CN112289983A - SiO (silicon dioxide)x-MWCNTs/C core-shell composite anode material and preparation method and application thereof - Google Patents
SiO (silicon dioxide)x-MWCNTs/C core-shell composite anode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a SiOxThe preparation method of the MWCNTs/C core-shell composite anode material comprises the following steps: s1, sequentially adding tetraethylammonium bromide, carboxylated multi-walled carbon nanotubes and ammonia water into an ethanol water solution for uniform dispersion, then adding vinyl triethoxysilane for uniform mixing, carrying out esterification reaction, centrifuging, washing the precipitate, and then uniformly dispersing the precipitate in a polyoxyethylene water solution to obtain a solution A; s2, carrying out electrostatic coaxial spinning by taking the solution A as an inner layer and the polyvinyl alcohol aqueous solution as an outer layer to obtain filaments; calcining the filaments in a mixed gas atmosphereTo obtain SiOx-MWCNTs/C core-shell composite anode material. The invention also discloses SiOx-MWCNTs/C core-shell composite anode material and application thereof. The invention not only improves the safety and stability of the whole silicon cathode, but also greatly improves the electrochemical performance, and can effectively improve the conductivity, the cycle performance, the rate performance and the like of the silicon cathode.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to SiOx-MWCNTs/C core-shell composite anode material, and a preparation method and application thereof.
Background
With the rapid development of electric vehicles and large-scale energy storage systems, lithium ion batteries with high energy density and long cycle life are increasingly desired in the market. Since the electrode material in a lithium ion battery determines the energy density of a cell, high capacity electrode materials have been developed. Silicon is accepted as the most ideal lithium ion negative electrode material because the silicon has high theoretical gram capacity of 3600mAh/g at room temperature, and has the advantages of safe lithium ion extraction/insertion platform, abundant resources and the like. However, silicon with excellent lithium storage capacity is accompanied by severe volume expansion during cycling, which results in unstable electrode structure, which causes safety hazard, and also has problems of poor conductivity, which becomes a great obstacle for application of silicon-based materials.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides SiOxThe MWCNTs/C core-shell composite anode material, the preparation method and the application thereof, the invention not only improves the safety and the stability of the whole anode material, but also greatly improves the electrochemical performance, and can effectively improve the conductivity, the cycle performance, the rate capability and the like of the silicon anode.
The invention provides SiOxThe preparation method of the MWCNTs/C core-shell composite anode material comprises the following steps:
s1, sequentially adding tetraethylammonium bromide, carboxylated multi-walled carbon nanotubes and ammonia water into an ethanol water solution for uniform dispersion, then adding vinyl triethoxysilane for uniform mixing, carrying out esterification reaction, centrifuging, washing the precipitate, and then uniformly dispersing the precipitate in a polyoxyethylene water solution to obtain a solution A;
s2, carrying out electrostatic coaxial spinning by taking the solution A as an inner layer and the polyvinyl alcohol aqueous solution as an outer layer to obtain filaments; calcining the filaments in a mixed gas atmosphere to obtain SiOx-MWCNTs/C core-shell composite anode material.
Preferably, in S1, the esterification reaction is carried out at a temperature of 25-60 ℃ for 1-3 h.
Preferably, in S1, the weight ratio of the carboxylated multi-walled carbon nanotubes to the vinyltriethoxysilane is 0.02-0.2: 1-10.
Preferably, in S1, the weight ratio of the tetraethylammonium bromide to the carboxylated multi-walled carbon nanotubes to the ammonia water is 0.1-0.5:0.02-0.2: 3.6-18.2.
The mass fraction of the ammonia water is about 25-28%.
Preferably, in S1, the weight volume (g/ml) of tetraethylammonium bromide and ethanol is 0.1-0.5: 10-30.
Preferably, in S1, the volume ratio of ethanol to water in the ethanol aqueous solution is 1-3: 5-7.
Preferably, in S1, the carboxylated multi-walled carbon nanotube is obtained by performing carboxylation modification on a multi-walled carbon nanotube, and the multi-walled carbon nanotube has a diameter of 5 to 12nm, a circumference of 30 to 50nm, and a length of 10 to 20 μm.
