CN113793914B - Reduced graphene oxide coated CNTs/SnO with hollow structure 2 Composite film and preparation method and application thereof - Google Patents

Reduced graphene oxide coated CNTs/SnO with hollow structure 2 Composite film and preparation method and application thereof Download PDF

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CN113793914B
CN113793914B CN202111064428.9A CN202111064428A CN113793914B CN 113793914 B CN113793914 B CN 113793914B CN 202111064428 A CN202111064428 A CN 202111064428A CN 113793914 B CN113793914 B CN 113793914B
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composite film
graphene oxide
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CN113793914A (en
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杨艳玲
孙瑜
郭文宁
薛帆
刘佳隽
和茹梅
锁国权
侯小江
冯雷
张荔
叶晓慧
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Shaanxi University of Science and Technology
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses reduced graphene oxide coated CNTs/SnO with a hollow structure 2 A composite film, a preparation method and application thereof, which belong to the technical field of sodium ion batteries, and the void structure can effectively shorten electrons/Na + Diffusion path, acceleration of SIB reaction kinetics, and Na + Provides abundant active sites. In addition, rGO can also effectively mitigate SnO 2 And as a ligament is whole rGO @ CNTs/SnO 2 The @ void composite film provides a channel for electron transport. Benefiting from the unique structural advantages, rGO @ CNTs/SnO 2 The @ void composite film shows excellent electrochemical performance as a negative electrode material of a sodium ion battery even at 1A g ‑1 The cycle life of the high-current-density capacitor can still reach 1000 circles, and ultrahigh cycle stability is shown.

Description

Reduced graphene oxide coated CNTs/SnO with hollow structure 2 Composite film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to reduced graphene oxide coated CNTs/SnO with a hollow structure 2 A composite film and a preparation method and application thereof.
Background
In recent decades, environmental pollution and energy crisis have attracted more and more attention worldwide due to rapid development of industrialization and increasing energy demand. In order to solve these problems, development and popularization of green renewable energy sources are urgently needed. Therefore, high performance energy storage devices have become a focus of research in recent years. Rechargeable ionic batteries are considered to be one of the most potential energy storage devices due to their significant advantages of high energy density, reasonable operating voltage, and good cyclability.
Since sony commercialized a Lithium Ion Battery (LIB) for the first time in 1991, LIB became the primary device of an energy storage battery and is being utilized in the aspects of human life. However, the problem of lithium resource shortage in the crust will severely limit the rapid development of LIB in the future. Sodium is considered to be one of the more suitable energy storage batteries that can replace LIB because of its similar physicochemical properties as lithium. Notably, na + Diameter size ratio of Li + Larger (Li) + Is composed of
Figure BDA0003257648940000012
Na + Is composed of
Figure BDA0003257648940000011
) Na of this larger size + This results in SIBs with lower electrochemical performance and more severe volume expansion problems, which slows down the pace of SIB marketization.
The tin (Sn) based material has very high theoretical specific capacity (Na) 15 Sn 4 Exhibit 847mA h g -1 High theoretical specific capacity), low cost, environmental friendliness and proper low charge and discharge potential, and is considered as a potential negative electrode material of the SIB. However, from Sn to Na 15 Sn 4 The reaction process of (a) is accompanied by a volume expansion phenomenon of about 520%, which seriously shortens the cycle life of the SIB and degrades the electrochemical performance of the SIB. In addition, due to the characteristic that nano-scale Sn-based particles are easy to agglomerate, the internal conductivity of the Sn-based material is poor. Therefore, how to effectively alleviate the volume expansion phenomenon of the Sn-based material during SIB charging and discharging still faces a serious challenge to increase the internal conductivity of the material.
Disclosure of Invention
The invention aims to overcome the defect that the Sn-based material has volume expansion in the SIB charging and discharging process in the prior art, and provides reduced graphene oxide coated CNTs/SnO with a hollow structure 2 A composite film and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
reduced graphene oxide coated CNTs/SnO with hollow structure 2 The preparation method of the composite film comprises the following steps:
step 1) preparation of polystyrene microspheres:
synthesizing polystyrene microspheres (PS) by a microemulsion polymerization method;
step 2) CNTs/SnO 2 Preparation of @ PS composite film:
SnCl 4 ·5H 2 Mixing O, polystyrene microspheres, hexadecyl trimethyl ammonium bromide, CNTs and deionized water, and sequentially cleaning and reactingDrying to obtain CNTs/SnO 2 @ PS composite film;
step 3) rGO @ CNTs/SnO 2 Preparation of @ void composite film:
CNTs/SnO 2 Mixing the @ PS composite film, ascorbic acid and graphene oxide, and drying and calcining the mixture in sequence after reaction to obtain reduced graphene oxide coated CNTs/SnO with a hollow structure 2 The composite film of (1).
