500 ℃ under the protection of argon atmosphere, heating at a rate of 10 ℃/min, and keeping the temperature for 3h to obtain a product Sn @ WS2a/rGO composite electrode material.
Example 3
The method comprises the following steps: under the condition of room temperature, 60mg of rGO is added into 60mL of deionized water and is subjected to ultrasonic treatment for 6 hours to form a uniform solution A, and the concentration of the uniform solution A is controlled to be 1 mol/L. The ultrasonic power is 500W;
step two: 0.59g of tungsten hexachloride and 1.125g of thioacetamide are added into the solution A, the stirring speed is 800r/min, the stirring is carried out for 2 hours, and the obtained solution is the solution B.
Step three: and transferring the solution C into a hydrothermal kettle, controlling the filling ratio to be 60%, then sealing the hydrothermal kettle, controlling the hydrothermal temperature to be 200 ℃ in a homogeneous reaction instrument, reacting for 24 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the reaction kettle, taking out the product, sequentially washing with absolute ethyl alcohol and deionized water, performing centrifugal separation, repeatedly washing for 4-6 times, placing in a freeze dryer with the temperature of-60 ℃ and the vacuum degree of 25Pa, and drying for 10h to obtain black WS2a/rGO composite material.
Step five: PVP and stannous chloride dihydrate are completely dissolved in 10mL of aqueous solution and stirred for 30min at the stirring speed of 800 r/min. Adding the above WS2the/rGO composite material is stirred for 0.5h at the stirring speed of 800 r/min. After mixing evenly, sodium borohydride is added, m (PVP) m (stannous chloride dihydrate) m (WS)2(rGO): sodium borohydride — 4:4: 1. Stirring for 1h at a stirring speed of 800 r/min.
Step six: washing the precursor solution with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 40Pa for 12 hr to obtain black Sn @ WS2a/rGO composite material.
Step seven: taking the Sn @ WS2Annealing the/rGO composite material in a low-temperature tubular furnace, calcining at 500 ℃ under the protection of argon atmosphere, heating at a rate of 10 ℃/min, and keeping the temperature for 2h to obtain a product Sn @ WS2a/rGO composite electrode material.
Example 4
The method comprises the following steps: under the condition of room temperature, 40mg of rGO is added into 60mL of deionized water and is subjected to ultrasonic treatment for 2-6 hours to form a uniform solution A, and the concentration of the uniform solution A is controlled to be 0.67 g/L. The ultrasonic power is 1000W;
step two: 0.358g of tungsten hexachloride and 1.08g of thioacetamide are added into the solution A, the stirring speed is 500r/min, and the solution is stirred for 3 hours, so that the solution B is obtained.
Step three: and transferring the solution C into a hydrothermal kettle, controlling the filling ratio to be 60%, then sealing the hydrothermal kettle, controlling the hydrothermal temperature to be 210 ℃ and the reaction time to be 36h in a homogeneous reaction instrument, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the reaction kettle, taking out the products and sequentially extractingWashing with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-40 deg.C and vacuum degree of 10Pa for 9 hr to obtain black WS2a/rGO composite material.
Step five: PVP and stannous chloride dihydrate are completely dissolved in 20mL of aqueous solution and stirred for 25min at the stirring speed of 500 r/min. Adding the above WS2the/rGO composite material is stirred for 1 hour at the stirring speed of 500 r/min. After mixing evenly, sodium borohydride is added, m (PVP) m (stannous chloride dihydrate) m (WS)2(rGO): sodium borohydride ═ 3:3:1: 0.5. Stirring for 1h at a stirring speed of 800 r/min.
Step six: washing the precursor solution with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 40Pa for 12 hr to obtain black Sn @ WS2a/rGO composite material.
Step seven: taking the Sn @ WS2Annealing the/rGO composite material in a low-temperature tubular furnace, calcining at 550 ℃, heating at a rate of 15 ℃/min and keeping the temperature for 3 hours under the protection of argon atmosphere to obtain a product Sn @ WS2a/rGO composite electrode material.
