CN109962214B - Carbon nano-layer coated silicon negative electrode material and preparation and application thereof - Google Patents
Carbon nano-layer coated silicon negative electrode material and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion negative electrode materials, in particular to a carbon nano-layer coated silicon negative electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: A. preparing a carbon precursor; B. preparing a carbon-silicon precursor; C. preparing the carbon nano-layer coated silicon cathode material. The prepared carbon-silicon negative electrode material is of a nano-sheet structure of porous carbon-coated nano silicon, and the coated silicon nano particles are distributed on the surface of the carbon layer. The volume expansion of silicon is greatly reduced by the coating structure; the porous structure with high porosity effectively relieves the influence of silicon expansion on the electrode structure; and the carbon nanolayers provide a better conductive network. The coating method is simple and convenient, has wide raw material sources, low price, easily controlled process conditions and low operation cost, and has great industrial prospect. Compared with the existing coating method, the method has the advantages of uniform coating layer, high coating speed and the like. The carbon nano-layer coated silicon negative electrode material has high specific capacity and excellent cycle performance and rate capability.
Description
Technical Field
The invention relates to the technical field of lithium ion negative electrode materials, in particular to a carbon nano-layer coated silicon negative electrode material and a preparation method thereof.
Background
The lithium ion battery, as an energy storage device with wide application, has the advantages of high energy density, small self-discharge, wide working voltage range, no memory effect, long service life, no environmental pollution and the like, and the final decisive factor of the performance of the lithium ion battery is an electrode material, wherein a negative electrode material plays a crucial role in improving the performance of the lithium ion battery. At present, the application of the negative electrode material is mainly based on the traditional graphite material, but the specific capacity of the graphite is close to the theoretical value of 372mAh/g, so that the space for improving the specific capacity is difficult to be provided, and the requirement of a high-specific-energy power lithium battery cannot be met, so that the development of other novel negative electrode materials so as to improve the performance of the lithium battery becomes a hotspot in the research field of negative electrode materials.
The theoretical specific capacity of silicon is 4200mAh/g, which is much higher than that of graphite material, and the voltage platform of silicon is slightly higher than that of graphite, which does not cause surface lithium precipitation during charging, and has better safety performance. But silicon is used as the lithium ion battery cathode material, and the volume expansion reaches 300 percent in the lithium intercalation process. In the charging and discharging process, lithium ions are repeatedly inserted and removed, the material is gradually pulverized, the structure is collapsed, finally, the electrode active substance is separated from the current collector, the electric contact is lost, and the cycle performance of the battery is greatly reduced; in addition, due to such a volume effect, silicon has difficulty in forming a stable Solid Electrolyte Interface (SEI) film in an electrolyte solution; with the destruction of the electrode structure, new SEI films are continuously formed on the exposed silicon surface, which aggravates silicon corrosion and capacity fade.
At present, a coating or high-dispersion system is formed mainly by surface modification, doping, compounding and other methods for modifying a high-capacity silicon negative electrode material, and the damage of internal stress generated by volume expansion in the lithium releasing and embedding process to a material structure is relieved by improving the mechanical property of the material, so that the electrochemical cycle stability of the material is improved. Most of carbon-silicon cathodes coated by organic carbon source surface polymerization (CN103531760B, CN104466185A) or hydrothermal carbonization are monodisperse carbon-silicon nanospheres, although the materials can be improved to a certain extent on the cyclicity, the electron conduction among particles is greatly limited, the effect is still not ideal, and the performance requirements of high-performance power lithium ion batteries cannot be met.
What the current cladding structure does is, what problems (in combination with the reference) compare with the advantages of the technical scheme of the invention
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides an effective method for coating a silicon cathode material with carbon for a lithium ion battery, which can obviously reduce the specific capacity attenuation speed of the carbon-silicon cathode material, improve the cycle performance of the carbon-silicon cathode material, provide a high-efficiency electron conduction channel and improve the rate capability of the battery. The invention is realized by adopting the following specific scheme:
(1) stirring polyol and inorganic acid uniformly, heating and vacuumizing to perform esterification reaction, adding amino compound-containing dispersion liquid into the obtained reaction product, mixing uniformly again, and heating to perform salt forming reaction to obtain a carbon precursor suspension:
(2) uniformly mixing the carbon precursor suspension obtained in the step (1) with nano silicon oxide;
(3) and (3) carbonizing the carbon-silicon precursor obtained in the step (2) at high temperature in an inert atmosphere and carrying out magnesiothermic reduction to obtain the carbon-silicon cathode.
