CN105047894A - Preparation method of halogen-doped carbon and silicon nano-material and application thereof - Google Patents

Preparation method of halogen-doped carbon and silicon nano-material and application thereof Download PDF

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Publication number
CN105047894A
CN105047894A CN201510559588.9A CN201510559588A CN105047894A CN 105047894 A CN105047894 A CN 105047894A CN 201510559588 A CN201510559588 A CN 201510559588A CN 105047894 A CN105047894 A CN 105047894A
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silicon nano
nano material
carbon
preparation
halogen
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CN105047894B (en
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顾宏伟
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Zhejiang Xingyue Electronic Technology Co ltd
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SUZHOU CHUANGKE MICROELECTRONIC MATERIAL Co Ltd
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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
    • 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
    • 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
    • H01M4/58—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
    • 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 relates to a preparation method of a halogen-doped carbon and silicon nano-material and an application thereof. The method comprises the steps that a carbon source with a specific structure is adopted, wrapping is conducted on the silicon nano-material through a simple mixing mode, and high temperature carbonization is further conducted to obtain the carbon and silicon nano-material with high specific capacity. When the obtained carbon and silicon nano-material is made to serve as an anode material of a lithium battery, the superior performance is achieved, the preparation method is simple, the cost is low, and wider prospect in the application field of lithium ion batteries for the high-performance carbon and silicon nano-material serving as the anode material is achieved.