Preferably, snCl 4 ·5H 2 The feeding ratio of O, polystyrene microspheres, cetyl trimethyl ammonium bromide, CNTs and deionized water is (0.2-1.0) g: (0.5 to 1.5) g: (0.1-0.5) g: (0.01-0.1) g: (30-150) ml.
Preferably, CNTs/SnO 2 The feeding ratio of the @ PS composite film to the ascorbic acid to the graphene oxide is (0.5-3.0) g: (0.2-0.5) g: (5-15) ml;
the concentration of the graphene oxide is 1-5 mg/ml.
Preferably, the reaction conditions in step 2) are:
firstly, snCl is added 4 ·5H 2 Mixing O, polystyrene microspheres, hexadecyl trimethyl ammonium bromide, CNTs and deionized water, and reacting for 1.0-5 hours to obtain a solution B;
secondly, placing the solution B at the temperature of between 150 and 220 ℃ for reacting for 8 to 15 hours to obtain a product C;
finally, the product C is alternately washed for 3 to 5 times by deionized water and ethanol to obtain CNTs/SnO 2 @ PS composite film.
Preferably, the reaction conditions in step 3) are:
first, CNTs/SnO 2 Stirring and reacting the @ PS composite film, ascorbic acid and graphene oxide for 2-5 h to obtain a mixed solution E;
secondly, drying the mixed solution E at 80-120 ℃ for 1-5 h to obtain gel F;
finally, calcining the gel F at 150-250 ℃ for 1-5 hours to obtain rGO @ CNTs/SnO 2 @ void composite film.
Preferably, the CNTs are single-walled carbon nanotubes;
the graphene oxide is a single layer of graphene oxide.
Reduced graphene oxide coated CNTs/SnO obtained based on preparation method 2 The composite film is prepared by reducing graphene oxide to coat CNTs/SnO 2 The composite film of (2) is a hollow structure, and the size of a gap in the hollow structure is 100-250 nm.
The reduced graphene oxide coated CNTs/SnO 2 The composite film of (2) is applied to the button cell, and the structure of the button cell is as follows:
the metal sodium is used as a counter electrode;
the electrolyte is NaPF 6 Ethyl carbonate and dimethyl carbonate;
the diaphragm is a celgard 2400 film;
rGO@CNTs/SnO 2 the @ void composite film is used as a negative electrode material of the sodium-ion battery and assembled into the button battery.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses reduced graphene oxide coated CNTs/SnO with a hollow structure 2 The composite film has a gap structure capable of effectively shortening electron/Na + Diffusion path, acceleration of SIB reaction kinetics, and Na + Provides abundant active sites. In addition, rGO can also effectively mitigate SnO 2 And as a ligament is whole rGO @ CNTs/SnO 2 The @ void composite film provides a channel for electron transport. Thanks to this unique structural advantage, rGO @ CNTs/SnO 2 The @ void composite film shows excellent electrochemical performance as a negative electrode material of a sodium ion battery even at 1A g -1 The cycle life of the high-current-density capacitor can still reach 1000 circles, and ultrahigh cycle stability is shown.
The invention also discloses reduced graphene oxide coated CNTs/SnO with a hollow structure 2 The preparation method of the composite film takes the polystyrene microspheres as the template, provides sufficient gaps for the structure after high-temperature calcination, and is favorable for relieving the volume expansion problem of the material. In order to improve rGO @ CNTs/SnO 2 @ void compoundingThin film conductivity, highly conductive CNTs are used as electron transport channels. CNTs and rGO have stronger conductivity, which is beneficial to electrons in rGO @ CNTs/SnO 2 The @ void composite film has rapid transport, and increases the conductivity inside the material. Synthetic rGO @ CNTs/SnO 2 The @ void composite film can effectively disperse SnO 2 Granular, moderated SnO 2 The volume expansion of the particles during charging and discharging.
Further, the reduced graphene oxide coated CNTs/SnO with a hollow structure is prepared by adopting a hydrothermal method and a tubular furnace calcination process 2 The composite film has simple synthesis process and easy operation.