The carboxylated multi-wall carbon nanotubes can be prepared by the conventional method for carboxylated modification in the field by the skilled person, and can also be prepared by the following method: mixing 0.1-2.0g of multi-walled carbon nanotube with 10-50ml of concentrated nitric acid, refluxing for 20-30h, centrifuging, washing the precipitate with water until the pH of the washing solution is 5-8, and vacuum drying at 60-100 deg.C for 20-30 h.
Preferably, in S1, the weight-to-volume (g/ml) ratio of polyoxyethylene to water in the polyoxyethylene aqueous solution is 1-5: 100-200.
Preferably, in S1, the weight ratio of precipitate to polyethylene oxide is 0.1-0.5: 1-5.
Preferably, in S2, the weight-to-volume (g/ml) ratio of the polyvinyl alcohol to the water in the aqueous solution of polyvinyl alcohol is 5-10: 100-200.
Preferably, in S2, the spinning voltage is 10-20kV, the diameter of the inner layer spinning needle is 0.6-0.8mm, the diameter of the outer layer spinning needle is 1-2mm, and the distance from the inner layer spinning needle to the spinning receiving plate is 10-14 cm.
Preferably, in S2, the mixed gas is hydrogen and argon, and the volume percentage of hydrogen is 2%.
Preferably, in S2, the flow rate of the mixed gas is 50-150 ml/min.
Preferably, in S2, the calcination temperature is 800-1500 ℃, and the calcination time is 2-5 h.
The invention also provides SiOx-MWCNTs/C core-shell composite anode material, according to the above SiOxThe preparation method of the-MWCNTs/C core-shell composite anode material.
The invention also provides the SiOxApplication of the MWCNTs/C core-shell composite negative electrode material in a lithium ion battery.
Has the advantages that:
SiO of the inventionxThe MWCNTs/C core-shell composite negative electrode material effectively improves the conductivity and electrochemical performance of the silicon-based material; SiO 2xThe MWCNTs/C core-shell composite negative electrode material has a three-dimensional network structure and a unique core-shell structure, the whole framework is a flexible carbon material, multi-walled carbon nanotubes (MWCNTs) are introduced, the volume expansion generated in the expansion of the material can be effectively accommodated, the stress is released, the matrix is the carbon material, the outer shell is an amorphous carbon material and the introduced MWCNTs are added, and the whole conductive capability of the material can be greatly improved; the invention not only improves the safety and stability of the whole silicon cathode, but also greatly improves the electrochemical performance, can effectively improve the conductivity, the cycle performance, the rate performance and the like of the silicon cathode, and is superior to the commercial silicon protoxide material at present;
mixing SiOxThe MWCNTs/C core-shell composite negative electrode material is used as a negative electrode of a lithium battery, is assembled into a button battery, shows excellent reversible capacity in initial recycling and is also excellent in timesThe silicon-based anode material has high rate performance and high cycle durability, effectively solves two problems (low conductivity and volume expansion) of silicon-based materials used as lithium ion batteries, and shows performance superior to that of silicon-based anode materials on the current market.
Drawings
FIG. 1 is SiO prepared in example 1xAn SEM image and a structural schematic diagram of the MWCNTs/C core-shell composite anode material, wherein a is the SEM image, and b is the structural schematic diagram.
FIG. 2 is SiO for example 1xA cyclicity diagram of a button cell made of the MWCNTs/C core-shell composite negative electrode material.
FIG. 3 is SiO for example 1x-a multiplying power performance diagram of a button cell made of MWCNTs/C core-shell composite negative electrode material.
Fig. 4 is a cycling diagram of a button cell made of silicon oxide.