Example 5
The method comprises the following steps: under the condition of room temperature, 60mg of rGO is added into 30mL of deionized water and is subjected to ultrasonic treatment for 2-6 hours to form a uniform solution A, and the concentration of the uniform solution A is controlled to be 2 g/L. The ultrasonic power is 800W;
step two: and (3) adding 0.298g of tungsten hexachloride and 0.875g of thioacetamide into the solution A, stirring at the speed of 500r/min for 3 hours to obtain a solution B.
Step three: and transferring the solution C into a hydrothermal kettle, controlling the filling ratio to be 30%, then sealing the hydrothermal kettle, controlling the hydrothermal temperature to be 240 ℃ in a homogeneous reaction instrument, reacting for 12 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 4 times, drying in a freeze dryer at-40 deg.C and vacuum degree of 10Pa for 8 hr to obtain black WS2rGO composite materialAnd (5) feeding.
Step five: PVP and stannous chloride dihydrate are completely dissolved in 30mL of aqueous solution and stirred for 60min at the stirring speed of 800 r/min. Adding the above WS2And stirring the/rGO composite material for 2 hours at the stirring speed of 800 r/min. After mixing evenly, sodium borohydride is added, m (PVP) m (stannous chloride dihydrate) m (WS)2(rGO): sodium borohydride ═ 1:2:4: 1. Stirring for 1h at a stirring speed of 800 r/min.
Step six: washing the precursor solution with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 40Pa for 12 hr to obtain black Sn @ WS2a/rGO composite material.
Step seven: taking the Sn @ WS2Annealing the/rGO composite material in a low-temperature tubular furnace, calcining at 400 ℃ under the protection of argon atmosphere, raising the temperature at the rate of 5 ℃/min, and preserving the heat for 3 hours to obtain a product Sn @ WS2a/rGO composite electrode material.
Example 6
The method comprises the following steps: under the condition of room temperature, 40mg of rGO is added into 40mL of deionized water and is subjected to ultrasonic treatment for 2-6 hours to form a uniform solution A, and the concentration of the uniform solution A is controlled to be 1 g/L. The ultrasonic power is 800W;
step two: 0.295g of tungsten hexachloride and 0.5625g of thioacetamide are added into the solution A, the stirring speed is 500r/min, the stirring is carried out for 3h, and the obtained solution is a solution B.
Step three: and transferring the solution C into a hydrothermal kettle, controlling the filling ratio to be 30%, then sealing the hydrothermal kettle, controlling the hydrothermal temperature to be 200 ℃ in a homogeneous reaction instrument, reacting for 12 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 4 times, drying in a freeze dryer at-40 deg.C and vacuum degree of 10Pa for 8 hr to obtain black WS2a/rGO composite material.
Step five: PVP and stannous chloride dihydrate are completely dissolved in 30mL of aqueous solution and stirred for 60min at the stirring speed of 800 r/min. Adding the above WS2And stirring the/rGO composite material for 2 hours at the stirring speed of 800 r/min. After mixing evenly, sodium borohydride is added, m (PVP) m (stannous chloride dihydrate) m (WS)2(rGO): sodium borohydride ═ 1:1:2: 0.2. Stirring for 1h at a stirring speed of 800 r/min.
Step six: washing the precursor solution with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 40Pa for 12 hr to obtain black Sn @ WS2a/rGO composite material.
Step seven: taking the Sn @ WS2Annealing the/rGO composite material in a low-temperature tubular furnace, calcining at 400 ℃ under the protection of argon atmosphere, raising the temperature at the rate of 5 ℃/min, and preserving the heat for 2 hours to obtain a product Sn @ WS2a/rGO composite electrode material.
In a word, the Sn @ WS is prepared by utilizing a solvothermal method and a normal-temperature liquid-phase reduction process under the auxiliary action of a template agent2/rGO composites, in WS2Sn nano particles are reduced and grown on tungsten disulfide nano sheets of the/rGO composite material, so that the conductivity of the material is effectively enhanced, and the electrochemical performance of the material is improved. The preparation method has the advantages of simple process, easily controlled process parameters and high repeatability, and the Sn @ WS prepared by the method2the/rGO composite material has wide research value and application value in the electrochemical field.
The invention is described in further detail below with reference to the accompanying drawings:
referring to FIG. 1, Sn @ WS prepared for example 32X-ray diffraction (XRD) patterns of/rGO composite electrode materials. Sn and WS can be clearly seen2Without the presence of other hetero-phases, indicates that the invention successfully prepares Sn @ WS2a/rGO composite electrode material.