Drawings
FIG. 1 shows reduced graphene oxide coated CNTs/SnO 2 The preparation process of the composite film of (1);
FIG. 2 shows reduced graphene oxide coated CNTs/SnO 2 Microscopic SEM images of the composite film of (a);
FIG. 3 is a diagram of reduced graphene oxide-coated CNTs/SnO according to example IV 2 A partially enlarged SEM image of the composite film of (a);
FIG. 4 is a diagram of reduced graphene oxide-coated CNTs/SnO according to example IV 2 High-power SEM image of the composite film;
FIG. 5 is a graph of the elemental content and elemental distribution of Line 1 of FIG. 4;
FIG. 6 is a diagram of reduced graphene oxide-coated CNTs/SnO according to example IV 2 The composite film is used as a high-stability long-cycle graph of an SIB negative electrode material.
Detailed Description
The invention is described in further detail below with reference to the accompanying drawings:
example one
Reduced graphene oxide coated CNTs/SnO 2 The preparation of the composite film, as shown in fig. 1, comprises the following steps:
step 1, preparation of PS microspheres:
the diameter of the Polystyrene (PS) microspheres synthesized by the Michelin Biochemical technology Limited, shanghai, is 300 nanometers.
Step 2, CNTs/SnO 2 Preparation of @ PS composite film:
first, 0.2g of SnCl 4 ·5H 2 O, 0.5g PS microspheres, 0.1g cetyltrimethylammonium bromide (CTAB) and 0.01g CNTs were added to 30mL of an aqueous solution and sonicated for about 0.5 hour to give solution A, which was then stirred for 0.5 hour to give solution B. And putting the solution B into a polytetrafluoroethylene reactor, and reacting the solution B for 8 hours at 150 ℃ to obtain a reaction product C. Finally, the reaction product C is centrifuged and washed for 3 times with deionized water and ethanol alternately to obtain a product D which is CNTs/SnO 2 @ PS composite film.
Step 3, self-supporting rGO @ CNTs/SnO 2 Preparation of @ void composite film:
0.5g of product D and 0.2g of ascorbic acid are dispersed to a concentration of 1mg mL in 5mL -1 And magnetically stirring for 2 hours to obtain a mixed solution E. Then, the mixed solution E was placed in an oven at 80 ℃ for 1 hour to obtain a gel F, i.e. rGO @ CNTs/SnO 2 @ PS gel. Finally, the gel F was sliced and calcined in a muffle furnace at 150 ℃ for 1 hour to form free-standing rGO @ CNTs/SnO 2 @ void composite film, namely reduced graphene oxide coated CNTs/SnO with hollow structure 2 The composite film of (1).
Self-supporting rGO @ CNTs/SnO 2 A @ void composite film based on the high-stability rGO coated CNTs/SnO 2 A preparation method and an application method of the @ void composite film. The rGO @ CNTs/SnO 2 The @ void composite film is used as a negative electrode material of the sodium ion battery and assembled into the button cell.
The specific method for assembling the button cell is as follows: rGO @ CNTs/SnO 2 The @ void composite film has the integrity and can be directly used as a self-supporting electrode and is cut into a negative plate for an experimental battery with the diameter of 10mm by a cutting machine.
Taking metal sodium as a counter electrode; the electrolyte is NaPF 6 Mixing the ethyl carbonate and dimethyl carbonate solution according to the volume ratio of 1; the diaphragm is a celgard 2400 film; the order of assembling the battery is negative electrode shell, sodium sheet, diaphragm, negative electrode sheet, gasket, spring sheet and positive electrode sheetAnd the polar shell is arranged in a glove box filled with inert atmosphere to form the button cell.
Example two
Step 1, preparation of PS microspheres:
the diameter of Polystyrene (PS) microspheres synthesized by the microemulsion polymerization method provided by Shanghai Michelin Biochemical technology Ltd is 400 nm.
Step 2, CNTs/SnO 2 Preparation of @ PS composite film:
first, 0.3g of SnCl 4 ·5H 2 O, 0.5g of PS microspheres, 0.3g of CTAB and 0.03g of CNTs are added into 50mL of aqueous solution and subjected to ultrasonic treatment for about 1 hour to obtain a solution A, and then the solution A is stirred for 1 hour to obtain a solution B. Putting the solution B into a polytetrafluoroethylene reactor, and reacting at 180 ℃ for 10 hours to obtain a reaction product C. Finally, centrifuging the reaction product C and alternately cleaning the reaction product C with deionized water and ethanol for 4 times to obtain a product D of CNTs/SnO 2 @ PS composite film.
