CN113054178B - Polo honey-like silicon-carbon shell-core structure composite negative electrode material and preparation method and application thereof - Google Patents
Polo honey-like silicon-carbon shell-core structure composite negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a polo honey-like silicon-carbon shell-core structure composite negative electrode material, which comprises the steps of grinding and sieving silicon powder to obtain superfine silicon powder, oxidizing the surface of the superfine silicon powder at high temperature, sintering the superfine silicon powder according to the characteristic of agglomeration of the superfine silicon powder, and after the sintering is finished, ball milling to homogenize the agglomerated grains, sintering in inert gas atmosphere to densify the grains, coating with asphalt/carbon source gas for carbonizing, HF is added to remove surface silicon oxide to prepare the polo honey-like silicon-carbon shell-core structure composite negative electrode material, the shell-core structure prepared by the preparation method can accommodate the volume expansion of the silicon material, sinter the nano-grade silicon material with uniform particles and smaller particle size, improve the conduction efficiency of electron ions on the silicon, meanwhile, the pulverization problem is avoided, so that the cycle performance and the first coulombic efficiency are effectively improved.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a polo honey-like silicon-carbon shell-core structure composite negative electrode material and a preparation method and application thereof.
Background
Graphite is a good conductive carbon material, has a layered structure and a stable structure, and is a mainstream negative electrode material for a lithium battery at present, but the theoretical gram capacity of a graphite negative electrode is low, so that the requirement of the market on a pure electric vehicle with high cruising ability cannot be met at present, the theoretical specific capacity of silicon is up to 4200mAh/g, which is ten times that of graphite, so that the graphite negative electrode material has good application potential, the silicon negative electrode has the limitations that the cycling performance is low due to volume expansion, easy pulverization and the like, and the first effect is poor, and the limitation of large-scale production and application of the silicon negative electrode is also located, so that the problems of volume expansion and pulverization of the silicon material are solved, and the problem to be solved is urgently researched and developed at present for the silicon negative electrode, in addition, the conductive capability of the silicon material is inferior to the graphite material, and how to improve the conductive capability of the silicon material is also a key point that the silicon negative electrode needs to be improved.
Both patent documents CN106784732B and CN106099113B show the preparation of a silicon-carbon negative electrode material with a core-shell structure, one of which adopts an oxidation method and is similar to the principle of the present invention, and the other of which adopts a magnesiothermic reduction method and is designed with a core-shell structure, which has been proved to be capable of accommodating silicon volume expansion and lead to pulverization, and no solution is mentioned in the two patents.
Disclosure of Invention
The invention aims to provide a polo honey-like silicon-carbon shell-core structure composite negative electrode material, and a preparation method and application thereof, and aims to solve the technical problems of low cycle performance and poor first effect caused by volume expansion, easy pulverization and the like in the prior art.
In order to achieve the above object, in a first aspect, the invention provides a method for preparing a porelike silicon-carbon shell-core structure composite anode material, which comprises the following steps:
(1) sieving the silicon powder with D50 of 5-15 μm with 2000 mesh sieve, and collecting superfine silicon powder with D50 of below 7 μm;
(2) placing the superfine silicon powder in the step (1) into a material barrel of a sand mill, taking ethanol as a solvent, taking the mass ratio of 10-20%, taking the rotating speed of 2200r/min-2800r/min, keeping the temperature of a system at 10-15 ℃ by using cooling circulating water, grinding for 4-8h, drying, crushing and sieving to obtain nanometer-grade superfine silicon powder;
(3) placing the nanoscale superfine silicon powder in the step (2) into a tank-type atmosphere furnace, raising the temperature to 500-700 ℃ in the air atmosphere at the heating rate of 10 ℃/min, keeping the temperature for 10-20min, and taking out the nanoscale superfine silicon powder after the temperature is reduced to normal temperature to obtain nanoscale superfine silicon powder with oxidized surface;
(4) placing the nano-grade ultra-fine silicon powder oxidized on the surface layer in the step (3) in a tank furnace, vacuumizing, filling argon atmosphere, keeping positive pressure of 1-2MPa in the furnace, raising the temperature to 1000-1200 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 1-2h, and taking out after cooling to normal temperature to obtain sintered compact silicon powder;
(5) ball-milling the sintered compact silicon powder in the step (4) in a ball mill at the rotation speed of 100-200r/min, and sieving with a 2000-mesh sieve to obtain sieved compact silicon powder;
(6) mixing the dense silicon powder obtained in the step (5) with high-temperature asphalt in a mass ratio of 1: 0.1-0.2, placing the mixed sample in a pot-type atmosphere furnace, heating in a nitrogen atmosphere in a stepped manner, heating to 350 ℃ at the speed of 3-5 ℃/min, keeping for 1-2h, and heating to 900 ℃ at the speed of 8-10 ℃/min to obtain carbon-coated compact silicon powder;
(7) and (4) leaching the carbon-coated compact silicon powder in the step (6) with strong acid such as hydrofluoric acid, removing a carbon layer on the surface of the silicon powder, and drying to obtain the polo-honey-like silicon-carbon shell-core structure composite negative electrode material.
