CN110137466B - Preparation method of silicon carbon-carbon nanotube composite microsphere negative electrode material of lithium ion battery - Google Patents
Preparation method of silicon carbon-carbon nanotube composite microsphere negative electrode material of lithium ion battery Download PDFInfo
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Abstract
The invention provides a preparation method of a silicon carbon-carbon nanotube composite microsphere negative electrode material of a lithium ion battery, belonging to the field of negative electrode materials of lithium ion batteries. The preparation method comprises the following specific steps: mixing nano silicon oxide and carbon nano tubes to prepare silicon-carbon nano tube composite microspheres; then carrying out magnesiothermic reduction to obtain porous silicon-carbon nanotube composite microspheres; then coating a layer of organic carbon source with dopamine hydrochloride, and obtaining the carbon-coated silicon carbon-carbon nanotube composite microsphere negative electrode material through pyrolysis. The composite negative electrode material takes porous nano silicon as a substrate material, the surface of the porous nano silicon is coated with a carbon layer, and carbon nanotubes penetrate through and are distributed in the interior and on the surface of the microsphere in an interlaced manner to form a unique multilevel conductive network, so that the conductivity of the material is improved, the specific capacity is higher, and the cycle life of the material is comprehensively prolonged.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a preparation method of a lithium ion battery silicon carbon-carbon nanotube composite microsphere cathode material.
Background
With the rapid development of the 3C industry, lithium ion batteries as power supplies have also become a sunrise industry with great prospects. The lithium ion battery has the advantages of high energy density, long cycle life, less self-discharge, high charging speed, environmental protection and the like, and is a secondary battery with the fastest development and the best market prospect at present. Meanwhile, the energy consumption is gradually increased, and the environmental pollution is increasingly serious, so that the new energy automobile which is environment-friendly and pollution-free is widely concerned by governments and enterprises of various countries. The power battery is used as a core part of the electric automobile, and the development plan of the power battery is clear from China manufacturing 2025: in 2020, the energy density of the battery reaches 300 Wh/kg; in 2025, the energy density of the battery reaches 400 Wh/kg.
To achieve the above object, the development of a high energy density lithium ion battery is urgently required. At present, the theoretical capacity of a graphite cathode commonly adopted by a lithium ion battery is only 372mAh/g, the actual capacity is close to the limit, the improvement is difficult, and the requirement of an electric automobile for higher and higher energy density of the battery is difficult to meet.
The theoretical capacity of silicon is 4200mAh/g, which is ten times of the capacity of graphite, and is the lithium ion battery cathode material with the most industrialization prospect at present. However, the volume change of silicon during charging and discharging is as high as 300%, which easily causes pulverization and falling of active materials, and finally, the rapid attenuation of the capacity of the conductive cell, further limiting the commercial application thereof. The silicon is subjected to nanocrystallization to prepare special structures such as silicon nanowires, nano particles, nano hollow spheres and the like, so that the volume effect of the silicon in the charging and discharging process can be greatly inhibited, and the pulverization of the particles is reduced. However, the large specific surface area of the nano material can cause serious agglomeration and low tap density, which is not beneficial to industrial application. Therefore, the preparation of silicon-based negative electrode materials with low surface area and high tap density has important practical significance for commercial nets of silicon.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a lithium ion battery silicon carbon-carbon nanotube composite microsphere negative electrode material with high tap density and low specific surface area.