Step 3, self-supporting rGO @ CNTs/SnO 2 Preparation of @ void composite film:
0.6g of product D and 0.3g of ascorbic acid are dispersed to a concentration of 2mg mL in 8mL -1 And magnetically stirring for 4 hours to obtain a mixed solution E. Then, the mixed solution E was placed in an oven at 100 ℃ for 3 hours to obtain a gel F, i.e. rGO @ CNTs/SnO 2 @ PS gel. Finally, the gel F was sliced and calcined in a muffle furnace at 180 ℃ for 2 hours to form free-standing rGO @ CNTs/SnO 2 @ void composite film, namely reduced graphene oxide coated CNTs/SnO with hollow structure 2 The composite film of (3).
Self-supporting rGO @ CNTs/SnO 2 The @ void composite film is based on the high-stability rGO coated CNTs/SnO 2 A preparation method and an application method of the @ void composite film. The rGO @ CNTs/SnO 2 The @ void composite film is used as a negative electrode material of the sodium ion battery and assembled into the button cell.
The specific method for assembling the button cell is as follows: rGO @ CNTs/SnO 2 The @ void composite film has integrity and can be directly used as a self-supporting electrode and is cut into a diameter of 10mm by a cutting machineThe negative electrode sheet for an experimental battery of (1).
Taking metal sodium as a counter electrode; the electrolyte is NaPF 6 Mixing the ethyl carbonate and the dimethyl carbonate solution according to the volume ratio of 1; the diaphragm is a celgard 2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
EXAMPLE III
Step 1, preparation of PS microspheres:
the diameter of Polystyrene (PS) microspheres synthesized by microemulsion polymerization, supplied by the shanghai mclin biochemical technologies, ltd, is about 350 nm.
Step 2, CNTs/SnO 2 Preparation of @ PS composite film:
first, 0.35g of SnCl 4 ·5H 2 O, 0.9g of PS microspheres, 0.35g of CTAB and 0.06g of CNTs are added into 90mL of aqueous solution and subjected to ultrasonic treatment for about 2 hours to obtain a solution A, and then the solution A is stirred for 1 hour to obtain a solution B. Putting the solution B into a polytetrafluoroethylene reactor, and reacting for 12 hours at 200 ℃ to obtain a reaction product C. Finally, the reaction product C is centrifuged and washed alternately with deionized water and ethanol for 5 times to obtain a product D of CNTs/SnO 2 @ PS composite film.
Step 3, self-supporting rGO @ CNTs/SnO 2 Preparation of @ void composite film:
1.3g of product D and 0.25g of ascorbic acid dispersed in 10mL of 3mg mL -1 And magnetically stirring for 4 hours to obtain a mixed solution E. Then, the mixed solution E was placed in an oven at 100 ℃ for 4 hours to obtain a gel F, i.e. rGO @ CNTs/SnO 2 @ PS gel. Finally, gel F was sliced and calcined in a muffle furnace at 200 ℃ for 3 hours to form free-standing rGO @ CNTs/SnO 2 @ void composite film, namely reduced graphene oxide coated CNTs/SnO with hollow structure 2 The composite film of (3).
Self-supporting rGO @ CNTs/SnO 2 The @ void composite film is based on the high-stability rGO coated CNTs/SnO 2 Of @ void composite filmsPreparation and application method thereof. The rGO @ CNTs/SnO 2 The @ void composite film is used as a negative electrode material of the sodium-ion battery and assembled into the button battery.
The specific method for assembling the button cell is as follows: rGO @ CNTs/SnO 2 The @ void composite film has integrity and can be directly used as a self-supporting electrode and is cut into a negative plate for an experimental battery with the diameter of 10mm by a cutting machine.
Taking metal sodium as a counter electrode; the electrolyte is NaPF 6 Mixing the ethyl carbonate and dimethyl carbonate solution according to the volume ratio of 1; the diaphragm is a celgard 2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Example four
Step 1, preparation of PS microspheres:
the diameter of Polystyrene (PS) microspheres synthesized by the microemulsion polymerization method, which is provided by Shanghai Michelin Biochemical technology Ltd, is about 450 nm.
Step 2, CNTs/SnO 2 Preparation of @ PS composite film:
first, 0.5g of SnCl 4 ·5H 2 O, 1.0g of PS microspheres, 0.35g of CTAB and 0.05g of CNTs are added into 80mL of aqueous solution for ultrasonic treatment for about 1 hour to obtain a solution A, and then the solution A is stirred for 1 hour to obtain a solution B. Putting the solution B into a polytetrafluoroethylene reactor, and reacting for 12 hours at 180 ℃ to obtain a reaction product C. Finally, centrifuging the reaction product C and alternately washing the reaction product C with deionized water and ethanol for 5 times to obtain a product D which is CNTs/SnO 2 @ PS composite film.