Description

A kind of preparation method of carbon silicon nano material of halogen doping and application thereof
Technical field
The invention belongs to field of lithium ion battery, particularly a kind of preparation method of carbon silicon nano material of simple and effective halogen doping, and as the application of lithium ion battery negative material.
Background technology
Lithium ion battery, because its cycle performance is superior and energy density high, has become main force's power supply of various portable type electronic product.Graphite is the main negative material of current commercial Li-ion battery, but graphite only has 372mAh/g as the theoretical specific capacity of lithium ion battery negative material, has been difficult to the demand of satisfied various high-energy-density consumer electronics product of today.Therefore, novel high-performance negative material of future generation is developed very urgent.Silicon has very high theoretical specific capacity (4200mAh/g) as lithium ion battery negative material, but at Lithium-ion embeding with in the process of deviating from, silicon electrode material has larger volumetric expansion and contraction change (volumetric expansion reaches 400%), cause the destruction of silicon electrode material further and lose with collector contacting, have impact on silicon greatly as the cycle performance of lithium cell cathode material and apply more widely.Secondly, compared with traditional graphite cathode material, silicon electrode material has poor electron conductivity.
Due to the poor electronic conductivity of silion cell material and the impact of its bulk effect, lot of domestic and foreign scholar have studied silicon electrode as the application of negative material in lithium battery from different aspects, mainly comprise preparation nanostructure silicium cathode material and at the coated carbon-coating of silicium cathode material surface.This method is the electronic conductivity in order to improve silicium cathode material, expect again on the other hand to alleviate the bulk effect of silicon electrode material in cyclic process, but total production procedure is complicated, is difficult to the demand meeting high performance lithium ion battery performance.
Summary of the invention
The technical problem that the present invention solves is the preparation method and the application thereof that provide a kind of simple lithium ion battery negative material efficiently.Silicon nano material, due to the high theoretical specific capacity of himself, has caused and has paid close attention to widely.But it is as lithium ion battery negative material, its poor conductivity and larger bulk effect, seriously limit its practical application in lithium ion battery, therefore its conductivity can effectively be improved at the uniform carbon-coating of its Surface coating, the bulk effect occurred in its charge and discharge process can be alleviated on the other hand, effectively improve its cyclical stability.
The present invention adopts the carbon source of ad hoc structure, carry out coated by simple hybrid mode to silicon nano material, further high temperature cabonization obtains the lithium cell cathode material with height ratio capacity, make the carbon silicon nano material obtained as having superior performance during lithium cell cathode material, and preparation method is simple, cost is low, for high performance silicon nano material has more wide prospect as negative material in the application of lithium ion battery.
By the following technical solutions, a kind of preparation method of carbon silicon nano material of halogen doping, comprises following steps in the present invention:
(1) carbon source of halogen doping is dispersed in ethanol, in ethanol decentralized medium, carrying out ball milling with the silicon nano material of size uniformity subsequently makes it mix, Ball-milling Time is no less than 3h, dry again, obtain persursor material, wherein the mass ratio of silicon nano material and carbon source is 1:(1-2), the carbon source of described halogen doping is the mixture of Kynoar, Vingon and polytetrafluoroethylene;
(2) under inert gas atmosphere, calcined by the persursor material obtained at 700-900 DEG C, calcination time is 2-5 hour, obtains the carbon silicon nano material of described halogen doping.
In an embodiment of the invention, in described step (a), silicon nano material is the homogeneous nano material of yardstick 50-200nm, is preferably the nano material of about 100nm.
In an embodiment of the invention, in described step (a), described bake out temperature is 80-100 DEG C, and drying time is 12-15h.
In an embodiment of the invention, in described step (a), the mol of Kynoar, Vingon and polytetrafluoroethylene is than being 1:(1-2): (0.5-1), is more preferably 1:2:1.
The carbon silicon nano material of the halogen doping that the present invention also protects above-mentioned preparation method to obtain, and above-mentioned carbon silicon nano material is as the application of lithium ion battery negative material.
The present invention also protects a kind of ion cathode material lithium, adopts the carbon silicon nano material of above-mentioned halogen doping as negative pole.
Compared with prior art, the present invention has following beneficial effect:
(1) fluorine, the carbon source of chlorine doping has higher caking property, be distributed to uniformly after in solvent, can effectively be coated on silicon nano material surface, and this macromolecular compound has higher stability, lower cost, the advantages such as environmentally safe, therefore, adopt fluorine, the carbon source of chlorine doping is with a wide range of applications.In addition, adopt the carbon source of above-mentioned composition and ratio can form thick solution, described thick liquid can form good mixture with silicon nano material, Kynoar, Vingon and polytetrafluoroethylene can be uniform at silicon nano material Surface coating, to this mixture high-temperature process, the evenly coated carbon-coating of one deck can be obtained on the surface of silicon nano material, effectively improve the conductivity of silicon nano material and alleviate the bulk effect of silicon nano material.
(2) the carbon silicon nano material of the halogen doping in the present invention is as lithium ion battery negative material, its electrochemical stability tool increases significantly, compared with simple silicon nano material, under identical current density, it is significantly higher than silicon nano material as the application of negative material on lithium ion battery as the specific capacity that negative material embodies in the application of electrode material of lithium battery, and its cycle performance is also more stable.Especially, when the mol of Kynoar, Vingon and polytetrafluoroethylene is than being 1:2:1, after it encloses as lithium ion battery negative material discharge and recharge 300, specific capacity is approximately 1000mAh/g, far above current ion cathode material lithium on the market.Halogen (fluorine provided by the present invention, chlorine) silicon nano material that improves of the carbon that adulterates has more excellent specific capacity performance, stability in use, more excellent battery performance and useful life can be brought for lithium ion battery, thus expand silicon nano material in the range of application of field of lithium ion battery, make it have application prospect more widely; And preparation method provided by the invention is simple to operate, reaction condition is easy to realize, and can be good at realizing industrial production, has good prospects for commercial application.
Accompanying drawing explanation
Figure 1 shows that the SEM spectrogram of silicon-carbon nano particle prepared by the present invention.
Figure 2 shows that carbon silicon nano material prepared by the present invention and the cyclic curve of simple silicon nano material under the current density of 500mA/g.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, method of modifying provided by the invention is described, but protection scope of the present invention is not limited to this.
Embodiment one:
Evenly spread in 200mL ethanolic solution by 10g silicon nano and 10g carbon source, wherein the mol of Kynoar, Vingon and polytetrafluoroethylene is than being 1:2:1, and after stirring, ball milling 3 hours, puts into dry 12h in 100 DEG C of baking ovens.Last carbonization in the atmosphere of nitrogen, heating rate 5 DEG C/min, is warming up to 800 DEG C of insulation 2h, obtains the carbon silicon nano material of halogen doping after cooling.
Electrochemical property test:
Prepared material is mixed for 8:1:1 in mass ratio with SuperP and PVDF respectively in 1-METHYLPYRROLIDONE solution, to be evenly coated in subsequently on Copper Foil and 120 DEG C of vacuumizes.With EC/DEC=1:1LiPF 6for electrolyte, PP is barrier film, and metal lithium sheet is in the glove box being full of argon gas, make button cell to electrode.The battery assembled is surveyed its charge-discharge performance on LAND battery test system, and voltage range is 0.01-2.0V.Above-mentioned battery is tested, under the current density of 500mA/g, charge and discharge cycles 300 is enclosed, its specific discharge capacity and recurrence relation curve are shown in Fig. 2 (A), relative to simple silicon nano material electrode material (Fig. 2 (C)), the carbon silicon nano material of the above-mentioned halogen doping specific discharge capacity after 300 circles that circulates under the current density of 500mA/g is approximately 1150mAh/g, respectively far away higher than simple silicon nano material electrode material (450mAh/g).
Embodiment two
The preparation embodiment one of the carbon silicon nano material of halogen doping is substantially identical, and just biased sample is at 900 DEG C of insulation 2h.
Battery performance test method is identical with embodiment one, gained battery circulate under the current density of 500mA/g 300 circle after specific discharge capacity be approximately 1100mAh/g respectively, far away higher than simple silicon nano material electrode material (450mAh/g).
Embodiment three
The preparation embodiment one of the carbon silicon nano material of halogen doping is substantially identical, and just the mass ratio of silicon nano material and carbon source is 1:2, and the quality of the Kynoar added in actual experiment, Vingon and polytetrafluoroethylene is 20g.Battery performance test method is identical with embodiment one, its specific discharge capacity and recurrence relation curve are shown in Fig. 2 (B), gained battery circulate under the current density of 500mA/g 300 circle after specific discharge capacity be approximately 1300mAh/g respectively, cyclical stability is far away higher than single silicon nano material (450mAh/g).
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.