The mass ratio of the polyhydric alcohol to the inorganic acid in the step (1) is 1: 3-1: 8; the ratio of the amounts of the inorganic acid to the amino compound is 5:1-1: 1.
the solvent in the step (1) is water, methanol, ethanol, glycol or a mixed solution of two or more of the above; the polyalcohol is one or more than two of pentaerythritol, xylitol and sorbitol; the inorganic acid is one or more than two of boric acid, phosphoric acid, sulfuric acid and nitric acid; the amino compound is one or more than two of urea, melamine, cyanamide and amino acid.
The mass concentration of the amino compound-containing dispersion liquid in the step (1) is 3-50%.
The esterification reaction in the step (1) is carried out for 0.5-5h at the temperature of 70-200 ℃; the vacuum degree is 0.03-0.2Mpa, and the salt-forming reaction condition is that the reaction is carried out for 2-24h at the temperature of 30-150 ℃.
In the step (2), the nano silicon oxide is one or two of silicon-containing natural minerals such as 10-100nm silicon oxide spheres, mesoporous silicon such as MCM-41, SBA-15 and the like, diatomite and the like.
The mass ratio of the nano silicon oxide to the carbon precursor in the step (2) is 1:50-1: 10.
The carbonization treatment conditions in the step (3) are as follows: heating to 300-600 ℃ and keeping for 0.5-3h, continuously heating to 700-1100 ℃, keeping the temperature for 0.5-3h, and cooling to room temperature.
The carbonization treatment condition in the step (3) is that the temperature rising rate is 2-10 ℃/min
And (3) the inert gas in the step (3) is one or a mixture of nitrogen and argon.
In the step (3), the mass ratio of the magnesium powder to the carbonized carbon-silicon composite in the magnesium thermal reduction step is 1:2-5:1, heating to 500-700 ℃ and keeping for 2-20h, wherein the heating rate is 2-10 ℃/min, cooling to room temperature, and the inert gas is one or a mixture of two of hydrogen and argon. And soaking, washing and drying the obtained product by using 1M hydrochloric acid to obtain the carbon-silicon negative electrode material.
Compared with the prior art, the carbon-silicon cathode material prepared by the invention is of a lamellar structure, and the coated silicon nano particles are distributed on the surface of the carbon layer. The volume expansion of silicon is greatly reduced by the coating structure; the gel structure with high porosity effectively relieves the influence of silicon expansion on the electrode structure; and the carbon nanolayers provide a better conductive network. Due to the protection of the carbon coating layer, the silicon material gradually participates in electrochemical reaction in the circulation process, and the circulation performance of the silicon material is obviously improved. The method is simple and convenient, has low operation cost and has great industrial prospect.
Drawings
FIG. 1: scanning electron micrographs of the silicon negative electrode material;
FIG. 2: scanning electron micrographs of the silicon negative electrode material;
FIG. 3: a transmission electron micrograph of the silicon negative electrode material;
FIG. 4: transmission electron micrographs of silicon negative electrode material.
Detailed Description
Example 1
6.8g of pentaerythritol is weighed in a flask, 29.40g of phosphoric acid is added, the mixture is stirred and decompressed (the vacuum degree is 0.1MPa), the mixture is heated to 120 ℃, and the temperature is kept for 1.5h, so that light yellow transparent viscous pentaerythritol phosphate liquid is obtained. Adding 120mL of ethanol and 16.38g of melamine into another round-bottom flask, fully stirring for 3h, pouring pentaerythritol phosphate synthesized in the previous step into the melamine filled with an ethanol dispersant, heating to 80 ℃, stirring and refluxing for 6h, performing rotary evaporation to obtain a precursor, uniformly mixing 2g of the precursor and 200mg of silicon oxide spheres with the diameter of 30nm, putting the mixture into a quartz boat, heating to 350 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping for 0.5h, continuously heating to 950 ℃ at the heating rate of 5 ℃/min, keeping for 2h, cooling to room temperature, and taking out. Heating the magnesium powder and the carbonized carbon-silicon composite to 600 ℃ according to the mass ratio of 3:1, keeping the temperature for 3 hours, cooling to room temperature at the heating rate of 5 ℃/min, and taking argon as inert gas. And soaking, washing and drying the obtained product by using 1M hydrochloric acid to obtain the carbon-silicon negative electrode material. The obtained silicon negative electrode material is composed of silicon nano particles embedded in a carbon nano layer as shown in a scanning electron microscope of figure 1.
