CN114314594A - Nano flaky silicon-carbon composite material used as lithium ion battery cathode material and preparation method thereof - Google Patents
Nano flaky silicon-carbon composite material used as lithium ion battery cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano flaky silicon-carbon composite material used as a lithium ion battery cathode material and a preparation method thereof. The composite material has excellent cycling stability and lithium storage capacity, and has the advantages of simple preparation process, controllable conditions and lower cost.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery cathode material, in particular to a preparation method of a nano flaky silicon-carbon composite material used as a lithium ion battery cathode material, and belongs to the technical field of lithium ion battery cathode materials.
Background
Silicon can form Li with lithium at room temperature15Si4The theoretical capacity of the alloy can reach 3590mAh g-1And has huge lithium intercalation potential. However, the silicon negative electrode material is Li-intercalated15Si4The phase causes a volume expansion of more than 300%, and repeated volume expansion and contraction during the lithium intercalation/deintercalation process causes particle breakage, and it is difficult to form a stable solid electrolyte interface film in the electrolyte, which increases corrosion of silicon and capacity fade. In addition, the defect of poor conductivity of silicon as a semiconductor limits the practical use of pure silicon negative electrode materials.
In the middle of the 90's of the 20 th century, the American Air Force Research Lab (AFRL) developed a nanostructured hybrid system of polyhedral oligomeric Silsesquioxane (Silesquioxane). Silsesquioxanes are a class of organic-inorganic hybrid molecules interconnected by Si-O bonds, having a chemical composition according to the empirical relationship (RSiO1.5) n, where R is a variety of organic groups attached to the silicon atom. The silsesquioxane can be used as a precursor for preparing a silicon/carbon composite material by magnesiothermic reduction due to the special nano hybrid structure and ingenious chemical bond bridging. At present, a magnesiothermic reduction method is mostly used for preparing pure-phase nano silicon cathode materials, and few reports are made on the research of preparing nano silicon/carbon composite materials by directly carrying out magnesium thermal reaction on the basis of cage-type silsesquioxane.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a nano flaky silicon-carbon composite material used as a negative electrode material of a lithium ion battery, so that the nano flaky silicon-carbon composite material has the advantages of good cycle stability and high lithium storage capacity.
The invention adopts the following technical scheme for realizing the purpose:
a preparation method of a nano flaky silicon-carbon composite material used as a lithium ion battery cathode material comprises the following steps:
(1) precursor powder preparation
Weighing cage type silsesquioxane, a carbon source and molten salt, placing the cage type silsesquioxane, the carbon source and the molten salt in a mortar, grinding uniformly, mixing in a ball mill, and drying to obtain precursor powder; wherein the mass ratio of the cage-type silsesquioxane to the molten salt is 0.05-0.1: 1, the mass ratio of the cage-type silsesquioxane to the carbon source is 1:0 to 0.5;
(2) high temperature magnesiothermic reduction
Placing the precursor powder at one end of a stainless steel burning boat, adding magnesium powder at the other end of the stainless steel burning boat, transferring the burning boat into a sealable reaction kettle, carrying out heat preservation reaction in a sealed high-temperature reactor at the temperature of 300-600 ℃ for 2-12 h under a protective atmosphere, and naturally cooling to room temperature; wherein the mass ratio of the cage-type silsesquioxane to the magnesium powder is 0.25-4: 1;
(3) washing and drying to obtain the composite material
And (3) placing the reaction product obtained in the step (2) in a beaker, adding deionized water and HCl solution, stirring at normal temperature for reaction for 1.5-3 h, centrifuging, washing, drying and grinding to obtain the nano flaky silicon-carbon composite material used as the lithium ion battery cathode material.
Further, in step 1, the cage-type silsesquioxane is at least one of hydrogen-based octahedral cage-type silsesquioxane, vinyl-based octahedral cage-type silsesquioxane or phenyl-based octahedral cage-type silsesquioxane.
Further, in step 1, the carbon source is at least one of sucrose, glucose and citric acid.
Further, in the step 1, the molten salt is 20-80% of two of sodium chloride, lithium chloride, potassium chloride and aluminum chloride by mass percent: 80-20% of the mixture.
Further, in the step 1, the rotation speed of ball milling is 100-1000 rpm, the ball milling time is 1.5-2.5 h, the drying temperature is 30-100 ℃, and the drying time is 1.5-5 h.
