CN115172726B - Silicon/graphite nano composite material and preparation method and application thereof - Google Patents
Silicon/graphite nano composite material and preparation method and application thereof Download PDFInfo
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- CN115172726B CN115172726B CN202210961356.6A CN202210961356A CN115172726B CN 115172726 B CN115172726 B CN 115172726B CN 202210961356 A CN202210961356 A CN 202210961356A CN 115172726 B CN115172726 B CN 115172726B
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- H01M4/00—Electrodes
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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Abstract
The invention discloses a silicon/graphite nano composite material and a preparation method and application thereof, belonging to the technical field of energy storage. The silicon/graphite nano composite material is obtained by compounding graphite recovered from waste batteries with silicon powder in a plasma ball milling grinding mixing mode. The invention does not need complex preparation conditions and materials, only needs to provide a plasma ball milling device to grind and mix the silicon material and the recycled graphite, does not involve high-temperature and high-pressure reaction in the preparation process, meets the safety standard, and has the advantages of improving the coulombic efficiency, the electrochemical performance, the safety and the like of a first loop, being capable of being applied industrially and having good application prospect.
Description
Technical Field
The invention relates to the technical field of energy storage, in particular to a silicon/graphite nano composite material and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of large energy density, long cycle life, high working voltage, no memory effect, wide working temperature range and the like, and is widely applied to various fields of electronic products, new energy automobiles, aerospace and the like. Currently, widely used lithium ion negative electrode materials include carbon-based negative electrode materials, silicon-based materials, novel alloys and other negative electrode materials. The traditional silicon-based material has the defects of poor conductivity, large volume change and the like, but has the advantages of high theoretical specific capacity (4200 mAh/g), abundant reserves and the like. The composite nano electrode material is prepared from the nano silicon-based material and the graphite recovered from the waste battery, so that the conductivity of the nano silicon-based material can be improved, the lithium layer contained on the surface of the recovered graphite can reduce the pre-lithiation process of the battery, and the coulomb efficiency, capacity and energy density of the first circle of the battery can be improved.
Disclosure of Invention
The invention aims to provide a silicon/graphite nano composite material and a preparation method and application thereof. Graphite (the surface of which contains an SEI (solid electrolyte interface) film formed by graphite and lithium and is equivalent to that of pre-lithiation) recovered from waste batteries is mixed with commercial silicon powder by a plasma ball milling technology, and the mixture is applied to a negative electrode of a lithium ion battery, so that the volume expansion of silicon can be effectively relieved in the charge and discharge processes, and the coulombic efficiency, the electrochemical performance and the safety of a first circle are improved.
In order to realize the purpose, the invention provides the following technical scheme:
the invention adopts one of the technical schemes: provides a silicon/graphite nano composite material, which is obtained by compounding graphite recovered from waste batteries with silicon powder.
The invention utilizes the recovered graphite in the waste battery as the raw material, the surface of the graphite material contains the SEI film, when the graphite is used as the raw material to prepare the lithium ion battery cathode material, the SEI film in the recovered graphite can reduce the amount of the SEI film formed again in the preparation of the cathode, and can effectively prevent the co-intercalation of solvent molecules, avoid the damage to the electrode material caused by the co-intercalation of the solvent molecules, thereby greatly improving the first-circle coulomb efficiency, the cycle performance and the service life of the electrode. Meanwhile, the SEI film in the recycled graphite is well bonded with the graphite layer, is rich in elasticity, and can be used for resisting a changeable electrochemical environment and a swellable active material (such as silicon powder).
Preferably, the waste battery comprises a lithium iron phosphate battery or a ternary battery.
Preferably, the mass ratio of the silicon powder to the graphite recovered from the waste battery is (5-20): (80-95).
Preferably, the purity of the silicon powder is more than 99.9%, the particle size is 30-50nm, and the specific surface area is 30-50m 2 /g。
The second technical scheme of the invention is as follows: the preparation method of the silicon/graphite nano composite material comprises the following steps: and (3) carrying out plasma ball milling and grinding on the graphite recovered from the waste batteries and the silicon powder, and mixing to obtain the silicon/graphite nano composite material.
Preferably, the mass ratio of the ball materials of the plasma ball milling is 30-70, the ball milling rotation speed is 900-1500rpm, the discharge frequency is 7-12kHz, and the ball milling time is 5-15h.
The third technical scheme of the invention is as follows: an application of the silicon/graphite nano composite material in the preparation of lithium ion batteries.
The invention has the following beneficial technical effects:
(1) The method is simple and feasible, and only one plasma ball milling device is needed to be provided without complex preparation conditions and materials so that the silicon material and the recovered graphite can be ground and mixed.