Preferably, in the step (1), the silicon powder is high-purity silicon powder, and the purity is 99.999% or more.
Preferably, in the step (2), the nanoscale ultrafine silicon powder D50 is at 600-800 nm.
Preferably, in the step (3), the nanoscale ultrafine silicon powder is placed in a pot-type atmosphere furnace, and the temperature is raised to 600 ℃ and kept for 10 min.
Preferably, in the step (3), the nanoscale ultrafine silicon powder is placed in a pot-type atmosphere furnace, heated to 600 ℃, and kept for 20 min.
Preferably, in the step (4), the form of the dense silicon powder is in the shape of a fruit of Artocarpus heterophyllus.
Preferably, in the step (5), zirconia balls of 10-20cm are selected for ball milling, and the ball-to-material ratio is 1: 1.4-1.8.
Preferably, in the step (6), the viscosity of the high-temperature asphalt is not more than 40mm2/s, and the D50 is 3-5 um.
In a second aspect, the invention provides a porelike silicon-carbon shell-core structure composite negative electrode material prepared by the preparation method in any one of the above technical schemes.
In a third aspect, the invention provides an application of the porelike silicon-carbon shell-core structured composite negative electrode material as a negative electrode material of a lithium ion battery.
In summary, the technical scheme of the preparation method of the porelike silicon-carbon shell-core structure composite negative electrode material has at least the following beneficial effects: the invention relates to a preparation method of a polo honey-like silicon-carbon shell-core structure composite negative electrode material, which comprises the steps of grinding and sieving silicon powder to obtain superfine silicon powder, oxidizing the surface of the superfine silicon powder at high temperature, sintering the superfine silicon powder according to the agglomeration characteristic, homogenizing agglomerated particles through ball milling after the sintering is finished, sintering the particles in an inert gas atmosphere to make the particles compact, coating and carbonizing the particles by using asphalt/carbon source gas preferably, and adding HF to remove surface silicon oxide after the carbonization is finished, thereby preparing the polo honey-like silicon-carbon shell-core structure composite negative electrode material. The shell-core structure prepared by the preparation method can accommodate the volume expansion of the silicon material, and can sinter the nano-grade silicon material with uniform particles and smaller particle size, so that the conduction efficiency of electron ions on the silicon can be improved, and the pulverization problem is avoided, thereby effectively improving the cycle performance and the first coulombic efficiency.
In order to make the present invention and other objects, advantages, features and functions more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) picture of a Polo honey-like silicon-carbon shell-core structure composite negative electrode material prepared by the preparation method of example 2 of the invention;
FIG. 2 is a comparison of Polo honey-like silicon carbon shell-core structure composite negative electrode materials prepared in example 2 and comparative example 2 of the present invention, wherein, a is a TEM image of the Polo honey-like silicon carbon shell-core structure composite negative electrode material prepared in example 2, and b is a TEM image of the Polo honey-like silicon carbon shell-core structure composite negative electrode material prepared in comparative example 2;
FIG. 3 is a graph showing capacity retention after 100 cycles of examples 1 to 3 of the present invention and comparative examples 1 to 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example 1
The embodiment 1 of the invention provides a preparation method of a polo honey-like silicon-carbon shell-core structure composite anode material, which comprises the following steps: sieving the silicon powder with D50 of 10um with a 2000-mesh sieve, and collecting the superfine silicon powder with D50 of below 7; placing the superfine silicon powder in a material barrel of a sand mill, taking ethanol as a solvent, keeping the mass ratio at 20%, rotating at 2800r/min, keeping the temperature of a system at 15 ℃ by cooling circulating water, grinding for 8 hours, drying, crushing and sieving to obtain nanometer-grade superfine silicon powder; placing the nanoscale superfine silicon powder in a pot-type atmosphere furnace, heating to 500 ℃ in air atmosphere at a heating rate of 10 ℃/min, keeping for 10min, cooling to normal temperature, and taking out to obtain the nanoscale superfine silicon powder with oxidized surface layer. Placing the nano-grade superfine silicon powder with the oxidized surface layer in a pot furnace, vacuumizing, filling argon atmosphere, keeping 2MPa positive pressure in the furnace, raising the temperature to 1200 ℃ at the heating rate of 10 ℃/min, keeping for 2 hours, and taking out after the temperature is reduced to normal temperature to obtain sintered compact silicon powder; and (3) ball-milling the sintered compact silicon powder in a ball mill at the rotating speed of 200r/min, and sieving with a 2000-mesh sieve to obtain the sieved compact silicon powder. Mixing the compact silicon powder with high-temperature asphalt in a mass ratio of 1: 0.2, placing the mixed sample in a pot-type atmosphere furnace, heating in a nitrogen atmosphere in a stepped manner, heating to 350 ℃ at the speed of 5 ℃/min, keeping for 2h, and heating to 900 ℃ at the speed of 10 ℃/min to obtain the carbon-coated compact silicon powder. And (3) leaching the carbon-coated compact silicon powder with strong acid such as hydrofluoric acid, removing a carbon layer on the surface of the silicon powder, and drying to obtain the polo-honey-like silicon-carbon shell-core structure composite negative electrode material.