Further, in the step 2, the protective atmosphere is nitrogen, or argon and hydrogen in a volume ratio of 90-100%: 10 to 0 percent of mixed gas.
Further, in step 3, the ratio of the reaction product to deionized water and a HCl solution with a mass concentration of 36% is 10 g: 200-500 mL: 5-10 mL.
Further, in the step 3, the centrifugal rotating speed is 5000-10000 rpm, the centrifugal time is 1-4 min, the washing is performed by alternately washing with deionized water and ethanol, the drying temperature is 60-100 ℃, and the drying time is 3-8 h.
The nano sheet silicon-carbon composite material prepared by the preparation method is formed by embedding silicon nano particles on a two-dimensional carbon nano sheet.
Compared with the prior art, the invention has the beneficial effects that:
1. most of reported nano-silicon is synthesized by methods such as chemical vapor deposition or directly uses commercialized nano-silicon particles, and the nano-silicon material is expensive, so that the cost in practical application is huge, and the practicability of the nano-silicon cathode material is not facilitated. According to the invention, cage type silsesquioxane with silicon element as a framework is used as a precursor, a magnesium thermal reduction reaction process based on a molten salt system is established, and in-situ conversion of organic siloxane is realized, so that the nano flaky silicon-carbon composite material is obtained. The composite material has the advantages of simple preparation process, controllable conditions, lower cost compared with the traditional nano silicon cathode material and better electrochemical performance.
2. Compared with the common silicon-based material, the silicon nanoparticles compounded on the two-dimensional carbon nanosheets can be better contacted with the electrolyte, so that the charge transmission efficiency in the charging and discharging process is effectively improved; and the nano-scale silicon material is embedded on the carbon sheet with better flexibility, so that the volume expansion of Si particles in the charging and discharging process can be better relieved, and the cycling stability and the lithium storage capacity of the material are greatly improved.
3. In the preparation method, the magnesium thermal reduction donor can obtain silicon nanoparticles with smaller particles by virtue of huge enthalpy change, so that the performance of the silicon nanoparticles as a negative electrode material is further improved.
Drawings
Fig. 1 is a TEM image of the nano sheet silicon carbon composite material prepared in example 1 of the present invention, wherein (a) and (b) correspond to different magnifications.
Fig. 2 is an EDS energy spectrum of the nano sheet silicon carbon composite material prepared in example 1 of the present invention.
Fig. 3 is an XRD pattern of the nano-sheet silicon carbon composite material prepared in example 1 of the present invention.
Fig. 4 is an XPS chart of the nano sheet silicon carbon composite prepared in example 1 of the present invention.
Fig. 5 is a graph of the cycle performance of the nano-sheet silicon-carbon composite material prepared in example 1 of the present invention.
Fig. 6 is an XRD chart of the nano-sheet silicon-carbon composite material prepared in example 2 of the present invention.
Fig. 7 is a cycle performance diagram of the nano sheet silicon carbon composite material prepared in example 2 of the present invention.
Fig. 8 is a graph of the cycle performance of the nano-sheet silicon-carbon composite material prepared in example 3 of the present invention.
Fig. 9 is a graph of the cycle performance of the nano-sheet silicon-carbon composite material prepared in example 4 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, but the present invention is not limited to the following examples, for better understanding of the technical features, objects and advantages of the present invention.
Example 1
In this example, the nano-sheet silicon-carbon composite material is prepared by the following steps:
(1) precursor powder preparation
0.5g of vinyl cage type octahedral silsesquioxane, 4.5g of lithium chloride and 5.5g of potassium chloride are weighed and put into a mortar for grinding for 10min, and the ground powder is ball-milled in a ball mill at 500rpm for 2 h. And drying the ball-milled mixture at 70 ℃ for 4h to obtain precursor powder.
(2) High temperature magnesiothermic reduction
The precursor powder was placed at one end of a stainless steel burn boat, 0.5g of magnesium powder was added at the other end, and the burn boat was transferred to a tube furnace. Then heating to 400 ℃ at the heating rate of 5 ℃/min under argon, carrying out heat preservation reaction for 4h, and naturally cooling to room temperature.
(3) Washing and drying to obtain the composite material
And (3) putting 10g of the reaction product obtained in the step (2) into a beaker, adding 500mL of deionized water and 10mL of 36% HCl solution, stirring at normal temperature for reaction for 2h, centrifuging at 7000rpm for 2min, alternately washing with deionized water and ethanol, drying at 80 ℃ for 5h, and grinding to obtain the nano flaky silicon-carbon composite material used as the lithium ion battery cathode material.