The invention provides a preparation method of a silicon carbon-carbon nanotube composite microsphere cathode material of a lithium ion battery, wherein the silicon carbon-carbon nanotube composite microsphere cathode material is formed by combining three materials of porous silicon, carbon nanotubes and amorphous carbon in a specific distribution mode, a carbon layer is coated on the surface of porous nano silicon, the porous nano silicon coated with the carbon is assembled into micron-sized spherical porous silicon, and the carbon nanotubes are distributed in and on the surface of a microsphere in a penetrating and interweaving manner; the porous silicon carbon microspheres are micropores and mesopores, and the silicon carbon microspheres are microspheres with the granularity of 1-50 mu m. The preparation method comprises the following specific steps:
(1) hydrophilic SiO2The synthesis of (2): according to the volume ratio of water to ethanol of 1: 8 preparing an ethanol solution, adding ammonia water and tetraethyl orthosilicate, and stirring for a certain time to obtain 200-400 nm hydrophilic SiO2；
(2)SiO2-carbon nanotube composite microsphere preparation: according to the weight ratio of silicon dioxide: water: oil proportion is 0.2-0.5 g: 5-10 mL: 30-40 mL of hydrophilic SiO obtained in the step 12Adding into deionized water, and adding hydrophilic SiO21-20% of hydrophilic carbon nano tubes, and stirring and dispersing; dripping the dispersion liquid into an octadecylene oil phase containing an emulsifier, stirring at a high speed for 2-3 min, and keeping the temperature at 98-100 ℃ for 3h to obtain SiO with a spherical center2-carbon nanotube composite microspheres;
(3) preparing the silicon-carbon nanotube composite microspheres: the SiO obtained in the step 22Mixing the-carbon nano tube composite microspheres with potassium chloride according to the mass ratio of 1: 21-30, and adding SiO2Grinding and mixing magnesium powder with the mass of 50-100%, heating to 600-800 ℃ under the protection of hydrogen-argon mixed gas, preserving heat for 1-5 h, cooling, cleaning with acid, and drying to obtain the silicon-carbon nanotube composite porous microspheres;
(4) preparing carbon-coated silicon-carbon nanotube composite microspheres: dispersing the sample prepared in the step (3) in a buffer solution, adding dopamine hydrochloride with the mass of 20-100% of that of the sample, stirring for a certain time at room temperature, centrifugally drying, placing the dried product in a tubular furnace, heating to 400-1000 ℃ at a certain heating rate under an inert atmosphere, keeping the temperature for 1-10 hours, and cooling to room temperature to obtain a carbon-coated silicon carbon-carbon nanotube composite microsphere negative electrode material;
further, the certain time in the step (1) is 2-10 hours.
Further, the oil in the step (2) is octadecene; the hydrophilic carbon nano tube is one or more of hydroxyl, carboxyl and aminated carbon nano tube; the emulsifier is one or more of Hypermer2296, Hypermer2524, Hypermer1031, Hypermer B-210 and Hypermer 2234.
Further, the acid in the step (3) is one or two of hydrochloric acid and hydrofluoric acid.
Further, the buffer solution in the step (4) is a Tris-base prepared solution with pH of 8; the stirring is carried out for 1-24 hours, preferably 5-24 hours; the protective atmosphere is nitrogen, argon or helium.
The steps (1), (2), (3) and (4) are an organic unified and inseparable integral scheme, and all the steps are organically matched to play a synergistic effect. The silicon-carbon composite porous microsphere negative electrode material is formed by combining three materials, namely porous silicon, carbon nano tubes and amorphous carbon in a specific distribution mode, wherein the surface of the porous nano silicon is coated with a carbon layer, the carbon-coated porous nano silicon is assembled into micron-sized spherical porous silicon, and the carbon nano tubes are distributed in the interior and on the surface of the microsphere in a penetrating and interweaving manner, so that a three-dimensional communicated conductive network is constructed in an auxiliary manner, the conductivity of the material is enhanced, and the impedance is reduced; the pore structure in the nano silicon and the gaps among the nano particles provide a releasing space for the volume expansion of the silicon; the micron-sized microspheres reduce the specific surface area and are beneficial to improving the tap density; the carbon coating on the surface of the silicon particles can improve the conductivity of silicon; the coordination of the above aspects comprehensively prolongs the cycle life of the material.
Drawings
FIG. 1 is an SEM image of a silicon carbon-carbon nanotube composite microsphere prepared in example 1 of the present invention;
FIG. 2 is an XRD photograph of a silicon carbon-carbon nanotube composite microsphere prepared in example 1 of the present invention;
FIG. 3 is a tap density optical photograph of the composite microsphere of silicon carbon-carbon nanotube prepared in example 1 of the present invention;
fig. 4 is a charge and discharge curve of the silicon carbon-carbon nanotube composite microsphere prepared in example 1 of the present invention.