Example 2
6.8g of pentaerythritol is weighed in a flask, 29.40g of phosphoric acid is added, the mixture is stirred and decompressed (the vacuum degree is 0.1MPa), the mixture is heated to 120 ℃, and the temperature is kept for 1.5h, so that light yellow transparent viscous pentaerythritol phosphate liquid is obtained. Adding 120mL of ethanol and 16.38g of melamine into another round-bottom flask, fully stirring for 3h, pouring pentaerythritol phosphate synthesized in the previous step into the melamine filled with an ethanol dispersant, heating to 80 ℃, stirring and refluxing for 6h, performing rotary evaporation to obtain a precursor, uniformly mixing 2g of the precursor and 100mg of silicon oxide spheres with the diameter of 50nm, putting the mixture into a quartz boat, heating to 350 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping for 0.5h, continuously heating to 950 ℃ at the heating rate of 5 ℃/min, keeping for 2h, cooling to room temperature, and taking out. Heating the magnesium powder and the carbonized carbon-silicon composite to 600 ℃ according to the mass ratio of 3:1, keeping the temperature for 3 hours, cooling to room temperature at the heating rate of 5 ℃/min, and taking argon as inert gas. And soaking, washing and drying the obtained product by using 1M hydrochloric acid to obtain the carbon-silicon negative electrode material. The obtained silicon negative electrode material is composed of silicon nano-particles embedded in a carbon nano-layer as shown in a scanning electron microscope of figure 2.
Example 3
6.8g of pentaerythritol is weighed in a flask, 29.40g of phosphoric acid is added, the mixture is stirred and decompressed (the vacuum degree is 0.1MPa), the mixture is heated to 120 ℃, and the temperature is kept for 1.5h, so that light yellow transparent viscous pentaerythritol phosphate liquid is obtained. Adding 120mL of ethanol and 16.38g of melamine into another round-bottom flask, fully stirring for 3h, pouring pentaerythritol phosphate synthesized in the previous step into the melamine filled with an ethanol dispersant, heating to 80 ℃, stirring and refluxing for 6h, performing rotary evaporation to obtain a precursor, uniformly mixing 2g of the precursor and 100mg of silicon oxide spheres with the diameter of 50nm, putting the mixture into a quartz boat, heating to 350 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping for 0.5h, continuously heating to 950 ℃ at the heating rate of 5 ℃/min, keeping for 2h, cooling to room temperature, and taking out. Heating the magnesium powder and the carbonized carbon-silicon composite to 600 ℃ according to the mass ratio of 3:1, keeping the temperature for 3 hours, cooling to room temperature at the heating rate of 5 ℃/min, and taking argon as inert gas. And soaking, washing and drying the obtained product by using 1M hydrochloric acid to obtain the carbon-silicon negative electrode material. The obtained silicon negative electrode material is composed of silicon nanoparticles embedded in a carbon nano layer as shown in fig. 3 and 4 transmission electron microscope, and the diameter of the silicon nanoparticles is about 50 nm.
Claims (10)
1. A carbon-silicon composite negative electrode material is characterized in that: the silicon nano-particles are embedded in the carbon nano-layer to form the nano-silicon nano-particle coating, the mass content of the silicon nano-particles is 20-80%, and the particle size of the silicon nano-particles is 10-100 nm;
the preparation method of the carbon-silicon composite negative electrode material comprises the following steps,
(1) stirring polyalcohol and inorganic acid uniformly, heating and vacuumizing to perform esterification reaction, adding amino compound-containing dispersion liquid into the obtained esterification reaction product, mixing uniformly again, heating to perform salt forming reaction to obtain carbon precursor suspension, and drying to obtain carbon precursor;
(2) uniformly mixing the carbon precursor obtained in the step (1) with nano silicon oxide;
(3) and (3) carbonizing the mixture obtained in the step (2) at high temperature in an inert atmosphere and carrying out magnesiothermic reduction to obtain the carbon-silicon cathode.