Fig. 1 is a TEM image of the nano-sheet silicon-carbon composite prepared in this example, wherein (a) and (b) correspond to different magnifications. Fig. 2 is an EDS energy spectrum of the nano-sheet silicon-carbon composite material prepared in this example. It can be seen from the figure that the obtained composite material is uniformly embedded with silicon nanoparticles with the diameter of between 5 and 20nm on a two-position carbon nano sheet. Since the thermal magnesium reduction vinyl cage-type octahedral silsesquioxane of the LiCl-KCl system belongs to a flow-solid phase non-catalytic reaction, the reaction can be presumed to be carried out by a core shrinkage model, and the Gibbs free energy of the core shrinkage model growing into spherical solid particles is minimum, so that the microsphere particles are in a solid sphere shape. The mass ratio of the two elements of silicon and carbon in the energy spectrum diagram is about 1:3, and the reduced silicon simple substance accounts for about 25% of the total mass.
Fig. 3 and 4 are an XRD chart and an XPS chart of the nano flaky silicon carbon composite prepared in this example, respectively. The XRD pattern shows a diffraction peak of amorphous carbon at 2 θ ═ 21.8 °, and shows diffraction peaks of (111) and (220) of crystalline Si at 2 θ ═ 28.4 ° and 2 θ ═ 47.4 °, respectively, indicating that elemental silicon is magnesiothermally reduced under the protection of an inert atmosphere. XRD pattern indicated that the nanoparticles were crystalline Si; XPS showed that the absorption of Si 2p was close to 99eV (elemental silicon), further indicating that the nanoparticles uniformly embedded on the carbon nanoplatelets are crystalline Si.
The nano flaky silicon-carbon composite material obtained in the embodiment is prepared into slurry with the ratio of Sodium Alginate (SA) to acetylene black of 6:2:2, and the slurry is uniformly coated on a copper foil to prepare a copper foilThe pole piece to assemble into CR2032 type button cell battery in being full of the argon gas glove box, the order of group commentaries on classics battery is: negative electrode shell-lithium piece-100 mul electrolyte-diaphragm-20 mul electrolyte-electrode piece-positive electrode shell. Wherein the electrolyte is lithium hexafluorophosphate (LiPF6) -Ethylene Carbonate (EC)/dimethyl carbonate (DMC), and the volume of the EC and DMC is 1: 1; the diaphragm was Celgard-2400 polypropylene. Within a voltage window of 0-3V, 100-2000 mAg-1And testing the electrochemical performance of the material under the current density.
FIG. 5 is a graph of the cycle performance of the nano-sheet silicon-carbon composite material prepared in this example, and it can be seen that the battery assembled by the nano-sheet silicon-carbon composite material is 500mAg-1The capacity can be kept at 1000mAhg after 100 cycles under the current density-1The battery capacity retention rate was 71%.
Example 2
In this example, the nano-sheet silicon-carbon composite material is prepared by the following steps:
(1) precursor powder preparation
0.5g of phenyl cage type octahedral silsesquioxane, 4.5g of lithium chloride and 5.5g of potassium chloride are weighed and put into a mortar for grinding for 10min, and the ground powder is ball-milled and mixed in a ball mill at 500rpm for 2 h. And drying the ball-milled mixture at 70 ℃ for 4h to obtain precursor powder.
(2) High temperature magnesiothermic reduction
The precursor powder was placed at one end of a stainless steel burn boat, 0.5g of magnesium powder was added at the other end, and the burn boat was transferred to a tube furnace. Then heating to 300 ℃ at the heating rate of 5 ℃/min under argon, carrying out heat preservation reaction for 4h, and naturally cooling to room temperature.
(3) Washing and drying to obtain the composite material
And (3) putting 10g of the reaction product obtained in the step (2) into a beaker, adding 500mL of deionized water and 10mL of 36% HCl solution, stirring at normal temperature for reaction for 2h, centrifuging at 7000rpm for 2min, alternately washing with deionized water and ethanol, drying at 80 ℃ for 5h, and grinding to obtain the nano flaky silicon-carbon composite material used as the lithium ion battery cathode material.