(2) The invention is green and environment-friendly, and pollution and toxic gas can not be generated; and the graphite in the waste batteries is recycled, so that the resources can be recycled, and the environmental protection standard is met.
(3) The method is safe and controllable, does not relate to high-temperature and high-pressure reaction, and meets the safety standard.
(4) According to the invention, silicon powder and graphite recovered from commercial batteries are used for preparing the silicon/graphite nano composite material, and the graphite with a fluffy structure can buffer the volume change of silicon in the charging and discharging processes, so that the method has the advantages of improving the coulombic efficiency, the electrochemical performance and the safety of the first circle, can be applied industrially, and has a good application prospect.
Drawings
Fig. 1 is a graph of cycle performance and coulombic efficiency for a lithium ion battery prepared in example 1 of the present invention.
Fig. 2 is a graph of cycle performance and coulombic efficiency for a lithium ion battery prepared in example 2 of the present invention.
Fig. 3 is a graph of cycle performance and coulombic efficiency for the lithium ion battery of the present invention prepared in comparative example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated value or intervening value in a stated range, and any other stated or intervening value in a stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including but not limited to.
The silicon powder used in the embodiment and the comparative example of the invention is commercial nano silicon powder, the purity of the commercial nano silicon powder is more than 99.9 percent, the particle size is between 30 and 50nm, and the specific surface area is between 30 and 50m 2 /g。
Example 1
Preparing a silicon/graphite nano composite material:
weighing 90g of graphite recovered from waste lithium iron phosphate batteries, weighing 10g of commercial nano silicon powder, taking 5000g of zirconia balls (3 mm specification), putting the zirconia balls into a plasma ball mill together, and grinding for 10 hours at the discharge frequency of 10KHz at the rotating speed of 1000rpm to obtain the uniformly mixed silicon/graphite nano composite material.
Energy storage performance study:
mixing conductive carbon black (SP) and polyvinylidene fluoride (PVDF) for 0.5h according to the mass ratio of 8: the dried electrode sheet was cut into a 13mm diameter circular electrode sheet by a punching machine, 1.0m li pf6inec dmc dec =1.
The electrochemical performance of the prepared button lithium ion battery is tested, after the button lithium ion battery is kept stand for 8 hours at 25 ℃, when the button lithium ion battery is subjected to charge-discharge circulation at the rate of 0.1C between 0.01V and 1.5V, the first discharge specific capacity can reach 570.2mAh/g and exceeds that of the existing commercial silicon-carbon material (428 mAh/g), the first-turn coulombic efficiency is as high as 93.07%, the specific capacity after 100 cycles is kept at 94.5%, the coulombic efficiency is kept at 100%, the level of the commercial silicon-carbon material is reached, the graphs of the circulation performance and the coulombic efficiency are shown in figure 1, the result shows that the silicon-carbon composite material prepared by the embodiment has higher discharge specific capacity and first-turn coulombic efficiency when being applied to the lithium ion battery as the negative electrode material, the performance is reached when exceeding that the existing commercial silicon-carbon material (comparative example 1), and the excellent electrochemical performance is a better negative electrode material in the lithium ion battery.
Example 2
Preparing a silicon/graphite nano composite material:
weighing 85g of graphite recovered from waste ternary batteries, weighing 15g of commercial nano silicon powder, taking 3000g of zirconia balls (3 mm specification), putting the zirconia balls into a plasma ball mill together, and grinding for 10 hours at the discharge frequency of 7kHz at the rotating speed of 900rpm to obtain the uniformly mixed silicon/graphite nano composite material.
The characterization was performed as in example 1, and a lithium ion battery was assembled to study the battery performance. The first discharge specific capacity can reach 744.4mAh/g, the first-turn coulombic efficiency reaches 90.1%, the specific capacity is kept at 88.6% after 100-turn circulation, and a circulation performance and coulombic efficiency curve chart is shown in figure 2.
Example 3
Preparing a silicon/graphite nano composite material:
firstly weighing 95g of graphite recovered from waste lithium iron phosphate batteries, then weighing 5g of commercial nano silicon powder, taking 7000g of zirconia balls (3 mm specification), putting the zirconia balls and the zirconia balls into a plasma ball mill together, and grinding for 8 hours at the discharge frequency of 12kHz at the rotation speed of 1500rpm to obtain the silicon/graphite nano composite material which is uniformly mixed.
The characterization was performed as in example 1, and a lithium ion battery was assembled to study the battery performance. The first discharge specific capacity can reach 522.9mAh/g, the first-turn coulombic efficiency reaches 92.8%, and the specific capacity is kept at 95.9% after 100 cycles.