Fig. 5 is a graph of rate performance of button cells made of silica.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
SiO (silicon dioxide)xThe preparation method of the MWCNTs/C core-shell composite anode material comprises the following steps:
s1, building a condensation reflux device, weighing 0.1g of MWCNTs, slowly adding 50ml of concentrated nitric acid, adjusting the temperature for refluxing for 30h, then cooling to room temperature, centrifuging at the speed of 4500rpm, pouring out supernatant, repeatedly washing and precipitating with deionized water until the pH of a washing solution is about 7, and drying in a vacuum oven at 80 ℃ for 24h to obtain the carboxylated multi-walled carbon nanotube;
uniformly mixing 25ml of absolute ethyl alcohol and 60ml of deionized water, adding 0.3g of tetraethylammonium bromide, quickly stirring uniformly, adding 0.05g of carboxylated multi-walled carbon nanotubes and 9.07g of ammonia water with the mass fraction of 25%, and quickly stirring for 30 min; then adding 5g of vinyltriethoxysilane, stirring until the solution is clear and uniformly mixed, then carrying out esterification reaction for 1h at 25 ℃, centrifuging, and repeatedly washing and precipitating with deionized water;
then 4g of polyoxyethylene is taken to be dissolved in 150ml of deionized water, 0.4g of precipitate is added under continuous stirring, and the solution A is obtained after the precipitate is uniformly dispersed;
s2, dissolving 5g of polyvinyl alcohol in 150ml of deionized water to obtain a polyvinyl alcohol aqueous solution; adopting electrostatic coaxial spinning equipment, taking the solution A as an inner layer and the polyvinyl alcohol aqueous solution as an outer layer, carrying out electrostatic spinning (the spinning voltage is 20kV, the diameter of a spinning needle head of the inner layer is 0.7mm, the diameter of a spinning needle head of the outer layer is 1mm, the distance from the spinning needle head of the inner layer to a spinning receiving plate is 12cm), collecting filaments, placing the filaments in a tube furnace, introducing mixed gas of hydrogen (the volume percentage is 2%) and argon, the flow is 100ml/min, calcining for 3h at 1000 ℃, naturally cooling to obtain SiOx-MWCNTs/C core-shell composite anode material.
FIG. 1 is SiO prepared in example 1xAn SEM image and a structural schematic diagram of the MWCNTs/C core-shell composite anode material, wherein a is the SEM image, and b is the structural schematic diagram.
As can be seen from fig. 1: SiO 2xThe structure of the-MWCNTs/C core-shell composite anode material is SiO with a multi-walled carbon nano tube grafted insidexAnd an amorphous carbon layer is coated outside the shell to form a core-shell structure, so that the expansion stress is relieved to a great extent, and the conductive capability is improved.
SiO prepared in example 1 was takenxAnd respectively taking MWCNTs/C core-shell composite negative electrode materials and commercially available silicon monoxide as negative electrode active substances, and assembling the materials into the button cell by the same method.
The preparation method of the button cell comprises the following steps: the button cell is CR2032, the negative active material comprises CMC, SBR and SP, the weight percentages of which are 95 percent to 1.5 percent to 2 percent to 1.5 percent are mixed into slurry, the counter electrode is a pure lithium sheet, a PE diaphragm (the thickness is 20 mu m) is adopted in the middle, and the electrolyte contains 1mol/L LiPF6And the electrolyte solvent is EC: EMC 1:1(v/v), a proper amount of foam nickel gasket can be added according to the residual space of the button cell, and finally the button cell is assembled in a glove box filled with argon.
The performance of the button cell is detected, the structure is shown in figures 2-5, figure 2 is SiO of example 1x-a cyclicity diagram of a button cell made of MWCNTs/C core-shell composite negative electrode material; FIG. 3 is SiO for example 1x-a rate performance diagram of a button cell made of MWCNTs/C core-shell composite negative electrode material; FIG. 4 is a cycle chart of a button cell made of silicon monoxide; fig. 5 is a graph of rate performance of button cells made of silica.
As can be seen from fig. 2-5: SiO 2xThe MWCNTs/C core-shell composite negative electrode material has more stable cycle performance and rate capability, the flexible nanotube and the amorphous carbon shell can accommodate volume expansion to a great extent, the pulverization degree of the silicon oxide particles is reduced, the charge and discharge life is prolonged, and longer cruising ability is provided. In addition, the carbon matrix provides outstanding electric conductivity, has promoted the electric conductivity of oxidation pressure silicon, reduces material polarization, promotes big multiplying power charge-discharge ability.