Fig. 6 is an XRD pattern of the nano-sheet silicon-carbon composite material prepared in this example. Similarly, the XRD pattern is 21 at 2 θThe diffraction peak of amorphous carbon appears at 8 °, and the diffraction peaks of (111) and (220) of crystalline Si appear at 2 θ ═ 28.4 ° and 2 θ ═ 47.4 °, respectively, but due to the endothermic heat of phenyl carbonization, part of the siloxane bonds are not broken, and crystalline SiO appears at 2 θ ═ 22.0 °2The (101) crystal plane diffraction peak of (a).
The composite material obtained in this example was assembled into a battery in the same manner as in example 1.
FIG. 7 is a graph of the cycle performance of the nano-sheet silicon-carbon composite material prepared in this example, the cycle performance of the material is affected by the presence of silica in the product, and the battery capacity is 500mAg-1The capacity can be kept at 500mAh g after 100 cycles under the current density-1The capacity was lower than that of example 1.
Example 3
In this example, the nano-sheet silicon-carbon composite material is prepared by the following steps:
(1) precursor powder preparation
0.5g of vinyl cage type octahedral silsesquioxane, 4.5g of lithium chloride and 5.5g of potassium chloride are weighed and put into a mortar for grinding for 10min, and the ground powder is ball-milled in a ball mill at 500rpm for 2 h. And drying the ball-milled mixture at 70 ℃ for 4h to obtain precursor powder.
(2) High temperature magnesiothermic reduction
The precursor powder was placed at one end of a stainless steel burn boat, 0.5g of magnesium powder was added at the other end, and the burn boat was transferred to a tube furnace. Then heating to 300 ℃ at the heating rate of 5 ℃/min under argon, carrying out heat preservation reaction for 4h, and naturally cooling to room temperature.
(3) Washing and drying to obtain the composite material
And (3) putting 10g of the reaction product obtained in the step (2) into a beaker, adding 500mL of deionized water and 10mL of 36% HCl solution, stirring at normal temperature for reaction for 2h, centrifuging at 7000rpm for 2min, alternately washing with deionized water and ethanol, drying at 80 ℃ for 5h, and grinding to obtain the nano flaky silicon-carbon composite material used as the lithium ion battery cathode material.
The composite material obtained in this example was assembled into a battery in the same manner as in example 1.
FIG. 8 is a graph of the cycle performance of the nano-sheet silicon-carbon composite material prepared in this example, and it can be seen that the battery assembled by the nano-sheet silicon-carbon composite material is 500mAg-1The capacity can be kept at 540mAhg after 100 cycles under the current density-1The capacity retention rate was 92%.
Example 4
In this example, the nano-sheet silicon-carbon composite material is prepared by the following steps:
(1) precursor powder preparation
0.5g of phenyl cage type octahedral silsesquioxane, 4.5g of lithium chloride and 5.5g of potassium chloride are weighed and put into a mortar for grinding for 10min, and the ground powder is ball-milled and mixed in a ball mill at 500rpm for 2 h. And drying the ball-milled mixture at 70 ℃ for 4h to obtain precursor powder.
(2) High temperature magnesiothermic reduction
The precursor powder was placed at one end of a stainless steel burn boat, 0.5g of magnesium powder was added at the other end, and the burn boat was transferred to a tube furnace. Then at 95% Ar/5% H2Then heating to 300 ℃ at the heating rate of 5 ℃/min, carrying out heat preservation reaction for 4h, and naturally cooling to room temperature.
(3) Washing and drying to obtain the composite material
And (3) putting 10g of the reaction product obtained in the step (2) into a beaker, adding 500mL of deionized water and 10mL of 36% HCl solution, stirring at normal temperature for reaction for 2h, centrifuging at 7000rpm for 2min, alternately washing with deionized water and ethanol, drying at 80 ℃ for 5h, and grinding to obtain the nano flaky silicon-carbon composite material used as the lithium ion battery cathode material.
The composite material obtained in this example was assembled into a battery in the same manner as in example 1.