Claims (7)

1. a preparation method for the carbon silicon nano material of halogen doping, comprises following steps:
(1) carbon source of halogen doping is dispersed in ethanol, in ethanol decentralized medium, carrying out ball milling with the silicon nano material of size uniformity subsequently makes it mix, Ball-milling Time is no less than 3h, dry again, obtain persursor material, wherein the mass ratio of silicon nano material and carbon source is 1:(1-2), described carbon source is the mixture of Kynoar, Vingon and polytetrafluoroethylene;
(2) calcined at 700-900 DEG C by the persursor material obtained, calcination time is 2-5 hour, obtains the carbon silicon nano material of described halogen doping.
2. preparation method according to claim 1, is characterized in that, in described step (a), silicon nano material is the homogeneous nano material of yardstick 50-200nm, is preferably the nano material of about 100nm.
3. preparation method according to claim 1, is characterized in that, in described step (a), described bake out temperature is 80-100 DEG C, and drying time is 12-15h.
4. preparation method according to claim 1, is characterized in that, in described step (a), the mol of Kynoar, Vingon and polytetrafluoroethylene is than being 1:(1-2): (0.5-1), is more preferably 1:2:1.
5. the carbon silicon nano material of the halogen doping that the preparation method according to any one of claim 1-4 obtains.
6. carbon silicon nano material according to claim 5 is as the application of lithium ion battery negative material.
7. an ion cathode material lithium, is characterized in that adopting the carbon silicon nano material of halogen doping according to claim 5 as negative pole.
CN201510559588.9A 2015-09-06 2015-09-06 A kind of preparation method and applications of the carbon silicon nano material of halogen doping Active CN105047894B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108417781A (en) * 2017-02-09 2018-08-17 硅力能股份有限公司 Conducing composite material and its negative material and secondary cell of preparation
CN110416532A (en) * 2019-08-20 2019-11-05 广东工业大学 A kind of battery composite material and preparation method thereof, electrode slice and battery
CN114883538A (en) * 2022-03-31 2022-08-09 蜂巢能源科技股份有限公司 Composite cathode material and preparation method and application thereof
WO2023016047A1 (en) * 2021-08-12 2023-02-16 贝特瑞新材料集团股份有限公司 Negative electrode material and preparation method therefor, lithium ion battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102646818A (en) * 2012-04-28 2012-08-22 中南大学 Preparation method for composite cathode material of lithium ion battery
CN104538607A (en) * 2014-12-19 2015-04-22 天津巴莫科技股份有限公司 Preparation method of silicon-carbon negative electrode material for lithium ion battery

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN102646818A (en) * 2012-04-28 2012-08-22 中南大学 Preparation method for composite cathode material of lithium ion battery
CN104538607A (en) * 2014-12-19 2015-04-22 天津巴莫科技股份有限公司 Preparation method of silicon-carbon negative electrode material for lithium ion battery

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108417781A (en) * 2017-02-09 2018-08-17 硅力能股份有限公司 Conducing composite material and its negative material and secondary cell of preparation
CN110416532A (en) * 2019-08-20 2019-11-05 广东工业大学 A kind of battery composite material and preparation method thereof, electrode slice and battery
WO2023016047A1 (en) * 2021-08-12 2023-02-16 贝特瑞新材料集团股份有限公司 Negative electrode material and preparation method therefor, lithium ion battery
CN114883538A (en) * 2022-03-31 2022-08-09 蜂巢能源科技股份有限公司 Composite cathode material and preparation method and application thereof
CN114883538B (en) * 2022-03-31 2024-02-20 蜂巢能源科技股份有限公司 Composite positive electrode material and preparation method and application thereof

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