Referring to FIG. 2, Sn @ WS prepared for example 32Scanning Electron Microscope (SEM) picture of/rGO composite electrode material. It can be seen that the Sn particles are distributed more uniformly in WS2The surface of the/rGO composite material can utilize the tin simple substance with excellent conductivity, and finally the whole electrochemical performance of the tin simple substance composite tungsten disulfide/reduced graphene oxide composite electrode material is improved。
Referring to FIG. 3, Sn @ WS prepared for example 32Cycle performance profile of/rGO composite electrode material. It was found that the concentration of the compound was 200mA · g-1After the current density of the capacitor is cycled for 200 circles, the capacity retention rate is 92%, and the cycle stability of the capacitor is good.
Referring to FIG. 4, Sn @ WS prepared for example 3 of the present invention2The rate capability graph of the/rGO composite electrode material is shown to be 20 A.g-1The capacity of the capacitor can still reach 100mAh g under the current density-1. Therefore, as can be seen from fig. 3 and 4, the elemental tin has better conductivity, that is, the elemental Sn serving as the negative electrode material of the sodium ion battery has higher theoretical capacity, so that on the premise of maintaining high capacity, the conductivity of the elemental Sn composite material is improved by using the elemental Sn composite material, so that the elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material finally prepared by the method has excellent cycle stability and rate capability.
Specifically, the above experimental test patterns correspond to: analysis of the samples (Sn @ WS) by means of a Japanese science D/max2000 PCX-ray diffractometer2/rGO composite electrode material), found with hexagonal WS of JCPDS numbers 08-02372The structures are consistent, which shows that the method can prepare high-purity tungsten disulfide. When the sample was observed with a Field Emission Scanning Electron Microscope (FESEM), it was found that Sn @ WS was produced2The product of the/rGO composite electrode material has better dispersibility.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (4)
1. A preparation method of a tin simple substance composite tungsten disulfide/reduced graphene oxide composite electrode material is characterized by comprising the following steps:
1) uniformly dispersing reduced graphene oxide, tungsten hexachloride and thioacetamide in water to obtain a reaction solution; cooling the reaction solution after hydrothermal reaction to obtain a product, centrifugally washing the product, and collecting powder through freeze drying to obtain the tungsten disulfide/reduced graphene oxide composite material;
2) adding polyvinylpyrrolidone, stannous chloride dihydrate, tungsten disulfide/reduced graphene oxide composite material and sodium borohydride into water, and stirring for 0.5-1 h to obtain precursor liquid; centrifuging and washing the precursor solution, and then freeze-drying and collecting powder to obtain the elemental tin composite tungsten disulfide/reduced graphene oxide composite material;
3) calcining and annealing the elemental tin composite tungsten disulfide/reduced graphene oxide composite material to obtain a elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material;
in the step 1), the hydrothermal reaction temperature is 200-240 ℃, and the reaction time is 12-48 h;
the calcination annealing treatment in the step 3) specifically comprises the following steps: under the protection of inert atmosphere, calcining at 400-600 ℃, heating at a rate of 5-20 ℃/min, and keeping the temperature for 1-3 h;
in the step 1), the reaction charge ratio of the reduced graphene oxide, water, tungsten hexachloride and thioacetamide is (30-60) mg, (30-60) mL, (0.295-0.59) g, (0.5625-1.125) g;
in the step 2), the reaction charge ratio of polyvinylpyrrolidone, stannous chloride dihydrate, tungsten disulfide/reduced graphene oxide composite material, sodium borohydride and water is (1-4) mg, (0.2-1) mg, (10-30) mL;
in the step 1) and the step 2), the temperature of freeze drying is-40 to-70 ℃, the time is 8 to 12 hours, and the vacuum degree of a freeze drying environment is 10 to 40 Pa.
2. The elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material prepared by the preparation method of claim 1.
3. The elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material of claim 2, wherein the elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material is at 200 mA-g-1At current density ofAfter 200 cycles, the capacity retention rate is 92%.
4. The use of the elemental tin composite tungsten disulfide/reduced graphene oxide composite electrode material of claim 2 or 3 as a battery negative electrode material.
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