Step 3, self-supporting rGO @ CNTs/SnO 2 Preparation of @ void composite film:
1.35g of product D and 0.3g of ascorbic acid dispersed in 10mL of 3mg mL -1 And magnetically stirring for 5 hours to obtain a mixed solution E. Then, the mixed solution E is put into an oven with the temperature of 90 ℃ for 1 to 5 hours to obtain the gel F, namely rGO @ CNTs/SnO 2 @ PS gel. Finally, gel F was sliced and calcined in a muffle furnace at 200 ℃ 3Hour, free-standing rGO @ CNTs/SnO was formed 2 @ void composite film, namely reduced graphene oxide coated CNTs/SnO with hollow structure 2 The composite film of (1).
rGO@CNTs/SnO 2 SEM images of the @ void composite film are shown in FIGS. 2, 3 and 4. SEM images of different scales can see rGO @ CNTs/SnO 2 The @ void composite film has a significant presence of voids, which facilitates rapid penetration of an electrolyte solution, thereby accelerating the progress of the reaction kinetics of the electrode. FIG. 5 is an EDX test performed on FIG. 4line 1, which is clearly specific to rGO @ CNTs/SnO 2 The ratio of each component in the @ void composite film is determined. Benefiting from the unique structural design, rGO @ CNTs/SnO 2 The @ void composite film as the SIB negative electrode material exhibited excellent electrochemical properties, as shown in FIG. 6. Even at 1 ag -1 The high-current density of the copper-based alloy can be cycled for 1000 times, can still maintain higher specific capacity, and simultaneously shows excellent cycling stability and long cycling life.
Self-supporting rGO @ CNTs/SnO 2 A @ void composite film based on the high-stability rGO coated CNTs/SnO 2 A preparation method and an application method of the @ void composite film. The rGO @ CNTs/SnO 2 The @ void composite film is used as a negative electrode material of the sodium-ion battery and assembled into the button battery.
The specific method for assembling the button cell is as follows: rGO @ CNTs/SnO 2 The @ void composite film has integrity and can be directly used as a self-supporting electrode and is cut into a negative plate for an experimental battery with the diameter of 10mm by a cutting machine.
Taking metal sodium as a counter electrode; the electrolyte is NaPF 6 Mixing the ethyl carbonate and the dimethyl carbonate solution according to the volume ratio of 1; the diaphragm is a celgard 2400 film; the order of assembling the battery is sequentially that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
EXAMPLE five
Step 1, preparation of PS microspheres:
the diameter of the Polystyrene (PS) microspheres synthesized by using a microemulsion polymerization method, which is provided by Shanghai Maxin Biochemical technology Co., ltd, is 500 nm.
Step 2, CNTs/SnO 2 Preparation of @ PS composite film:
first, 0.6g of SnCl 4 ·5H 2 O, 1.2g of PS microspheres, 0.4g of CTAB and 0.06g of CNTs are added into 100mL of aqueous solution and subjected to ultrasonic treatment for about 3 hours to obtain a solution A, and then the solution A is stirred for 2 hours to obtain a solution B. The solution B was placed in a Teflon reactor and reacted at 210 ℃ for 13 hours to produce a reaction product C. Finally, the reaction product C is centrifuged and washed alternately with deionized water and ethanol for 5 times to obtain a product D of CNTs/SnO 2 @ PS composite film.
Step 3, self-supporting rGO @ CNTs/SnO 2 Preparation of @ void composite film:
1.8g of product D and 0.4g of ascorbic acid dispersed in 10mL of 4mg mL -1 And magnetically stirring for 5 hours to obtain a mixed solution E. Then, the mixed solution E was placed in an oven at 100 ℃ for 2 hours to obtain a gel F, i.e. rGO @ CNTs/SnO 2 @ PS gel. Finally, gel F was sliced and calcined in a muffle furnace at 200 ℃ for 2 hours to form free-standing rGO @ CNTs/SnO 2 @ void composite film, namely reduced graphene oxide coated CNTs/SnO with hollow structure 2 The composite film of (3).