Example 2
SiO (silicon dioxide)xThe preparation method of the MWCNTs/C core-shell composite anode material comprises the following steps:
s1, building a condensation reflux device, weighing 0.1g of MWCNTs, slowly adding 50ml of concentrated nitric acid, adjusting the temperature for refluxing for 30h, then cooling to room temperature, centrifuging at the speed of 4500rpm, pouring out supernatant, repeatedly washing and precipitating with deionized water until the pH of a washing solution is about 7, and drying in a vacuum oven at 80 ℃ for 24h to obtain the carboxylated multi-walled carbon nanotube;
uniformly mixing 25ml of absolute ethyl alcohol and 60ml of deionized water, adding 0.1g of tetraethylammonium bromide, quickly stirring uniformly, adding 0.02g of carboxylated multi-walled carbon nanotubes and 3.6g of ammonia water with the mass fraction of 25%, and quickly stirring for 30 min; then adding 5g of vinyltriethoxysilane, stirring until the solution is clear and uniformly mixed, then carrying out esterification reaction for 1h at 25 ℃, centrifuging, and repeatedly washing and precipitating with deionized water;
then 4g of polyoxyethylene is taken to be dissolved in 150ml of deionized water, 0.4g of precipitate is added under continuous stirring, and the solution A is obtained after the precipitate is uniformly dispersed;
s2, dissolving 5g of polyvinyl alcohol in 150ml of deionized water to obtain a polyvinyl alcohol aqueous solution; adopting electrostatic coaxial spinning equipment, using solution A as inner layer and polyvinyl alcohol aqueous solution as outer layer to make electrostatic spinning (spinning voltage is 20kV, diameter of inner layer spinning needle head0.7mm, the diameter of the outer layer spinning needle is 1mm, the distance between the inner layer spinning needle and the outer layer spinning needle and a spinning receiving plate is 12cm, the filaments are collected and placed in a tube furnace, mixed gas of hydrogen (the volume percentage is 2 percent) and argon is introduced, the flow is 100ml/min, the mixture is calcined for 3 hours at the temperature of 1000 ℃, and SiO is obtained by natural coolingx-MWCNTs/C core-shell composite anode material.
Example 3
SiO (silicon dioxide)xThe preparation method of the MWCNTs/C core-shell composite anode material comprises the following steps:
s1, building a condensation reflux device, weighing 0.2g of MWCNTs, slowly adding 100ml of concentrated nitric acid, adjusting the temperature for refluxing for 30h, then cooling to room temperature, centrifuging at the speed of 4500rpm, pouring out supernatant, repeatedly washing and precipitating with deionized water until the pH of a washing solution is about 7, and drying in a vacuum oven at 80 ℃ for 24h to obtain the carboxylated multi-walled carbon nanotube;
uniformly mixing 25ml of absolute ethyl alcohol and 60ml of deionized water, adding 0.5g of tetraethylammonium bromide, rapidly stirring uniformly, adding 0.1g of carboxylated multi-walled carbon nanotubes and 18.1g of ammonia water with the mass fraction of 25%, and rapidly stirring for 30 min; then adding 5g of vinyltriethoxysilane, stirring until the solution is clear and uniformly mixed, then carrying out esterification reaction for 1h at 25 ℃, centrifuging, and repeatedly washing and precipitating with deionized water;
then 4g of polyoxyethylene is taken to be dissolved in 150ml of deionized water, 0.4g of precipitate is added under continuous stirring, and the solution A is obtained after the precipitate is uniformly dispersed;
s2, dissolving 5g of polyvinyl alcohol in 150ml of deionized water to obtain a polyvinyl alcohol aqueous solution; adopting electrostatic coaxial spinning equipment, taking the solution A as an inner layer and the polyvinyl alcohol aqueous solution as an outer layer, carrying out electrostatic spinning (the spinning voltage is 20kV, the diameter of a spinning needle head of the inner layer is 0.7mm, the diameter of a spinning needle head of the outer layer is 1mm, the distance from the spinning needle head of the inner layer to a spinning receiving plate is 12cm), collecting filaments, placing the filaments in a tube furnace, introducing mixed gas of hydrogen (the volume percentage is 2%) and argon, the flow is 100ml/min, calcining for 3h at 1000 ℃, naturally cooling to obtain SiOx-MWCNTs/C core-shell composite anode material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. SiO (silicon dioxide)xThe preparation method of the MWCNTs/C core-shell composite anode material is characterized by comprising the following steps:
s1, sequentially adding tetraethylammonium bromide, carboxylated multi-walled carbon nanotubes and ammonia water into an ethanol water solution for uniform dispersion, then adding vinyl triethoxysilane for uniform mixing, carrying out esterification reaction, centrifuging, washing the precipitate, and then uniformly dispersing the precipitate in a polyoxyethylene water solution to obtain a solution A;
s2, carrying out electrostatic coaxial spinning by taking the solution A as an inner layer and the polyvinyl alcohol aqueous solution as an outer layer to obtain filaments; calcining the filaments in a mixed gas atmosphere to obtain SiOx-MWCNTs/C core-shell composite anode material.