Example 4
Preparing a silicon/graphite nano composite material:
firstly weighing 95g of graphite recovered from waste lithium iron phosphate batteries, then weighing 5g of commercial nano silicon powder, taking 7000g of zirconia balls (3 mm specification), putting the zirconia balls and the zirconia balls into a plasma ball mill together, and grinding for 8 hours at the discharge frequency of 12kHz at the rotation speed of 1500rpm to obtain the silicon/graphite nano composite material which is uniformly mixed.
The characterization was performed as in example 1, and a lithium ion battery was assembled to study the battery performance. The first discharge specific capacity can reach 415.2mAh/g, the first-turn coulombic efficiency reaches 91.5%, and the specific capacity is kept at 95.8% after 100-turn circulation.
Example 5
Preparing a silicon/graphite nano composite material:
weighing 80g of graphite recovered from waste lithium iron phosphate batteries, weighing 20g of commercial nano silicon powder, taking 6000g of zirconia balls (3 mm specification), putting the zirconia balls into a plasma ball mill together, and grinding for 15h at the discharge frequency of 10KHz at the rotating speed of 1200rpm to obtain the silicon/graphite nano composite material which is uniformly mixed.
The characterization was performed in the manner of example 1, and a lithium ion battery was assembled to investigate the battery performance. The first discharge specific capacity can reach 663.5mAh/g, the first turn of coulombic efficiency reaches 89.1%, and the specific capacity is maintained at 81.0% after 100 cycles of circulation.
Example 6
Referring to the method of example 5, composite materials were prepared according to the following different mass ratios of silicon to carbon in table 1 below, and lithium ion batteries were assembled to study the battery performance, the specific capacity after cycling for 100 cycles at a rate of 0.1C, and the results are shown in table 1:
TABLE 1
Comparative example 1
Preparation of commercial silicon/graphite composite:
weighing commercial graphite and silicon according to the mass ratio of the silicon to the graphite of 7.
The characterization was performed as in example 1, and a lithium ion battery was assembled to study the battery performance. The first discharge specific capacity is only 428.7mAh/g, the first-turn coulombic efficiency is 92.4%, the specific capacity is kept at 94.9% after 100-turn circulation, and the circulation performance and coulombic efficiency curve chart is shown in figure 3. The comparison of electrochemical performance graphs shows that the commercial silicon/graphite composite material has low specific capacity and low coulombic efficiency of the first circle, and is not suitable for being applied to the negative electrode of a lithium ion battery.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (4)
1. A silicon/graphite nano composite material is characterized in that the material is obtained by compounding graphite recovered from waste batteries with silicon powder;
the waste battery comprises a lithium iron phosphate battery or a ternary battery;
the mass ratio of the silicon powder to the graphite recovered from the waste battery is 15;
the purity of the silicon powder is more than 99.9 percent, the particle size is 30-50nm, and the specific surface area is 30-50m 2 /g。
2. A method for preparing the silicon/graphite nanocomposite material as claimed in claim 1, comprising the steps of: and (3) carrying out plasma ball milling and grinding on the graphite recovered from the waste batteries and the silicon powder, and mixing to obtain the silicon/graphite nano composite material.
3. The preparation method of the silicon/graphite nanocomposite material as claimed in claim 2, wherein the mass ratio of the ball material of the plasma ball milling is 30-70, the ball milling rotation speed is 900-1500rpm, the discharge frequency is 7-12kHz, and the ball milling time is 5-15h.
4. Use of the silicon/graphite nanocomposite material according to claim 1 for the preparation of lithium ion batteries.
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| CN104638233A (en) * | 2014-12-01 | 2015-05-20 | 贾晓玲 | Method for preparing silicon/artificial graphite composite by virtue of high energy ball milling |
| CN106129522A (en) * | 2016-08-31 | 2016-11-16 | 合肥国轩高科动力能源有限公司 | A kind of preparation method utilizing lithium ion battery negative to reclaim graphite |
| CN107706360A (en) * | 2017-07-25 | 2018-02-16 | 深圳市沃特玛电池有限公司 | A kind of preparation method of composite cathode material for lithium ion cell |
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| US11189822B2 (en) * | 2019-01-02 | 2021-11-30 | Global Graphene Group, Inc. | Graphite protected anode active material particles for rechargeable lithium batteries |
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| CN111977646A (en) * | 2020-07-20 | 2020-11-24 | 中南大学 | Method for preparing expanded graphite/silicon carbon material from graphite cathode of waste battery |
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