Detailed Description
In order to make the density, technical scheme and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and the detailed description. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all 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 understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example one
(1) Preparing a mixed solution containing 10mL of water and 80mL of ethanol, adding 3mL of ammonia water, uniformly stirring, quickly adding 6mL of tetraethyl orthosilicate, and stirring for 2 hours to obtain the hydrophilic nano SiO2And centrifugally drying;
(2) 500mg of hydrophilic nano SiO2Dispersing the hydroxyl carbon nano tube and 5mg of the hydroxyl carbon nano tube in 10mL of water, and performing ultrasonic dispersion to obtain a dispersion liquid; weighing 30mL of octadecene and 100mg of Hypermer2296, and uniformly stirring to obtain an oil phase; dropping the dispersion into oil phase, stirring at high speed for 2min with a homogenizer, maintaining the temperature at 98 deg.C for 3h, and centrifuging and drying to obtain SiO2-carbon nanotube composite microspheres;
(3) to obtain SiO2Mixing the carbon nano tube composite microspheres with potassium chloride according to the mass ratio of 1:21, and then adding SiO2Grinding and mixing magnesium powder with the mass of 50%, heating to 600 ℃ under the protection of hydrogen-argon mixed gas, preserving heat for 1h, cooling, washing with hydrochloric acid, and centrifugally drying to obtain the silicon-carbon nanotube composite porous microspheres;
(4) dispersing 500mg of silicon-carbon nanotube composite porous microspheres in a buffer solution, adding 200mg of dopamine hydrochloride in sample mass, stirring at room temperature for 1h, centrifugally drying, placing the dried product in a tube furnace, heating to 400 ℃ at a certain heating rate under an inert atmosphere, keeping the temperature for 1h, and cooling to room temperature to obtain the carbon-coated silicon-carbon nanotube composite microsphere cathode material.
SEM test is carried out on the obtained silicon carbon-carbon nano tube composite microsphere negative electrode material, and the result is shown in figure 1. As can be seen from FIG. 1, the silicon carbon-carbon nanotube composite material is spherical, and the carbon nanotubes are uniformly inserted and coated outside the composite material, wherein the particle size is about 1-10 μm.
XRD (X-ray diffraction) test is carried out on the obtained silicon-carbon composite anode material, and the result is shown in figure 2. As can be seen from fig. 2, a characteristic diffraction peak of silicon occurs, and a diffraction peak without carbon nanotubes is caused by too small a content.
The tap density test of the obtained silicon carbon-carbon nanotube composite microsphere negative electrode material was carried out, and the result is shown in fig. 3. From the left, only the nano-silicon, the silicon oxide and the silicon carbon-carbon nano tube composite microspheres are respectively arranged, and the tap density of the silicon carbon-carbon nano tube composite microspheres can be seen to be the maximum in the figure.
Grinding and mixing the silicon carbon-carbon nanotube composite microsphere negative electrode material prepared in the embodiment, a conductive agent Super P and a binder sodium alginate according to a mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil by using a scraper, baking the copper foil for 10 hours in a vacuum box at 80 ℃, punching the copper foil, and assembling the button cell by using metal lithium as a counter electrode. FIG. 4 is a charge-discharge curve at a current density of 1C and a reversible specific capacity of 660 mAh/g.
The rate of heating is not particularly limited and claimed in the present invention, and may be at a rate of temperature rise known to those skilled in the art.