Example 2
The embodiment 2 of the invention provides a preparation method of a polo honey-like silicon-carbon shell-core structure composite anode material, which comprises the following steps: sieving the silicon powder with D50 of 10um with a 2000-mesh sieve, and collecting the superfine silicon powder with D50 of below 7; placing the superfine silicon powder in a material barrel of a sand mill, taking ethanol as a solvent, keeping the mass ratio at 20%, rotating at 2800r/min, keeping the temperature of a system at 15 ℃ by cooling circulating water, grinding for 8 hours, drying, crushing and sieving to obtain nanometer-grade superfine silicon powder; placing the nanoscale superfine silicon powder in a pot-type atmosphere furnace, heating to 600 ℃ at the heating rate of 10 ℃/min in the air atmosphere, keeping for 10min, cooling to normal temperature, and taking out to obtain the nanoscale superfine silicon powder with oxidized surface layer. Placing the nano-grade superfine silicon powder with the oxidized surface layer in a pot furnace, vacuumizing, filling argon atmosphere, keeping 2MPa positive pressure in the furnace, raising the temperature to 1200 ℃ at the heating rate of 10 ℃/min, keeping for 2 hours, and taking out after the temperature is reduced to normal temperature to obtain sintered compact silicon powder; and (3) ball-milling the sintered compact silicon powder in a ball mill at the rotating speed of 200r/min, and sieving with a 2000-mesh sieve to obtain the sieved compact silicon powder. Mixing the compact silicon powder with high-temperature asphalt in a mass ratio of 1: 0.2, placing the mixed sample in a pot-type atmosphere furnace, heating in a nitrogen atmosphere in a stepped manner, heating to 350 ℃ at the speed of 5 ℃/min, keeping for 2h, and heating to 900 ℃ at the speed of 10 ℃/min to obtain the carbon-coated compact silicon powder. And (3) leaching the carbon-coated compact silicon powder with strong acid such as hydrofluoric acid, removing a carbon layer on the surface of the silicon powder, and drying to obtain the polo-honey-like silicon-carbon shell-core structure composite negative electrode material.
Example 3
The embodiment 3 of the invention provides a preparation method of a polo honey-like silicon-carbon shell-core structure composite anode material, which comprises the following steps: sieving the silicon powder with D50 of 10um with a 2000-mesh sieve, and collecting the superfine silicon powder with D50 of below 7; placing the superfine silicon powder in a material barrel of a sand mill, taking ethanol as a solvent, keeping the mass ratio at 20%, rotating at 2800r/min, keeping the temperature of a system at 15 ℃ by cooling circulating water, grinding for 8 hours, drying, crushing and sieving to obtain nanometer-grade superfine silicon powder; placing the nanoscale superfine silicon powder in a pot-type atmosphere furnace, heating to 600 ℃ at the heating rate of 10 ℃/min in the air atmosphere, keeping the temperature for 20min, cooling to normal temperature, and taking out to obtain the nanoscale superfine silicon powder with oxidized surface layer. Placing the nano-grade superfine silicon powder with the oxidized surface layer in a pot furnace, vacuumizing, filling argon atmosphere, keeping 2MPa positive pressure in the furnace, raising the temperature to 1200 ℃ at the heating rate of 10 ℃/min, keeping for 2 hours, and taking out after the temperature is reduced to normal temperature to obtain sintered compact silicon powder; and (3) ball-milling the sintered compact silicon powder in a ball mill at the rotating speed of 200r/min, and sieving with a 2000-mesh sieve to obtain the sieved compact silicon powder. Mixing the compact silicon powder with high-temperature asphalt in a mass ratio of 1: 0.2, placing the mixed sample in a pot-type atmosphere furnace, heating in a nitrogen atmosphere in a stepped manner, heating to 350 ℃ at the speed of 5 ℃/min, keeping for 2h, and heating to 900 ℃ at the speed of 10 ℃/min to obtain the carbon-coated compact silicon powder. And (3) leaching the carbon-coated compact silicon powder with strong acid such as hydrofluoric acid, removing a carbon layer on the surface of the silicon powder, and drying to obtain the polo-honey-like silicon-carbon shell-core structure composite negative electrode material.