2. SiO as in claim 1xThe preparation method of the MWCNTs/C core-shell composite anode material is characterized in that in S1, the temperature of esterification reaction is 25-60 ℃, and the time is 1-3 h.
3. SiO according to claim 1 or 2xThe preparation method of the MWCNTs/C core-shell composite anode material is characterized in that in S1, the weight ratio of the carboxylated multi-walled carbon nanotube to the vinyl triethoxysilane is 0.02-0.2: 1-10; preferably, in S1, the weight ratio of the tetraethylammonium bromide to the carboxylated multi-walled carbon nanotubes to the ammonia water is 0.1-0.5:0.02-0.2: 3.6-18.2; preferably, in S1, the weight volume (g/ml) of tetraethylammonium bromide and ethanol is 0.1-0.5: 10-30; preferably, in S1, the volume ratio of ethanol to water in the ethanol aqueous solution is 1-3: 5-7.
4. SiO according to any of claims 1 to 3x-MWCNTs/C core-shell composite negative electrode materialThe preparation method of the material is characterized in that in S1, the carboxylated multi-wall carbon nano-tube is obtained by performing carboxylation modification on the multi-wall carbon nano-tube, the diameter of the multi-wall carbon nano-tube is 5-12nm, the perimeter of the multi-wall carbon nano-tube is 30-50nm, and the length of the multi-wall carbon nano-tube is 10-20 mu m.
5. SiO according to any of claims 1 to 4xThe preparation method of the MWCNTs/C core-shell composite anode material is characterized in that in S1, the weight-volume (g/ml) ratio of polyoxyethylene to water in polyoxyethylene aqueous solution is 1-5: 100-200; preferably, in S1, the weight ratio of precipitate to polyethylene oxide is 0.1-0.5: 1-5.
6. SiO according to any of claims 1 to 5xThe preparation method of the MWCNTs/C core-shell composite anode material is characterized in that in S2, the weight-volume (g/ml) ratio of polyvinyl alcohol to water in a polyvinyl alcohol aqueous solution is 5-10: 100-200.
7. SiO according to any of claims 1 to 6xThe preparation method of the MWCNTs/C core-shell composite negative electrode material is characterized in that in S2, the spinning voltage is 10-20kV, the diameter of an inner layer spinning needle is 0.6-0.8mm, the diameter of an outer layer spinning needle is 1-2mm, and the distances from the inner layer spinning needle and the outer layer spinning needle to a spinning receiving plate are 10-14 cm.
8. SiO according to any of claims 1 to 7xThe preparation method of the MWCNTs/C core-shell composite anode material is characterized in that in S2, mixed gas is hydrogen and argon, and the volume percentage of the hydrogen is 2%; preferably, in S2, the flow rate of the mixed gas is 50-150 ml/min; preferably, in S2, the calcination temperature is 800-1500 ℃, and the calcination time is 2-5 h.
9. SiO (silicon dioxide)x-MWCNTs/C core-shell composite negative electrode material, characterized in that the SiO according to any of claims 1 to 8xThe preparation method of the-MWCNTs/C core-shell composite anode material.
10. SiO as claimed in claim 9xApplication of the MWCNTs/C core-shell composite negative electrode material in a lithium ion battery.
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