Example two
(1) Preparing a mixed solution containing 10mL of water and 80mL of ethanol, adding 3mL of ammonia water, uniformly stirring, quickly adding 6mL of tetraethyl orthosilicate, and stirring for 2 hours to obtain the hydrophilic nano SiO2And centrifugally drying;
(2) 300mg of hydrophilic nano SiO2Dispersing 40mg of carboxylated carbon nanotubes in 10mL of water, and performing ultrasonic dispersion to obtain a dispersion liquid; weighing 40mL of octadecene and 90mg of Hypermer2524, and uniformly stirring to obtain an oil phase; dropping the dispersion into oil phase, stirring at high speed for 3min with a homogenizer, keeping the temperature at 99 deg.C for 3h, and centrifuging and drying to obtain SiO2-carbon nanotube composite microspheres;
(3) to obtain SiO2Mixing the carbon nano tube composite microspheres with potassium chloride according to the mass ratio of 1:25, and then adding SiO2Grinding and mixing 80% magnesium powder, heating to 800 ℃ under the protection of hydrogen-argon mixed gas, preserving heat for 5 hours, cooling, cleaning with hydrochloric acid and hydrofluoric acid, and centrifugally drying to obtain the silicon-carbon nanotube composite porous microspheres;
(4) dispersing 500mg of silicon-carbon nanotube composite porous microspheres in a buffer solution, adding 500mg of dopamine hydrochloride with the sample mass, stirring at room temperature for 24h, centrifugally drying, placing the dried product in a tube furnace, heating to 1000 ℃ at a certain heating rate under an inert atmosphere, keeping the temperature for 3h, and cooling to room temperature to obtain the carbon-coated silicon-carbon nanotube composite microsphere cathode material. The silicon carbon-carbon nanotube composite microsphere negative electrode material has the structure and the performance similar to those of the embodiment 1.
The rate of heating is not particularly limited and claimed in the present invention, and may be at a rate of temperature rise known to those skilled in the art.
EXAMPLE III
(1) Preparing a mixed solution containing 10mL of water and 80mL of ethanol, adding 3mL of ammonia water, uniformly stirring, quickly adding 6mL of tetraethyl orthosilicate, and stirring for 2 hours to obtain the hydrophilic nano SiO2And centrifugally drying;
(2) 500mg of hydrophilic nano SiO2Dispersing the carbon nano tube and 100mg of carboxylated carbon nano tube in 8mL of water, and performing ultrasonic dispersion to obtain a dispersion liquid; measuring 40mL of octadecene and 80mg of Hypermer B-210, and uniformly stirring to obtain an oil phase; dropping the dispersion into oil phase, stirring at high speed for 2min with a homogenizer, keeping the temperature at 100 deg.C for 3h, and centrifuging and drying to obtain SiO2-carbon nanotube composite microspheres;
(3) to obtain SiO2Mixing the carbon nano tube composite microspheres with potassium chloride according to the mass ratio of 1:25, and then adding SiO2Grinding and mixing 90% magnesium powder, heating to 700 ℃ under the protection of hydrogen-argon mixed gas, preserving heat for 4 hours, cooling, cleaning with hydrochloric acid and hydrofluoric acid, and centrifugally drying to obtain the silicon-carbon nanotube composite porous microspheres;
(4) dispersing 500mg of silicon-carbon nanotube composite porous microspheres in a buffer solution, adding dopamine hydrochloride with the mass of 400mg of a sample, stirring at room temperature for 5h, centrifugally drying, placing the dried product in a tube furnace, heating to 800 ℃ at a certain heating rate under an inert atmosphere, keeping the temperature for 4h, and cooling to room temperature to obtain the carbon-coated silicon-carbon nanotube composite microsphere cathode material.
The tap density test of the obtained silicon carbon-carbon nanotube composite microsphere negative electrode material was carried out, and the result is shown in fig. 3. From the left, only the nano-silicon, the silicon oxide and the silicon carbon-carbon nano tube composite microspheres are respectively arranged, and the tap density of the silicon carbon-carbon nano tube composite microspheres can be seen to be the maximum in the figure.
The silicon carbon-carbon nanotube composite microsphere negative electrode material has the structure and the performance similar to those of the embodiment 1.
The rate of heating is not particularly limited and claimed in the present invention, and may be at a rate of temperature rise known to those skilled in the art.
