CN113184898B - Tin dioxide-carbon core-shell nanosphere composite material, and preparation method and application thereof - Google Patents

Tin dioxide-carbon core-shell nanosphere composite material, and preparation method and application thereof Download PDF

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CN113184898B
CN113184898B CN202110496425.6A CN202110496425A CN113184898B CN 113184898 B CN113184898 B CN 113184898B CN 202110496425 A CN202110496425 A CN 202110496425A CN 113184898 B CN113184898 B CN 113184898B
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tin dioxide
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carbon core
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nanospheres
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CN113184898A (en
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李奇
刘肖
张翠
白锋
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Henan University
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Abstract

The invention discloses a tin dioxide-carbon core-shell nanosphere composite material, a preparation method and application thereof, and belongs to the technical field of lithium ion battery electrode materials. The tin dioxide-carbon core-shell nanosphere composite material is a composite material consisting of a shell layer formed by nitrogen-doped carbon and a core in which tin dioxide is uniformly embedded in carbon, wherein the tin dioxide-carbon center nanosphere is completely wrapped by the conductive nitrogen-doped carbon shell layer, and meanwhile, the particle size of tin dioxide particles is about 2nm to 5nm and does not contain large tin dioxide particles with the particle size of more than 50 nm. The composite material not only effectively relieves SnO 2 The volume of the conductive layer is expanded, the conductivity is remarkably improved, and a rapid electron transfer path is provided. At the same time, the nitrogen-doped carbon shell also serves as armor to ensure SnO in the cyclic process 2 The structure stability of the/carbon composite nanosphere.

Description

Tin dioxide-carbon core-shell nanosphere composite material, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery electrode materials, and particularly relates to a tin dioxide-carbon core-shell nanosphere composite material, and a preparation method and application thereof.
Background
With the rapid development of electric vehicles, people put higher demands on lithium ion batteries. The specific capacity of the common graphite cathode is low (372 mAh g) -1 ) The high energy consumption requirement cannot be met. Metal oxides of high theoretical capacity as replacements for high efficiency lithium ion batteriesAnode materials have received a wide range of attention. Tin dioxide (SnO) 2 ) Because of its higher theoretical capacity (1494 mAh g) -1 ) Low toxicity and high natural abundance, and has been widely researched. Alloying process of Sn and Li (Sn +4.4 Li +4.4 e) - ⇋ li4.4sn) has a significant contribution to LIBs capacity, but this process leads to milling, aggregation, rapid capacity fade, poor rate performance due to large volume expansion (ca 300% when fully lithiated). For the past decades, the exploration of SnO has been pursued 2 A great deal of effort is made as a next-generation anode, but the problems of rapid capacity fade and poor rate performance are still not solved.
To solve these problems, further development of advanced-architecture SnO is required 2 And (3) a base anode material. Reasonably designed nano SnO 2 The structure is capable of effectively controlling the internal strain caused by lithiation/delithiation, and is a strategy that can provide better reversibility. Furthermore, nano SnO 2 And the diffusion path of Li ions can be effectively shortened, and the contact area with the electrolyte is increased, so that the rate capability is improved. However, since nano SnO 2 Self-aggregation and low conductivity resulting in nanosized SnO 2 The cycling performance of the anode material is still limited. The second strategy is to design a tin dioxide-soft material nanocomposite (such as SnO) 2 Carbon) to solve self-aggregation and the like. Carbon matrix as barrier layer against Li x Sn gathers and acts as a conductive layer, promoting electron conduction. Meanwhile, the porous structure of the carbon matrix may partially contain Li x The volume of Sn changes, facilitating rapid migration of Li +. A third effective method is in nano SnO 2 The particles are coated with a highly conductive material (e.g., N-doped carbon) to significantly increase conductivity, stabilize Solid Electrolyte Interface (SEI), and maintain mechanical integrity during charging and discharging. Although the above three approaches to solve the problem can improve SnO to some extent 2 Based on the electrochemical properties of LIBs, but synthesizing SnO with high rate performance and stable cycle performance 2 The base anode material remains a formidable challenge.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a tin dioxide-carbon core-shell nanosphere composite material, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a stannic oxide-carbon core-shell nanosphere composite material comprises the following steps:
(1) Preparation of polymeric microspheres (pMS): dissolving ethylene glycol dimethacrylate (1.5-2.5 g), alpha-methacrylic acid (6.0-10.0 g) and azobisisobutyronitrile (0.1-0.4 g) in acetonitrile of 300-500 mL in a drying flask, distilling, precipitating and copolymerizing, and standing and passivating a product by using absolute ethyl alcohol to obtain polymer microspheres (pMS) with the particle size range of 200-500 nm;
(2) Preparation of tin polymer microspheres (Sn-pMS) by cation exchange: dissolving anhydrous sodium acetate (0.7-1.2 g) in absolute ethyl alcohol, then adding the synthesized polymer microsphere pMS (0.1-0.4 g) under stirring, stirring for 10-15 hours, centrifuging, cleaning the precipitate with absolute ethyl alcohol for several times, then pouring the solution in which SnCl is dissolved 2 •2H 2 Stirring the mixture for 20 to 30 hours in an absolute ethanol solution of O (0.5 to 0.8 g). Centrifuging, separating and precipitating, washing with absolute ethyl alcohol, and finally freezing and drying to obtain a tin polymer microsphere Sn-pMS;
(3) Preparing monodisperse pre-oxidized nanospheres: sn-pMS powder is put in air at a temperature of less than 5 ℃ for min -1 The temperature is raised to 280-320 ℃ at the temperature raising speed, and the mixture is heated and oxidized for 2-5 hours. Dispersing the nanospheres (0.1-0.3 g) in water by using ultrasonic waves, transferring the nanospheres into a reaction kettle, preserving the heat for 4-6 hours at the temperature of 120-180 ℃, and performing centrifugal separation to obtain monodisperse pre-oxidized nanospheres after the nanospheres are cooled to room temperature;
(4) Tin dioxide-carbon core-shell composite nanospheres: dispersing 0.1-0.3 g of the pre-oxidized nanospheres in a tris (hydroxymethyl) aminomethane hydrochloric acid buffer solution, adding dopamine with the same mass as the pre-oxidized nanospheres, continuously stirring for 20-30h, centrifuging, freezing and drying to obtain dopamine-coated nanospheres, and finally calcining the dopamine-coated nanospheres at 400-600 ℃ for 1-5 hours under a protective atmosphere to obtain the tin dioxide-carbon core-shell nanosphere composite material.
Further, in the step (2), 0.7 g to 1.2g of anhydrous sodium acetate is dissolved in 100mL of anhydrous ethanol, and 0.5 g to 0.8 g of SnCl is added 2 •2H 2 O is dissolved in 100mL of absolute ethanol and freeze-dried means freeze-dried to a solid at 5 ℃ or below.
Further, in the step (3), the tin polymer microspheres are placed in the air for less than 5 ℃ for min -1 The temperature is raised to 300 ℃ at the temperature raising speed, the oxidation is carried out for 4h, and the temperature is kept in the reaction kettle for 5h at the temperature of 150 ℃.
Further, in the step (4), 0.1 g to 0.3 g of the pre-oxidized nanospheres are dispersed in 150mL of tris (hydroxymethyl) aminomethane hydrochloride buffer solution, wherein the tris (hydroxymethyl) aminomethane hydrochloride buffer solution is prepared by dissolving 186 mg of tris (hydroxymethyl) aminomethane hydrochloride in 150mL of water, and freeze drying refers to dissolving a product obtained after centrifugal separation in a proper amount of tert-butyl alcohol and freeze drying the product at a temperature of below 5 ℃ to obtain a solid.
Further, in the step (4), the dopamine-coated nanospheres are coated in N 2 Calcining for 3h at 500 ℃ under the atmosphere.
The stannic oxide-carbon core-shell nanosphere composite material prepared by the preparation method.
The tin dioxide-carbon core shell nanosphere composite material is mixed with acetylene black and polyvinylidene fluoride according to a mass ratio of 8 to 1, mixed with methyl-2-pyrrolidone to form slurry, coated on a copper foil, dried in vacuum, and put in a glove box filled with Ar inert gas, with Li foil as a counter electrode and a reference electrode and 1M LiPF 6 The ethylene carbonate/diethyl carbonate is taken as electrolyte and assembled into a battery.