Self-supporting rGO @ CNTs/SnO 2 The @ void composite film is based on the high-stability rGO coated CNTs/SnO 2 A preparation method and an application method of the @ void composite film. The rGO @ CNTs/SnO 2 The @ void composite film is used as a negative electrode material of the sodium ion battery and assembled into the button cell.
The specific method for assembling the button cell is as follows: rGO @ CNTs/SnO 2 The @ void composite film has integrity and can be directly used as a self-supporting electrode and is cut into a negative plate for an experimental battery with the diameter of 10mm by a cutting machine.
Taking metal sodium as a counter electrode; the electrolyte is NaPF 6 Mixing the ethyl carbonate and the dimethyl carbonate solution according to the volume ratio of 1; the diaphragm is a celgard 2400 film; the order of assembling the battery is negativeThe battery comprises a pole shell, a sodium sheet, a diaphragm, a negative plate, a gasket, a spring piece and a positive shell, wherein the button battery is assembled in a glove box filled with inert atmosphere.
EXAMPLE six
Step 1, preparation of PS microspheres:
the diameter of the Polystyrene (PS) microspheres synthesized by using a microemulsion polymerization method, which is provided by Shanghai Maxin Biochemical technology Co., ltd, is 500 nm.
Step 2, CNTs/SnO 2 Preparation of @ PS composite film:
first, 0.8g of SnCl 4 ·5H 2 O, 1.3g of PS microspheres, 0.45g of CTAB and 0.08g of CNTs are added into 100mL of aqueous solution and subjected to ultrasonic treatment for about 2 hours to obtain a solution A, and then the solution A is stirred for 1 hour to obtain a solution B. Putting the solution B into a polytetrafluoroethylene reactor, and reacting at 200 ℃ for 12 hours to obtain a reaction product C. Finally, centrifuging the reaction product C and alternately cleaning the reaction product C with deionized water and ethanol for 4 times to obtain a product D of CNTs/SnO 2 @ PS composite film.
Step 3, self-supporting rGO @ CNTs/SnO 2 Preparation of @ void composite film:
2.8g of product D and 0.45g of ascorbic acid dispersed in 13mL of 4mg mL -1 And magnetically stirring for 5 hours to obtain a mixed solution E. Then, the mixed solution E was placed in an oven at 110 ℃ for 3 hours to obtain a gel F, i.e. rGO @ CNTs/SnO 2 @ PS gel. Finally, the gel F was sliced and calcined in a muffle furnace at 240 ℃ for 3 hours to form free-standing rGO @ CNTs/SnO 2 @ void composite film, namely reduced graphene oxide coated CNTs/SnO with hollow structure 2 The composite film of (1).
Self-supporting rGO @ CNTs/SnO 2 A @ void composite film based on the high-stability rGO coated CNTs/SnO 2 A preparation method and an application method of the @ void composite film. The rGO @ CNTs/SnO 2 The @ void composite film is used as a negative electrode material of the sodium ion battery and assembled into the button cell.
The specific method for assembling the button cell is as follows: rGO @ CNTs/SnO 2 The @ void composite film has integrityThe lithium ion battery negative electrode can be directly used as a self-supporting electrode and is cut into a negative electrode plate with the diameter of 10mm by a cutting machine.
Taking metal sodium as a counter electrode; the electrolyte is NaPF 6 Mixing the ethyl carbonate and the dimethyl carbonate solution according to the volume ratio of 1; the diaphragm is a celgard 2400 film; the order of assembling the battery is sequentially that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
EXAMPLE seven
Step 1, preparation of PS microspheres:
the diameter of Polystyrene (PS) microspheres synthesized by the microemulsion polymerization method provided by Shanghai Michelin Biochemical technology Ltd is 500 nm.
Step 2, CNTs/SnO 2 Preparation of @ PS composite film:
first, 0.9g of SnCl 4 ·5H 2 O, 1.35g of PS microspheres, 0.45g of CTAB and 0.08g of CNTs are added into 140mL of aqueous solution and subjected to ultrasonic treatment for about 2.5 hours to obtain a solution A, and then the solution A is stirred for 1.5 hours to obtain a solution B. The solution B was placed in a Teflon reactor and reacted at 210 ℃ for 13 hours to produce a reaction product C. Finally, the reaction product C is centrifuged and washed alternately with deionized water and ethanol for 5 times to obtain a product D of CNTs/SnO 2 @ PS composite film.
