CN110518194B - Method for preparing core-shell silicon/carbon composite material by in-situ carbon coating and application thereof - Google Patents

Method for preparing core-shell silicon/carbon composite material by in-situ carbon coating and application thereof Download PDF

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CN110518194B
CN110518194B CN201910593483.3A CN201910593483A CN110518194B CN 110518194 B CN110518194 B CN 110518194B CN 201910593483 A CN201910593483 A CN 201910593483A CN 110518194 B CN110518194 B CN 110518194B
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silicon
composite material
carbon composite
core
reactor
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CN110518194A (en
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黄辉
余佳阁
梁初
张文魁
夏阳
卞飞翔
张俊
甘永平
贺馨平
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Yuheng Battery Co ltd
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Zhejiang University of Technology ZJUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a novel method for preparing a core-shell type silicon/carbon composite material by in-situ carbon coating. Ball-milling lithium carbonate and silicon powder in a certain proportion for 3-96h, and transferring the mixture into a closed reactor; heating the reactor to 400-800 ℃ at a heating rate of 0.2-20 ℃/min, and preserving heat for 0.5-20 h; after the reaction is finished, cooling to room temperature, taking out the product in the reactor, and sequentially soaking for 3 hours in 1M dilute hydrochloric acid, soaking for half an hour in 10% hydrofluoric acid, and washing for three times in deionized water and alcohol. Then, the mixture is filtered and dried in vacuum at the temperature of 80 ℃ to obtain the silicon/carbon composite material. The patent provides a new method for preparing the core-shell type silicon/carbon composite material, which has the advantages of simple process, low reaction temperature, strong operability and easy industrial implementation, the obtained product has a core-shell type structure, has excellent electrochemical performance as a lithium ion battery cathode material, and is 1A g‑1The discharge capacity after 50 cycles under the current density is close to 1300 mAh/g.