Preferably, the vacuum drying refers to vacuum drying at 110 ℃ for 10 hours, and the loading capacity of the stannic oxide-carbon core-shell nanosphere composite material is 1.0 mg cm -2 The Li foil diameter is 16 mm.
The invention synthesizes the tin dioxide-carbon core-shell nanosphere composite lithium ion battery cathode material by a simple cation exchange method and subsequent calcination, and the composite material is uniformly distributed on nano SnO of the porous carbon nanosphere 2 Is a coreAnd the core is coated with a shell layer formed by nitrogen-doped carbon. The composite material not only effectively relieves SnO 2 The volume of the conductive layer is expanded, the conductivity is remarkably improved, and a rapid electron transfer path is provided. At the same time, the nitrogen-doped carbon shell also serves as armor to ensure SnO in the cyclic process 2 The structure stability of the carbon composite nanosphere.
Drawings
FIG. 1 is an SEM image of polymer microspheres (pMS) prepared by distillation precipitation and a corresponding statistical size distribution;
FIG. 2 shows Sn 2+ Exchange for Na + SEM picture of the polymer microsphere prepared later;
FIG. 3 is SEM, TEM and corresponding XRD patterns of monodisperse microspheres prepared after hydrothermal treatment of pre-oxidized microspheres;
FIG. 4 is SEM, TEM and high resolution TEM images of the prepared pitaya-like tin dioxide-carbon core-shell nanosphere composite;
FIG. 5 shows electrochemical impedance spectrum (a), cyclic voltammogram (b), 0.1A g of lithium ion battery assembled by the prepared stannic oxide/carbon @ nitrogen carbon core-shell nano-microspheres -1 Under current density, testing the cycling stability of the battery and corresponding coulombic efficiency (c), and multiplying power performance (d) of the battery under different current densities;
fig. 6 is a schematic structural diagram of the tin dioxide-carbon core-shell nanosphere composite lithium ion battery negative electrode material prepared in the present application.
Detailed Description
In order to make the technical purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are further described below with reference to specific examples, but the examples are intended to illustrate the present invention and should not be construed as limiting the present invention, and those who do not specify any particular technique or condition in the examples are performed according to techniques or conditions described in documents in the art or according to product specifications.
Example 1
A method for preparing a stannic oxide-carbon core-shell nanosphere composite material comprises the following steps:
(1) Ethylene glycol dimethacrylate (2.0 g,10.1 mmol), α -methacrylic acid (8.0 g, 93.1 mmol), azobisisobutyronitrile (0.2067 g, 1.26mmol) were dissolved in 400 mL acetonitrile in a 500 mL dry two-necked flask and subjected to a typical distillation precipitation copolymerization process (see Polymer 2006, 47, 5775-5784) to produce polymeric microspheres (denoted pMS) having a particle size of about 400 nm. After polymerization, centrifuging, adding absolute ethyl alcohol again, centrifuging, finally dispersing the polymer microspheres in absolute ethyl alcohol to ensure that the concentration of the polymer microspheres in the absolute ethyl alcohol is 100 mg/ml, and a scanning electron microscope image and particle size statistics are shown in figure 1, wherein the figure 1 shows that the particle size of the prepared polymer microspheres is about 400 nm.
(2) Dissolving anhydrous sodium acetate (0.984 g) in 100mL anhydrous ethanol, adding 3mL ethanol dispersion of polymer microsphere under stirring (i.e. pMS addition amount is 0.3 g), stirring for 12 hr, centrifuging, washing precipitate with anhydrous ethanol for 2-3 times, pouring SnCl dissolved therein 2 •2H 2 And (3) adding O (0.68 g) into 100mL of absolute ethyl alcohol solution, stirring for 24 hours, centrifuging, separating and precipitating, washing for 2-3 times by using absolute ethyl alcohol, and freeze-drying for 48 hours at the temperature of 5 ℃ to obtain the Sn-pMS, wherein the basic morphology of the pMS is basically maintained as shown in figure 2.