Example four
(1) Preparing a mixed solution containing 10mL of water and 80mL of ethanol, adding 3mL of ammonia water, uniformly stirring, quickly adding 6mL of tetraethyl orthosilicate, and stirring for 2 hours to obtain the hydrophilic nano SiO2And centrifugally drying;
(2) 200mg of hydrophilic nano SiO2Dispersing the carbon nano tube and 20mg of aminated carbon nano tube in 5mL of water, and performing ultrasonic dispersion to obtain a dispersion liquid; weighing 40mL of octadecene and 100mg of Hypermer2234, and uniformly stirring to obtain an oil phase; dropping the dispersion into oil phase, stirring at high speed for 2min with a homogenizer, maintaining the temperature at 98 deg.C for 3h, and centrifuging and drying to obtain SiO2-carbon nanotube composite microspheres;
(3) to obtain SiO2Mixing the carbon nano tube composite microspheres with potassium chloride according to the mass ratio of 1:30, and then adding SiO2Grinding and mixing 100% magnesium powder, heating to 600 ℃ under the protection of hydrogen-argon mixed gas, preserving heat for 5 hours, cooling, cleaning with hydrochloric acid and hydrofluoric acid, and centrifugally drying to obtain the silicon-carbon nanotube composite porous microspheres;
(4) dispersing 500mg of silicon-carbon nanotube composite porous microspheres in a buffer solution, adding 300mg of dopamine hydrochloride in sample mass, stirring at room temperature for 8h, centrifugally drying, placing the dried product in a tube furnace, heating to 900 ℃ at a certain heating rate under an inert atmosphere, keeping the temperature for 5h, and cooling to room temperature to obtain the carbon-coated silicon-carbon nanotube composite microsphere cathode material.
The silicon carbon-carbon nanotube composite microsphere negative electrode material has the structure and the performance similar to those of the embodiment 1.
The rate of heating is not particularly limited and claimed in the present invention, and may be at a rate of temperature rise known to those skilled in the art.
EXAMPLE five
(1) Preparing a mixed solution containing 10mL of water and 80mL of ethanol, adding 3mL of ammonia water, uniformly stirring, quickly adding 6mL of tetraethyl orthosilicate, and stirring for 2 hours to obtain the hydrophilic nano SiO2And centrifugally drying;
(2) 400mg of hydrophilic nano SiO2Dispersing the mixture and 80mg of aminated carbon nano tube in 10mL of water, and performing ultrasonic dispersion to obtain a dispersion liquid; measuring 40mL of octadecene and 95mg of Hypermer1031, and uniformly stirring to obtain an oil phase; dropping the dispersion into oil phase, stirring at high speed for 2min with a homogenizer, keeping the temperature at 99 deg.C for 3h, and centrifuging and drying to obtain SiO2-carbon nanotube composite microspheres;
(3) to obtain SiO2Mixing the carbon nano tube composite microspheres with potassium chloride according to the mass ratio of 1:25, and then adding SiO2Grinding and mixing 100% magnesium powder, heating to 650 ℃ under the protection of hydrogen-argon mixed gas, preserving heat for 4 hours, cooling, cleaning with hydrochloric acid and hydrofluoric acid, and centrifugally drying to obtain the silicon-carbon nanotube composite porous microspheres;
(4) dispersing 500mg of silicon-carbon nanotube composite porous microspheres in a buffer solution, adding 200mg of dopamine hydrochloride in sample mass, stirring at room temperature for 20h, centrifugally drying, placing the dried product in a tube furnace, heating to 700 ℃ at a certain heating rate under an inert atmosphere, keeping the temperature for 4h, and cooling to room temperature to obtain the carbon-coated silicon-carbon nanotube composite microsphere cathode material.
The silicon carbon-carbon nanotube composite microsphere negative electrode material has the structure and the performance similar to those of the embodiment 1.
The rate of heating is not particularly limited and claimed in the present invention, and may be at a rate of temperature rise known to those skilled in the art.