Description

Method for preparing core-shell silicon/carbon composite material by in-situ carbon coating and application thereof
Technical Field
The invention relates to a novel method for obtaining a carbon-coated core-shell type silicon/carbon composite material by utilizing direct reaction of lithium carbonate and silicon and application of the carbon-coated core-shell type silicon/carbon composite material as a lithium ion battery cathode material.
Background
With the rapid development of society and economy, energy density of lithium ion batteries is required to be improved for various electronic devices and storage devices, especially for new energy electric vehicles and the like. At present, graphite is the most widely used negative electrode material of the lithium ion battery, but the theoretical specific capacity of the lithium ion battery is only 372mAh/g, and the application requirement of the high-energy density lithium ion battery cannot be met. Silicon has higher theoretical specific capacity (up to 4200mAh/g) and lower lithium intercalation/deintercalation potential, and is a high-specific-capacity negative electrode material which can replace a graphite negative electrode. However, silicon has the disadvantage of poor conductivity of the material compared to graphite, and the volume expansion during cyclic charge and discharge is large, which leads to a sharp capacity fade. Compared with pure silicon, the silicon and carbon material composite can effectively buffer the volume expansion effect of silicon, and can also improve the electronic conductivity and lithium ion diffusion coefficient of the material.
T.Zhang et al (Pure applied chem, 2006, 78: 1889-2The reversible specific capacity of the capacitor is still 594mAh/g after 20 times of circulation under the current density. The specific capacity and the cycle performance of the nano silicon/carbon composite material are improved, but the method has high preparation cost and low yield and is difficult to reach the level of practical application. The invention provides a novel in-situ carbon coating method, which utilizes lithium carbonate as a carbon source, is mixed with silicon powder and heated to directly react to obtain a core-shell type silicon/carbon composite material, has excellent electrochemical performance as a lithium ion battery cathode material, and is a high-performance lithium ion battery cathode material with great application prospect. Compared with the prior art, the method has the advantages of simple and controllable process, mild reaction conditions and no environmental pollution, can prepare the core-shell silicon/carbon composite material through one-step solid-phase reaction, and is easy for industrial implementation.
Disclosure of Invention
The invention aims to provide a novel method for preparing a core-shell silicon/carbon composite material by in-situ carbon coating, which has the advantages of simple process, strong operability and easy industrial implementation, and is characterized in that the core-shell silicon/carbon composite material can be obtained by directly mixing and heating lithium carbonate and silicon for reaction.
The second purpose of the invention is to provide the application of the core-shell type silicon/carbon composite material as a lithium ion battery negative electrode material.
The technical scheme of the invention is specifically explained as follows:
the preparation technology of the core-shell silicon/carbon composite material takes lithium carbonate as a carbon source, the lithium carbonate and silicon powder are ball-milled and mixed uniformly according to a certain mass ratio, and then the mixture is directly heated to 650 ℃ to react for a period of time, so that the carbon-coated core-shell silicon/carbon composite material is obtained. The method has the advantages that the silicon/carbon composite materials with different carbon contents can be obtained by adjusting the mass ratio of the lithium carbonate to the silicon, and the specific preparation method comprises the following steps:
(1) ball-milling lithium carbonate and silicon powder in a certain mass ratio for 3-96h, and transferring the mixture into a closed reactor;
(2) heating the reactor to 400-800 ℃ at a heating rate of 0.2-20 ℃/min, and preserving heat for 0.5-20 h;
(3) and after the reaction is finished, cooling to room temperature, taking out a product in the reactor, sequentially soaking for 3 hours in 1M dilute hydrochloric acid, soaking for half an hour in 10% hydrofluoric acid, washing for three times in deionized water and alcohol, then performing suction filtration, and performing vacuum drying at 80 ℃ to obtain the silicon/carbon composite material.
In the invention, the purity of the raw materials lithium carbonate and silicon powder is not lower than the chemical purity.
Preferably, in the step (1), the silicon powder is selected from one or a mixture of any of the following materials: nano silicon, micron silicon, silicon/aluminum alloy.
Preferably, in the step (1), the mass ratio of the lithium carbonate to the silicon is preferably 1: 1 to (1-20), and most preferably 1: 10. The ball milling time is preferably 6 to 24h, most preferably 12 h.
Preferably, in the step (2), the heating rate is preferably 0.5-5 ℃/min, and most preferably 5 ℃/min; the heating temperature is preferably 400-800 ℃, and most preferably 650 ℃; the heat preservation time is preferably 1 to 20 hours, and most preferably 10 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a novel method for preparing the core-shell silicon/carbon composite material, which has the advantages of simple and controllable process, mild reaction conditions, environmental pollution, strong operability and easy industrial implementation.
(2) The method needs lower reaction temperature, can react when being heated to 400 ℃, and can efficiently, quickly and massively prepare the core-shell silicon/carbon composite material after being heated to 650 ℃.
(3) The core-shell silicon/carbon composite material provided by the invention has the characteristics of high specific capacity and good cycle performance as a lithium ion battery cathode material.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the core-shell silicon/carbon composite prepared in example 1;
FIG. 2 is a Scanning Electron Micrograph (SEM) of the core-shell silicon/carbon composite prepared in example 1;
fig. 3 is a cycle performance of the core-shell type silicon/carbon composite prepared in example 1.
Detailed description of the invention
The technical solution of the present invention is further described below by using specific examples, but the scope of the present invention is not limited thereto.
Example 1
Uniformly grinding 5g of micron silicon powder and 0.5g of lithium carbonate, putting the ground materials into a closed heating pipe for vacuumizing, heating the ground materials to 650 ℃ at a heating rate of 5 ℃/min for reaction, and keeping the temperature for 10 hours; after the reaction was completed, it was cooled to room temperature. The product is soaked for 3 hours in 1M dilute hydrochloric acid, soaked for half an hour in 10% hydrofluoric acid, and washed with deionized water and alcohol for three times. Then carrying out suction filtration, and carrying out vacuum drying at 80 ℃ to obtain the core-shell silicon/carbon composite material. Fig. 1 is an XRD diffractogram of the composite material, compared to a standard card, which is elemental silicon. Fig. 2 is an SEM image of the composite material, and it can be seen that the product is a silicon/carbon composite material having a core-shell structure with a carbon coating layer on the surface of the silicon powder.
An electrode was prepared from the core-shell type silicon/carbon composite material obtained in example 1 in the following manner.
Respectively weighing the core-shell silicon/carbon composite material according to the mass ratio of 80: 10: Super-P: grinding polyvinylidene fluoride uniformly to prepare an electrode, taking metal lithium as a counter electrode and 1mol/L LiPF as electrolyte6the/EC-DMC (1: 1), the polypropylene microporous film is the diaphragm, assemble the simulation lithium ion battery. FIG. 3 shows the corresponding cell at 1Ag-1And the cycle performance curve in the voltage range of 0.01-3.0V indicates that the measured battery has good cycle performance, capacity retention rate and coulombic efficiency close to 99%, and it can be seen that the core-shell silicon/carbon composite material prepared in example 1 is applied to 1Ag-1The discharge capacity after 50 times of circulation under the current density is close to 1300mAh/g (figure 3), and the circulation performance is excellent.
Example 2
Uniformly grinding 8g of nano silicon powder and 1g of lithium carbonate, putting the ground nano silicon powder and 1g of lithium carbonate into a closed heating pipe, vacuumizing, heating to 500 ℃ at a heating rate of 5 ℃/min, and reacting for 10 hours; after the reaction was completed, it was cooled to room temperature. The product is soaked for 3 hours in 1M dilute hydrochloric acid, soaked for half an hour in 10% hydrofluoric acid, and washed with deionized water and alcohol for three times. And then carrying out suction filtration and vacuum drying at 80 ℃ to obtain the core-shell silicon/carbon composite material.
Example 3
Uniformly grinding 10g of silicon/aluminum alloy powder and 2g of lithium carbonate, putting the ground silicon/aluminum alloy powder and 2g of lithium carbonate into a sealed heating pipe, vacuumizing, heating to 800 ℃ at a heating rate of 5 ℃/min, and reacting for 10 hours; after the reaction was completed, it was cooled to room temperature. The product is soaked for 3 hours in 1M dilute hydrochloric acid, soaked for half an hour in 10% hydrofluoric acid, and washed with deionized water and alcohol for three times. Then carrying out suction filtration, and carrying out vacuum drying at 80 ℃ to obtain the core-shell silicon/carbon composite material.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (2)