Comparative example 1
The experimental procedure of comparative example 1 was identical to that of example 1 except that the sintering step was eliminated and the carbon coating was directly performed.
Comparative example 2
The experimental procedure of comparative example 2 was identical to that of example 2 except that the sintering step was eliminated and the carbon coating was directly performed.
Comparative example 3
The experimental procedure of comparative example 3 was identical to that of example 3 except that the sintering step was eliminated and the carbon coating was directly performed.
Application example
In the preparation of all pole pieces, carbon black (SP) is used as a conductive agent, sodium carboxymethyl cellulose (CMC) is used as a binder, and the mass ratio of the conductive agent to the synthesized active material is 1: 1: 8, mixing and dissolving the mixture in deionized water and a small amount of alcohol, and magnetically stirring for more than 8 hours to prepare uniformly dispersed battery slurry for later use. And (3) uniformly coating the battery slurry on the surface of an electrode (the cut foam copper or copper foil), carrying out vacuum drying at 85 ℃ for 12h, tabletting and weighing for later use. The electrochemical performance of the electrodes was tested by assembling a button-type half cell (CR 2025) using a glove box (model Mbraun) from Labstar, Germany. The button half cell assembly completely adopts a lithium sheet as a counter electrode, a foam nickel sheet as a buffer gasket, and the water oxygen content of the manufacturing environment is respectively as follows: water concentration < 2 ppm, oxygen concentration < 2 ppm. The electrolyte used was 1M LiPF6 dissolved in EC and DMC organic solvents. Cell cycle formation was tested on novice devices.
The following methods were used to compare the effects of examples 1 to 3 and comparative examples 1 to 3.
The electron microscope image described in the invention adopts American Saimer Feishell Phonom Generation 5 to test the morphology.
Ultrastructural observations were performed using TECNAIG2F20 from philips, the netherlands.
TABLE 1
| Gram capacity (mAh/g) | First cycle efficiency (%) | Capacity retention after 100 cycles (%) | |
| Example 1 | 1820 | 85.4 | 82.1 |
| Example 2 | 1760 | 92.7 | 87.3 |
| Example 3 | 1610 | 89.8 | 85.2 |
| Comparative example 1 | 1310 | 71.5 | 59.3 |
| Comparative example 2 | 1280 | 78.1 | 62.1 |
| Comparative example 3 | 1260 | 77.6 | 60.8 |
Referring to fig. 1-3 and table 1, it can be seen that the oxidation temperature and time are closely related to gram volume, first effect and volume retention rate, and the low oxidation temperature in example 1 may cause insufficient surface oxidation, and further the oxide layer is not removed uniformly during the HF rinsing, resulting in poor asphalt coating effect; in the embodiment 3, the oxidation temperature is sufficient, but the oxidation time is too long, so that the oxidation layer is too thick, and the capacity loss is easily caused; the conditions of example 2 were optimized. The comparison of examples 1-3 with the three comparative examples 1-3, respectively, shows that sintering can prevent pulverization and has stronger electron ion conduction performance, thereby improving the first effect and the cycle capacity retention rate.
According to the preparation method of the polo honey-like silicon-carbon shell-core structure composite negative electrode material, silicon powder is ground and sieved to obtain superfine silicon powder, the surface of the superfine silicon powder is oxidized at high temperature, the superfine silicon powder is sintered according to the agglomeration characteristic, agglomerated particles are homogenized through ball milling after the sintering is finished, the agglomerated particles are sintered in an inert gas atmosphere to be compact, the pitch/carbon source gas is preferably used for coating and carbonizing, and HF is added to remove surface silicon oxide after the carbonization is finished, so that the polo honey-like silicon-carbon shell-core structure composite negative electrode material is prepared. The shell-core structure prepared by the preparation method can accommodate the volume expansion of the silicon material, and can sinter the nano-grade silicon material with uniform particles and smaller particle size, so that the conduction efficiency of electron ions on the silicon can be improved, and the pulverization problem is avoided, thereby effectively improving the cycle performance and the first coulombic efficiency.