Step 3, self-supporting rGO @ CNTs/SnO 2 Preparation of @ void composite film:
0.25g of product D and 0.35g of ascorbic acid dispersed in 14mL of 3mg mL -1 And magnetically stirring for 5 hours to obtain a mixed solution E. Then, the mixed solution E was placed in an oven at 100 ℃ for 4 hours to obtain a gel F, i.e. rGO @ CNTs/SnO 2 @ PS gel. Finally, gel F was sliced and calcined in a muffle furnace at 240 ℃ for 3 hours to form free-standing rGO @ CNTs/SnO 2 @ void composite film, namely reduced graphene oxide coated CNTs/SnO with hollow structure 2 The composite film of (1).
Self-supporting rGO @ CNTs/SnO 2 @ void composite film based onHigh-stability rGO coated CNTs/SnO 2 A preparation method and an application method of the @ void composite film. The rGO @ CNTs/SnO 2 The @ void composite film is used as a negative electrode material of the sodium-ion battery and assembled into the button battery.
The specific method for assembling the button cell is as follows: rGO @ CNTs/SnO 2 The @ void composite film has integrity and can be directly used as a self-supporting electrode and is cut into a negative plate for an experimental battery with the diameter of 10mm by a cutting machine.
Taking metal sodium as a counter electrode; the electrolyte is NaPF 6 Mixing the ethyl carbonate and the dimethyl carbonate solution according to the volume ratio of 1; the diaphragm is a celgard 2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Example eight
Step 1, preparation of PS microspheres:
the diameter of Polystyrene (PS) microspheres synthesized by the microemulsion polymerization method provided by Shanghai Michelin Biochemical technology Ltd is 500 nm.
Step 2, CNTs/SnO 2 Preparation of @ PS composite film:
first, 1.0g of SnCl 4 ·5H 2 O, 1.5g of PS microspheres, 0.5g of cetyltrimethylammonium bromide (CTAB) and 0.1g of CNTs were added to 150mL of an aqueous solution and subjected to ultrasonication for about 3 hours to obtain a solution A, and then the solution A was stirred for 2 hours to obtain a solution B. The solution B was placed in a polytetrafluoroethylene reactor and reacted at 220 ℃ for 15 hours to obtain a reaction product C. Finally, the reaction product C is centrifuged and washed alternately with deionized water and ethanol for 5 times to obtain a product D of CNTs/SnO 2 @ PS composite film.
Step 3, self-supporting rGO @ CNTs/SnO 2 Preparation of @ void composite film:
3.0g of product D and 0.5g of ascorbic acid dispersed in 15mL of 5mg mL -1 And magnetically stirring for 5 hours to obtain a mixed solution E. Then, the mixed solution E was put in an oven at 120 ℃ for 5 hours to obtain a gel F, i.e., rGO @CNTs/SnO 2 @ PS gel. Finally, the gel F was sliced and calcined in a muffle furnace at 250 ℃ for 5 hours to form free-standing rGO @ CNTs/SnO 2 @ void composite film, namely reduced graphene oxide coated CNTs/SnO with hollow structure 2 The composite film of (1).
Self-supporting rGO @ CNTs/SnO 2 The @ void composite film is based on the high-stability rGO coated CNTs/SnO 2 A preparation method and an application method of the @ void composite film. The rGO @ CNTs/SnO 2 The @ void composite film is used as a negative electrode material of the sodium-ion battery and assembled into the button battery.
The specific method for assembling the button cell is as follows: rGO @ CNTs/SnO 2 The @ void composite film has integrity and can be directly used as a self-supporting electrode and is cut into a negative plate for an experimental battery with the diameter of 10mm by a cutting machine.
Taking metallic sodium as a counter electrode; the electrolyte is NaPF 6 Mixing the ethyl carbonate and dimethyl carbonate solution according to the volume ratio of 1; the diaphragm is a celgard 2400 film; the order of assembling the battery is that a negative electrode shell, a sodium sheet, a diaphragm, a negative electrode sheet, a gasket, a spring piece and a positive electrode shell are assembled into a button battery in a glove box filled with inert atmosphere.
Taking example four as an example, rGO @ CNTs/SnO 2 The microstructure results of the @ void composite film are shown in fig. 2, 3 and 4, and it can be seen that there are significant voids in the structure, providing sufficient reaction space for the structure. In addition, the coated rGO of the CNTs outer layer can greatly alleviate the problem of volume expansion of the structure, and can also serve as a tie for connecting the entire composite film. Benefiting from unique structural design, rGO @ CNTs/SnO 2 The @ void composite film as the negative electrode material of the sodium-ion battery shows excellent electrochemical stability even at 1A g -1 The cycle life can still reach 1000 circles under the high current density.