Claims (6)
1. A preparation method of a silicon carbon-carbon nanotube composite microsphere cathode material of a lithium ion battery is characterized in that the silicon carbon-carbon nanotube composite microsphere cathode material is formed by combining three materials of porous nano-silicon, carbon nanotubes and amorphous carbon in a specific distribution mode, a carbon layer is coated on the surface of the porous nano-silicon, the porous nano-silicon coated with the carbon is assembled into micron-sized spherical porous silicon, and the carbon nanotubes are distributed in and on the surface of the microsphere in a penetrating and interweaving manner; the porous structure is a micropore and a mesopore, and the silicon carbon-carbon nanotube composite microsphere negative electrode material is a microsphere with the granularity of 1-50 mu m; the preparation method comprises the following specific steps:
(1) hydrophilic SiO2The synthesis of (2): according to the volume ratio of water to ethanol of 1: 8 preparing an ethanol solution, adding ammonia water and tetraethyl orthosilicate, and stirring for a certain time to obtain 200-400 nm hydrophilic SiO2；
(2)SiO2-carbon nanotube composite microsphere preparation: according to the weight ratio of silicon dioxide: water: oil proportion is 0.2-0.5 g: 5-10 mL: 30-40 mL of hydrophilic SiO in the step (1)2Adding into deionized water, and adding hydrophilic SiO21-20% by mass of hydrophilic carbon nanotubes, and stirring and dispersing to obtain a dispersion liquid; dripping the dispersion liquid into an octadecylene oil phase containing an emulsifier, stirring at a high speed for 2-3 min, and keeping the temperature at 98-100 ℃ for 2.5-3.5h to obtain SiO of a spherical center2-carbon nanotube composite microspheres;
(3) preparing the silicon-carbon nanotube composite microspheres: the SiO obtained in the step (2) is2Mixing the-carbon nano tube composite microspheres with potassium chloride according to the mass ratio of 1: 21-30, and adding SiO2Grinding and mixing magnesium powder with the mass of 50-100%, heating to 600-800 ℃ under the protection of hydrogen-argon mixed gas, preserving heat for 1-5 h, cooling, cleaning with acid, and drying to obtain the silicon-carbon nanotube composite porous microspheres;
(4) preparing carbon-coated silicon-carbon nanotube composite microspheres: dispersing the sample prepared in the step (3) in a buffer solution, adding dopamine hydrochloride with the mass of 20-100% of that of the sample, stirring for a certain time at room temperature, centrifugally drying, placing the dried product in a tubular furnace, heating to 400-1000 ℃ at a certain heating rate under an inert atmosphere, keeping the temperature for 1-10 hours, and cooling to room temperature to obtain the carbon-coated silicon carbon-carbon nanotube composite microsphere negative electrode material.
2. The preparation method of the silicon carbon-carbon nanotube composite microsphere negative electrode material of the lithium ion battery according to claim 1, wherein the certain time in the step (1) is 2-10 hours.
3. The method for preparing the silicon-carbon nanotube composite microsphere anode material of the lithium ion battery according to claim 1, wherein the oil in the step (2) is octadecene; the hydrophilic carbon nano tube is one or more of hydroxyl, carboxyl and aminated carbon nano tube; the emulsifier is one or more of Hypermer2296, Hypermer2524, Hypermer1031, Hypermer B-210 and Hypermer 2234.
4. The method for preparing the silicon carbon-carbon nanotube composite microsphere anode material of the lithium ion battery according to claim 1, wherein the acid in the step (3) is one or two of hydrochloric acid and hydrofluoric acid.
5. The method for preparing the silicon-carbon nanotube composite microsphere anode material of the lithium ion battery according to claim 1, wherein the buffer solution in the step (4) is a solution with a pH value of 8 prepared by Tris-base; stirring for a certain time of 1-24 hours; the inert atmosphere is nitrogen, argon or helium.
6. The preparation method of the silicon carbon-carbon nanotube composite microsphere anode material for the lithium ion battery according to claim 5, wherein the stirring is carried out for a certain time of 5-20 hours.
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| CN114156445B (en) * | 2021-10-28 | 2023-12-19 | 西安交通大学 | Electrode material with bionic shell lamellar structure and preparation method and application thereof |
| CN113793931B (en) * | 2021-11-18 | 2022-02-08 | 河南电池研究院有限公司 | Iron oxide negative electrode material for lithium ion battery and preparation method thereof |
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Effective date of registration: 20211123 Address after: 046700 Mishan Industrial Park, Gaoping economic and Technological Development Zone, Gaoping City, Jincheng City, Shanxi Province Patentee after: Shanxi Beike Qiantong Energy Storage Technology Research Institute Co.,Ltd. Address before: 100083 No. 30, Haidian District, Beijing, Xueyuan Road Patentee before: University OF SCIENCE AND TECHNOLOGY BEIJING |