(3) 0.2 g of Sn-pMS powder is put in air at 1 ℃ for min -1 The temperature is increased to 300 ℃ and oxidized for 4h at 300 ℃, and the temperature is naturally reduced to room temperature, so as to obtain the pre-oxidized nanospheres. The pre-oxidized nanospheres (0.2 g) were then dispersed into 70 mL of water using 400W ultrasonic sonication for 2 min. Then, transferring the product into a 100mL stainless steel autoclave lined with polytetrafluoroethylene, preserving the heat for 5h at 150 ℃, opening the autoclave, cooling to room temperature, performing centrifugal separation to obtain monodisperse pre-oxidized nanospheres, wherein a scanning and transmission electron microscope is shown as figure 3, the monodisperse pre-oxidized nanospheres inherit the appearance of the precursor after pretreatment, and the polymer microspheres can be seen to be in a monodisperse state from the large-range SEM scanning result 2 Nanoparticles are small (<5 nm), which also corresponds to a broader diffraction peak in XRD. The X-ray diffraction (XRD) result shows that the crystallization degree is also improved to some extent.
(4) Dispersing monodisperse pre-oxidized nanosphere (0.2 g) in 150mL buffer of Tris hydrochloride (prepared by dissolving 186 mg Tris hydrochloride in 150mL water), adding dopamine (200 mg), stirring for 24 hr, polymerizing dopamine on nanosphere surface, centrifuging, dispersing the obtained product in 5 mL tert-butanol, freeze drying (drying at 5 deg.C for 24 hr), and freeze drying at 500 deg.C (at 1 deg.C for min) -1 Heating to 500 ℃ N 2 Calcining for 3h under the atmosphere to obtain the tin dioxide-carbon core-shell nanosphere composite material shown in figure 4. From TEM results, snO was observed 2 The particle diameter increases after heat treatment and the polymer microsphere has a uniform carbon layer on the outside. From the results of high resolution TEM, snO can be seen 2 The particle is about 5nm, and the thickness of the coating carbon layer is about 2-5 nm.
Mixing the prepared stannic oxide-carbon core-shell nanosphere composite material with acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 8 -2 Left and right. And the cell was assembled in a glove box filled with Ar inert gas, with Li foil (diameter 16 mm) as the counter electrode and reference electrode, and 1M LiPF6 ethylene carbonate/diethyl carbonate (EC/DEC 1. Cyclic Voltammograms (CVs), discharge-charge measurements (voltage range of 0.005-3.0V) and Electrochemical Impedance Spectroscopy (EIS) measurements were performed with electrochemical performance as shown in figure 5.
As shown in fig. 5, the electrochemical impedance spectrum shows that the charge transfer resistance of the assembled lithium ion battery is about 80 Ω; the significant reduction peak at the first cycle of 0.72V in the Cyclic Voltammetry (CV) curve is attributed to SnO 2 Reduction to Sn and formation of solid electrolyte interphase layer (SEI), another reduction peak at 0.05V due to the alloying process of Li and Sn, a strong peak at 0.59V and a broad peak at 1.22V corresponding to Li, respectively, during anode scanning x Sn is detinned into Sn and the metallic Sn is reversibly oxidized. In subsequent cycles, the CV curves almost overlapped, indicating that the polymer electrode had excellent performanceElectrochemical reversibility of (c); galvanostatic charge/discharge test evaluation the above samples were tested at 0.1 ag at a potential window of 3.0-0.005V -1 The prepared electrode can still provide 936.8 mAh g after 100 cycles -1 The coulombic efficiency of (1) is close to 99.0%. (ii) a FIG. 5d shows current densities of 0.1, 0.2, 0.4, 0.8, 1.6 and 3.2 ag -1 Rate capability of the prepared electrode, even at 3.2 ag -1 The average specific capacity is still kept at 460.0 mA h g under the high current density -1 To (3). In addition, when the current density returns to 0.1 ag -1 Then, the discharge capacity can be recovered to 805.2 mA h g -1 。
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (9)

1. A preparation method of a stannic oxide-carbon core-shell nanosphere composite material is characterized by comprising the following steps:
(1) Preparing polymer microspheres with the particle size range of 200nm to 500 nm, and dispersing the prepared polymer microspheres in ethanol;
(2) Preparing tin polymer microspheres by a cation exchange method: dissolving 0.7 to 1.2g of anhydrous sodium acetate in ethanol, adding the ethanol dispersion of the synthesized polymer microspheres under stirring, wherein the addition amount of the polymer microspheres is 0.1 to 0.4g, stirring for 10 to 15 hours, centrifuging, washing precipitates, and pouring the washed solid into a solution containing 0.5 to 0.8 g of SnCl 2 •2H 2 Stirring in ethanol of O for 20 to 30 hours, centrifuging, precipitating, washing, and freeze-drying to obtain tin polymer microspheres;
(3) Preparing monodisperse pre-oxidized nanospheres: the tin polymer microspheres are put in the air for less than 5 ℃ min -1 Heating to 280-320 ℃ at a heating speed, oxidizing for 2-5 hours, then dispersing 0.1-0.3 g of the oxidized nanospheres into water, transferring the nanospheres into a reaction kettle, and preserving heat for 4-6 hours at 120-180 DEG CAfter the temperature is reduced to room temperature, performing centrifugal separation to obtain monodisperse pre-oxidized nanospheres;
(4) Tin dioxide-carbon core-shell composite nanospheres: dispersing 0.1-0.3 g of the pre-oxidized nanospheres in a tris (hydroxymethyl) aminomethane hydrochloric acid buffer solution, adding dopamine with the same mass as the pre-oxidized nanospheres, continuously stirring for 20-30h, centrifuging, freezing and drying to obtain dopamine-coated nanospheres, and finally calcining the dopamine-coated nanospheres at 400-600 ℃ for 1-5 hours under a protective atmosphere to obtain the tin dioxide-carbon core-shell nanosphere composite material.
2. The preparation method of the tin dioxide-carbon core-shell nanosphere composite material according to claim 1, wherein in the step (2), 0.7-1.2g of anhydrous sodium acetate is dissolved in 100mL of anhydrous ethanol, and 0.5-0.8 g of SnCl is dissolved in the anhydrous ethanol 2 •2H 2 O is dissolved in 100mL of absolute ethanol, and freeze-drying means freeze-drying at 5 ℃ or below to obtain a solid.
3. The method for preparing the tin dioxide-carbon core-shell nanosphere composite material of claim 1, wherein in step (3), the tin polymer microspheres are exposed to air at a temperature of less than 5 ℃ for a period of time -1 The temperature is raised to 300 ℃ at the temperature raising speed, the oxidation is carried out for 4 hours, and the temperature is kept in the reaction kettle for 5 hours at the temperature of 150 ℃.
4. The method for preparing the tin dioxide-carbon core-shell nanosphere composite material according to claim 1, wherein in the step (4), 0.1 to 0.3 g of the pre-oxidized nanosphere is dispersed in 150mL of Tris-HCl buffer prepared by dissolving 186 mg of Tris-HCl in 150mL of water, and the freeze-drying is to dissolve the product obtained after the centrifugal separation in a proper amount of t-butanol and freeze-dry the product to be solid at a temperature below 5 ℃.
5. The method for preparing the tin dioxide-carbon core-shell nanosphere composite material as claimed in claim 1, wherein in the step (4), dopamine-coated nanospheres are coated on N 2 Atmosphere(s)Calcining at 500 ℃ for 3h.
6. The tin dioxide-carbon core-shell nanosphere composite prepared by the preparation method of any one of claims 1 to 5.
7. The use of the tin dioxide-carbon core shell nanosphere composite of claim 6 as a lithium ion battery negative electrode material.
8. The use according to claim 7, characterized in that the tin dioxide-carbon core-shell nanosphere composite is mixed with acetylene black, polyvinylidene fluoride in a mass ratio of 8 6 The ethylene carbonate/diethyl carbonate is used as electrolyte to assemble the battery.
9. The use as claimed in claim 8, wherein the vacuum drying is performed at 110 ℃ for 10h, and the loading capacity of the stannic oxide-carbon core-shell nanosphere composite material is 1.0 mg cm -2 The Li foil diameter is 16 mm.
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