In addition, the preparation process of the embodiment of the invention is safe and environment-friendly, and meanwhile, a large number of process procedures are not required to be added on the original basis, so that the operation is simple and easy, the cost is low, and the preparation method is suitable for industrial application.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a polo-honey-like silicon-carbon shell-core structure composite negative electrode material is characterized by comprising the following steps:
(1) sieving the silicon powder with D50 of 5-15 μm with 2000 mesh sieve, and collecting superfine silicon powder with D50 of below 7 μm;
(2) placing the superfine silicon powder in the step (1) into a material barrel of a sand mill, taking ethanol as a solvent, taking the mass ratio of 10-20%, taking the rotating speed of 2200r/min-2800r/min, keeping the temperature of a system at 10-15 ℃ by using cooling circulating water, grinding for 4-8h, drying, crushing and sieving to obtain nanometer-grade superfine silicon powder;
(3) placing the nanoscale superfine silicon powder in the step (2) into a tank-type atmosphere furnace, raising the temperature to 500-700 ℃ in the air atmosphere at the heating rate of 10 ℃/min, keeping the temperature for 10-20min, and taking out the nanoscale superfine silicon powder after the temperature is reduced to normal temperature to obtain nanoscale superfine silicon powder with oxidized surface;
(4) placing the nano-grade ultra-fine silicon powder oxidized on the surface layer in the step (3) in a tank furnace, vacuumizing, filling argon atmosphere, keeping positive pressure of 1-2MPa in the furnace, raising the temperature to 1000-1200 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 1-2h, and taking out after cooling to normal temperature to obtain sintered compact silicon powder;
(5) ball-milling the sintered compact silicon powder in the step (4) in a ball mill at the rotation speed of 100-200r/min, and sieving with a 2000-mesh sieve to obtain sieved compact silicon powder;
(6) mixing the dense silicon powder obtained in the step (5) with high-temperature asphalt in a mass ratio of 1: 0.1-0.2, placing the mixed sample in a pot-type atmosphere furnace, heating in a nitrogen atmosphere in a stepped manner, heating to 350 ℃ at the speed of 3-5 ℃/min, keeping for 1-2h, and heating to 900 ℃ at the speed of 8-10 ℃/min to obtain carbon-coated compact silicon powder;
(7) and (4) leaching the carbon-coated compact silicon powder in the step (6) with strong acid such as hydrofluoric acid, removing a carbon layer on the surface of the silicon powder, and drying to obtain the polo-honey-like silicon-carbon shell-core structure composite negative electrode material.
2. The method for preparing the polo-honey-like silicon-carbon shell-core structure composite anode material according to claim 1, wherein in the step (1), the silicon powder is high-purity silicon powder with the purity of 99.999 percent or more.
3. The method for preparing a polo-honey-like silicon-carbon shell-core structure composite anode material as claimed in claim 1, wherein in the step (2), the nanometer-level ultrafine silicon powder D50 is at 600-800 nm.
4. The preparation method of the polo honey-like silicon-carbon shell-core structure composite anode material as claimed in claim 1, wherein in the step (3), the nano-grade ultra-fine silicon powder is placed in a pot-type atmosphere furnace, and the temperature is raised to 600 ℃ and kept for 10 min.
5. The preparation method of the polo honey-like silicon-carbon shell-core structure composite anode material as claimed in claim 1, wherein in the step (3), the nano-grade ultra-fine silicon powder is placed in a pot-type atmosphere furnace, and the temperature is raised to 600 ℃ and is kept for 20 min.
6. The preparation method of the polenta honey-like silicon-carbon shell-core structure composite anode material as claimed in claim 1, wherein in the step (4), the form of the dense silicon powder is in the shape of polenta honey fruits.
7. The preparation method of the polo-honey-like silicon-carbon shell-core structure composite anode material as claimed in claim 1, wherein in the step (5), zirconia balls of 10-20cm are selected for ball milling, and the ball-to-material ratio is 1: 1.4-1.8.
8. The preparation method of the porelike silicon-carbon shell-core structure composite anode material as claimed in claim 1, wherein in the step (6), the viscosity of the high-temperature asphalt is not more than 40mm2And the D50 is 3-5 um.
9. A porcellanite-like silicon-carbon shell-core structured composite anode material prepared by the preparation method as set forth in any one of claims 1 to 8.
10. The use of the porelike silicon carbon shell core structured composite anode material of claim 9 as an anode material for a lithium ion battery.
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| JP2002316876A (en) * | 2001-04-20 | 2002-10-31 | Sumitomo Electric Ind Ltd | Silicon nitride based composite powder and production method therefor |
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