It should be noted that the Carbon Nanotubes (CNTs) used in the present invention are all multi-walled carbon nanotubes, and the Graphene Oxide (GO) used in the present invention is all single-layer graphene oxide.
In summary, the invention provides a portable electronic deviceReduced graphene oxide coated CNTs/SnO with hollow structure 2 The preparation method of the composite film adopts a hydrothermal method and a tubular furnace calcination process, and the synthesis process is simple and easy to operate. Synthetic rGO @ CNTs/SnO 2 The @ void composite film can effectively disperse SnO 2 Particles, moderated SnO 2 The volume expansion of the particles during charging and discharging. In addition, CNTs and rGO have stronger conductivity, which is beneficial to electrons at rGO @ CNTs/SnO 2 The @ void composite film has rapid transport, and increases the conductivity inside the material. The void structure effectively shortens electron/Na + Diffusion path, acceleration of SIB reaction kinetics, and Na + Provides abundant active sites. rGO can also be effective in relieving SnO 2 And as a ligament is whole rGO @ CNTs/SnO 2 The @ void composite film provides a channel for electron transport.
The above contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention should not be limited thereby, and any modification made on the basis of the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims (6)

1. Reduced graphene oxide coated CNTs/SnO with hollow structure 2 The preparation method of the composite film is characterized by comprising the following steps:
step 1) preparation of polystyrene microspheres PS:
synthesizing polystyrene microspheres PS by adopting a microemulsion polymerization method;
step 2) CNTs/SnO 2 Preparation of @ PS composite film:
firstly, snCl is added 4 •5H 2 O, polystyrene microspheres PS, hexadecyl trimethyl ammonium bromide, CNTs and deionized water are mixed and react for 1.0 to 5 hours to obtain a solution B;
secondly, placing the solution B at the temperature of 150 to 220 ℃ for reaction for 8 to 15 hours to obtain a product C;
finally, the product C is alternately washed for 3 to 5 times by deionized water and ethanol to obtain CNTs/SnO 2 @ PS composite film;
step 3) reduced graphene oxide coated CNTs/SnO with hollow structure 2 The preparation of the composite film of (2):
first, CNTs/SnO 2 Stirring and reacting the @ PS composite film, ascorbic acid and graphene oxide for 2 to 5 hours to obtain a mixed solution E;
secondly, drying the mixed solution E for 1 to 5 hours at the temperature of 80 to 120 ℃ to obtain a gel F;
finally, calcining the gel F at the temperature of 150 to 250 ℃ for 1 to 5 hours to obtain the reduced graphene oxide coated CNTs/SnO with a hollow structure 2 The composite film of (1).
2. Reduced graphene oxide-coated CNTs/SnO with hollow structure according to claim 1 2 The preparation method of the composite film is characterized in that the SnCl 4 •5H 2 The feeding ratio of O, polystyrene microspheres PS, hexadecyl trimethyl ammonium bromide, CNTs and deionized water is (0.2 to 1.0) g: (0.5 to 1.5) g: (0.1 to 0.5) g: (0.01 to 0.1) g: (30 to 150) ml.
3. Reduced graphene oxide-coated CNTs/SnO with hollow structure according to claim 1 2 The preparation method of the composite film is characterized in that the composite film is prepared from CNTs/SnO 2 The feeding ratio of the @ PS composite film to the ascorbic acid to the graphene oxide is (0.5-3.0) g: (0.2 to 0.5) g: (5 to 15) ml;
the concentration of the graphene oxide is 1 to 5mg/ml.
4. Reduced graphene oxide-coated CNTs/SnO with hollow structure according to claim 1 2 The preparation method of the composite film is characterized in that CNTs are single-walled carbon nanotubes;
the graphene oxide is a single layer of graphene oxide.
5. Reduced graphene oxide coated CNTs/SnO with hollow structure obtained based on preparation method of any one of claims 1-4 2 The composite film of (a) to (b),the hollow structure is characterized in that the size of a gap in the hollow structure is 100 to 250nm.
6. CNTs/SnO coated with reduced graphene oxide with hollow structure according to claim 5 2 The application of the composite film in the button cell is characterized in that the structure of the button cell is as follows:
the metal sodium is used as a counter electrode;
the electrolyte is NaPF 6 Ethyl carbonate and dimethyl carbonate;
the diaphragm is a celgard 2400 film;
reduced graphene oxide coated CNTs/SnO with hollow structure 2 The composite film is used as a working electrode and assembled into a button cell.
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