FIG. 9 is a graph of the cycle performance of the nano-sheet silicon-carbon composite material prepared in this example, showing that the assembled battery has a capacity of 500mAg-1The capacity can be kept at 300mAh g after 100 cycles under the current density-1。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a nano flaky silicon-carbon composite material used as a lithium ion battery cathode material is characterized by comprising the following steps:
(1) precursor powder preparation
Weighing cage type silsesquioxane, a carbon source and molten salt, placing the cage type silsesquioxane, the carbon source and the molten salt in a mortar, grinding uniformly, mixing in a ball mill, and drying to obtain precursor powder; wherein the mass ratio of the cage-type silsesquioxane to the molten salt is 0.05-0.1: 1, and the mass ratio of the cage-type silsesquioxane to the carbon source is 1: 0-0.5;
(2) high temperature magnesiothermic reduction
Placing the precursor powder at one end of a stainless steel burning boat, adding magnesium powder at the other end, then carrying out heat preservation reaction at 300-600 ℃ for 2-12 h under a protective atmosphere, and naturally cooling to room temperature; wherein the mass ratio of the cage-type silsesquioxane to the magnesium powder is 0.25-4: 1;
(3) washing and drying to obtain the composite material
And (3) placing the reaction product obtained in the step (2) in a beaker, adding deionized water and HCl solution, stirring at normal temperature for reaction for 1.5-3 h, centrifuging, washing, drying and grinding to obtain the nano flaky silicon-carbon composite material used as the lithium ion battery cathode material.
2. The method of claim 1, wherein: in the step 1, the cage-type silsesquioxane is at least one of hydrogen-based octahedral cage-type silsesquioxane, vinyl-based octahedral cage-type silsesquioxane or phenyl-based octahedral cage-type silsesquioxane.
3. The method of claim 1, wherein: in step 1, the carbon source is at least one of sucrose, glucose and citric acid.
4. The method of claim 1, wherein: in the step 1, the molten salt is 20-80% of two of sodium chloride, lithium chloride, potassium chloride and aluminum chloride by mass percent: 80-20% of the mixture.
5. The method of claim 1, wherein: in the step 1, the rotation speed of ball milling is 100-1000 rpm, the ball milling time is 1.5-2.5 h, the drying temperature is 30-100 ℃, and the drying time is 1.5-5 h.
6. The method of claim 1, wherein: in the step 2, the protective atmosphere is nitrogen, or argon and hydrogen in a volume ratio of 90-100%: 10 to 0 percent of mixed gas.
7. The method of claim 1, wherein: in the step 3, the proportion of the reaction product, deionized water and 36% by mass of HCl solution is 10 g: 200-500 mL: 5-10 mL.
8. The method of claim 1, wherein: in the step 3, the centrifugal rotating speed is 5000-10000 rpm, the centrifugal time is 1-4 min, the washing is performed by alternately washing with deionized water and ethanol, the drying temperature is 60-100 ℃, and the drying time is 3-8 h.
9. A nano-sheet silicon-carbon composite material prepared by the preparation method of any one of claims 1 to 8.
10. The method of claim 9, wherein: the nano sheet silicon-carbon composite material is formed by embedding silicon nano particles on a two-dimensional carbon nano sheet.
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| CN115148975A (en) * | 2022-07-29 | 2022-10-04 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Silicon oxide/carbon negative electrode material of self-supporting lithium ion battery and preparation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867947A (en) * | 2011-07-06 | 2013-01-09 | 东丽纤维研究所（中国）有限公司 | Method for preparing carbon/silicon composite anode material based on oligomeric silsesquioxane |
| WO2017175812A1 (en) * | 2016-04-08 | 2017-10-12 | Jnc株式会社 | Method for producing negative electrode active material for lithium ion secondary batteries |
| CN107994225A (en) * | 2017-12-11 | 2018-05-04 | 徐军红 | A kind of porous silicon-carbon composite cathode material and preparation method thereof, lithium ion battery |
| CN113479890A (en) * | 2021-06-30 | 2021-10-08 | 松山湖材料实验室 | Silicon-based negative electrode material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867947A (en) * | 2011-07-06 | 2013-01-09 | 东丽纤维研究所（中国）有限公司 | Method for preparing carbon/silicon composite anode material based on oligomeric silsesquioxane |
| WO2017175812A1 (en) * | 2016-04-08 | 2017-10-12 | Jnc株式会社 | Method for producing negative electrode active material for lithium ion secondary batteries |
| CN107994225A (en) * | 2017-12-11 | 2018-05-04 | 徐军红 | A kind of porous silicon-carbon composite cathode material and preparation method thereof, lithium ion battery |
| CN113479890A (en) * | 2021-06-30 | 2021-10-08 | 松山湖材料实验室 | Silicon-based negative electrode material and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115148975A (en) * | 2022-07-29 | 2022-10-04 | 合肥综合性国家科学中心能源研究院(安徽省能源实验室) | Silicon oxide/carbon negative electrode material of self-supporting lithium ion battery and preparation method |
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