2. A method for preparing the carbon-silicon composite anode material of claim 1, which is characterized by comprising the following steps:
comprises the following steps of (a) carrying out,
(1) stirring polyalcohol and inorganic acid uniformly, heating and vacuumizing to perform esterification reaction, adding amino compound-containing dispersion liquid into the obtained esterification reaction product, mixing uniformly again, heating to perform salt forming reaction to obtain carbon precursor suspension, and drying to obtain carbon precursor;
(2) uniformly mixing the carbon precursor obtained in the step (1) with nano silicon oxide;
(3) and (3) carbonizing the mixture obtained in the step (2) at high temperature in an inert atmosphere and carrying out magnesiothermic reduction to obtain the carbon-silicon cathode.
3. The method of claim 2, wherein:
the mass ratio of the polyhydric alcohol to the inorganic acid in the step (1) is 2:1-1: 8; the mass ratio of the inorganic acid to the amino compound is 5:1-1: 5;
the solvent adopted by the amino compound-containing dispersion liquid in the step (1) is water, methanol, ethanol, ethylene glycol or a mixed solution of two or more of the two; the polyalcohol is one or more than two of pentaerythritol, xylitol and sorbitol; the inorganic acid is one or more than two of boric acid, phosphoric acid, sulfuric acid and nitric acid; the amino compound is one or more than two of urea, melamine, cyanamide and amino acid;
the mass concentration of the amino compound-containing dispersion liquid is 3-50%.
4. The method of claim 2, wherein: the esterification reaction in the step (1) is carried out for 0.5-5h at the temperature of 70-200 ℃; the vacuum degree is 0.03-0.2Mpa, and the salt-forming reaction condition is that the reaction is carried out for 2-24h at the temperature of 30-150 ℃.
5. The method of claim 2, wherein: the nano silicon oxide in the step (2) is one or more than two of silicon oxide spheres of 10nm-100nm, MCM-41 and SBA-15;
the mass ratio of the nano silicon oxide to the carbon precursor in the step (2) is 1:50-1: 10.
6. The method of claim 2, wherein: the carbonization treatment conditions in the step (3) are as follows: raising the temperature from room temperature to 300-600 ℃ and keeping the temperature for 0.5-3h, continuously raising the temperature to 700-1100 ℃, keeping the temperature for 0.5-3h, and cooling to room temperature.
7. The method of claim 6, wherein:
in the carbonization treatment process in the step (3), the temperature rise rate is 2-10 ℃/min;
and (3) the inert atmosphere gas in the step (3) is one or a mixture of nitrogen and argon.
8. The method of claim 1, wherein:
in the step (3), the mass ratio of the magnesium powder to the carbonized carbon-silicon composite in the magnesiothermic reduction step is 1:2-5:1, the temperature is raised from room temperature to 500-700 ℃ and kept for 2-20h, the temperature raising rate is 2-10 ℃/min, the magnesium is reduced and then cooled to room temperature, and the magnesiothermic reduction atmosphere is one or two of hydrogen and argon.
9. The method of claim 1, wherein: soaking, washing and drying the obtained product by hydrochloric acid to obtain the carbon-silicon composite negative electrode material; the molar concentration of the hydrochloric acid is 0.2-2 mol/L.
10. The application of the carbon-silicon composite negative electrode material as claimed in claim 1, which is characterized in that: the carbon-silicon cathode is a lithium ion battery cathode.
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| CN104466185A (en) * | 2014-11-12 | 2015-03-25 | 中国科学院深圳先进技术研究院 | Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof |
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| CN106898491A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of electrode of super capacitor and its preparation |
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| CN101826612A (en) * | 2009-03-06 | 2010-09-08 | 五邑大学 | Preparation method of lithium ion battery silicon-carbon cathode material |
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