1. A method for preparing a core-shell silicon/carbon composite material by in-situ carbon coating is characterized by comprising the following steps:
(1) ball-milling lithium carbonate and silicon powder in a certain proportion for 3-96h, and transferring the mixture into a closed reactor;
(2) heating the reactor to 400-800 ℃ at a heating rate of 0.2-20 ℃/min, and preserving heat for 0.5-20 h;
(3) after the reaction is finished, cooling to room temperature, taking out a product in the reactor, sequentially soaking for 3 hours in 1M dilute hydrochloric acid, soaking for half an hour in 10% hydrofluoric acid, washing for three times in deionized water and alcohol, then performing suction filtration, and performing vacuum drying at 80 ℃ to obtain the silicon/carbon composite material;
the purity of the lithium carbonate and the silicon powder in the step (1) is not lower than the chemical purity, and the silicon powder is selected from one or the mixture of the following materials: nano-silicon or micro-silicon;
in the step (1), the mass ratio of the lithium carbonate to the silicon powder is 1: 10;
in the step (1), the ball milling time is 12 h;
in the step (2), the heating rate is 5 ℃/min, and the heating temperature is 650 ℃; the incubation time was 10 hours.
2. The use of the core-shell silicon/carbon composite material prepared by the method of any one of claim 1 as a negative electrode material for lithium ion batteries.
CN201910593483.3A 2019-07-03 2019-07-03 Method for preparing core-shell silicon/carbon composite material by in-situ carbon coating and application thereof Active CN110518194B (en)

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CN107565103A (en) * 2017-07-20 2018-01-09 广东东岛新能源股份有限公司 A kind of porous silicon/graphene composite material and its production and use
CN109546122A (en) * 2018-11-23 2019-03-29 浙江众泰汽车制造有限公司 A kind of Si-C composite material of surface modification and its preparation method and application

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JP2014073942A (en) * 2012-10-05 2014-04-24 Osaka Titanium Technologies Co Ltd Method of producing lithium-containing silicon oxide powder, and lithium-containing silicon oxide powder

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CN107565103A (en) * 2017-07-20 2018-01-09 广东东岛新能源股份有限公司 A kind of porous silicon/graphene composite material and its production and use
CN109546122A (en) * 2018-11-23 2019-03-29 浙江众泰汽车制造有限公司 A kind of Si-C composite material of surface modification and its preparation method and application

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