CN103647061B - The preparation method of silicon-base alloy negative material - Google Patents
The preparation method of silicon-base alloy negative material Download PDFInfo
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- CN103647061B CN103647061B CN201310568825.9A CN201310568825A CN103647061B CN 103647061 B CN103647061 B CN 103647061B CN 201310568825 A CN201310568825 A CN 201310568825A CN 103647061 B CN103647061 B CN 103647061B
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- silicon
- negative material
- base alloy
- alloy negative
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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
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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
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- 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 belongs to the preparation field of chemical cell, the preparation method particularly relating to a kind of silicon-base alloy negative material. This silicon-base alloy negative material is by by high purity lithium powder, silica flour and magnesium powder, and mix homogeneously in molar ratio, high-energy ball milling 12-16h, last vacuum drying removes dehydrated alcohol, obtains described silicon-base alloy negative material. Utilizing the silicon-base alloy negative material containing lithium, magnesium that method provided by the invention is prepared from, capacity is high, can ensure that the high voltage of battery, and the chemical property of silicon electrode is greatly enhanced.
Description
Technical field
The invention belongs to the preparation field of chemical cell, the preparation method particularly relating to a kind of silicon-base alloy negative material.
Background technology
Current business-like negative material is mainly graphite, and its actual capacity is close to theoretical value (372mAh/g), it is impossible to meet high-performance high-capacity lithium ion cell, particularly the requirement of high-energy-density film lithium ion micro cell. On the other hand, the intercalation potential of graphite-like material with carbon element is concentrated mainly in 100-0mV (vs.Li/Li+) scope, and the closely deposition potential of lithium metal is unfavorable for the safety of battery. Therefore, the important directions that preparation specific capacity is high, the reliable Novel cathode material for lithium ion battery of security performance has become scientific research and industry development.
Silicon is the negative material of theoretical capacity the highest (theoretical specific capacity is 4212mAh/g) up to now, thus has been also affected by studying widely. But the maximum problem of silicon be its in charge and discharge process, along with huge change in volume, its cubical expansivity is up to 270%, and the efflorescence of silicon makes active material peel off, and ultimately results in the capacity of electrode and significantly declines even complete failure. While making silicon materials have high power capacity, also having good cycle performance, people are mainly through preparing silicon based composite material, prepare amorphous silicon material and preparing three kinds of methods of silicon-base alloy to improve cycle performance.
The research of silicon-base alloy is concentrated mainly on Si-M Binary Alloy System, and wherein M can be the metal of inertia, such as Co,
Fe, Mn, Ni, V and Zr etc. do not have embedding lithium/de-lithium activity in whole charge and discharge process, purely play supporting construction effect; Can also be able to participate in the metal of the deintercalation reaction of lithium, such as Sn, Ag, Ca, Mg etc., itself there is embedding lithium/de-lithium activity, but different from the current potential of silicon, and therefore the volumetric expansion making material is occurred under different potentials by their compound, alleviate consequent internal stress, thus improving the cyclical stability of material.Compared with pure silicon, silicon alloy is used as negative material and reduces the bulk effect of electrode material to a certain extent, improves cycle performance. At present conventional aluminosilicate alloy material has Fe-Si alloy, due to Fe,
Ni etc. are inert elements, although improve cycle performance, but greatly reduce negative material specific capacity, thus cannot meet reality
With the needs changed.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
The preparation method of a kind of silicon-base alloy negative material, it is characterised in that comprise the following steps:
(1) take high purity lithium powder, silica flour and magnesium powder, in molar ratio example mix homogeneously, obtain mixture A;
(2) feed the mixture in dehydrated alcohol, high speed ball milling 12 ~ 16h, obtain mixture B;
(3) by mixture B vacuum drying at 105-150 DEG C, described silicon-base alloy negative material is obtained.
Preferably, the molar ratio described in step (1) is lithium powder: silica flour: magnesium powder=22:4:(0.1 ~ 1).
Preferably, the ball milling described in step (2) carries out in blanket of nitrogen.
Beneficial effects of the present invention is as follows:
1. negative material provided by the invention, employing Si is primary raw material, the rich reserves of silicon, and environmentally friendly, is the very promising lithium ion battery negative material of one.
2. the current potential average out to 0.25V of negative material Li+/Li provided by the invention, with the high voltage that positive pole pairing can ensure that battery; Negative material provided by the invention contains Li and Si, and its capacity can reach 4000mAhg-1, is significantly larger than graphite cathode; Containing inactive metal Mg in negative material provided by the invention, it is possible to provide conductive network for electrode, thus the charge transfer improving silicon and lithium is reacted, to strengthen the chemical property of silicon electrode.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail. Following example will assist in those skilled in the art and are further appreciated by the present invention, but do not limit the present invention in any form. It should be pointed out that, to those skilled in the art, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement. These broadly fall into protection scope of the present invention.
Embodiment 1
A kind of silicon-base alloy negative material; prepared by following steps: take high purity lithium powder, silica flour and magnesium powder; vacuum sphere grinding jar is uniformly put into by the mixed in molar ratio of 22:4:1; it is simultaneously introduced ball milling controlling agent dehydrated alcohol; it is filled with nitrogen as protective gas; high-energy ball milling 15h, is then placed in vacuum drying oven and heats (temperature controls at 100-150 DEG C) removing dehydrated alcohol, obtain described silicon-base alloy negative material.
Embodiment 2
A kind of silicon-base alloy negative material; prepared by following steps: take high purity lithium powder, silica flour and magnesium powder; vacuum sphere grinding jar is uniformly put into by the mixed in molar ratio of 22:4:0.5; it is simultaneously introduced ball milling controlling agent dehydrated alcohol; it is filled with nitrogen as protective gas; high-energy ball milling 14h, is then placed in vacuum drying oven and heats (temperature controls at 100-125 DEG C) removing dehydrated alcohol, obtain described silicon-base alloy negative material.
Embodiment 3
A kind of silicon-base alloy negative material; prepared by following steps: take high purity lithium powder, silica flour and magnesium powder; vacuum sphere grinding jar is uniformly put into by the mixed in molar ratio of 22:4:0.8; it is simultaneously introduced ball milling controlling agent dehydrated alcohol; it is filled with nitrogen as protective gas; high-energy ball milling 12h, is then placed in vacuum drying oven and heats (temperature controls at 125-150 DEG C) removing dehydrated alcohol, obtain described silicon-base alloy negative material.
Claims (2)
1. the preparation method of a silicon-base alloy negative material, it is characterised in that comprise the following steps:
(1) take high purity lithium powder, silica flour and magnesium powder, in molar ratio example mix homogeneously, obtain mixture A;
(2) feed the mixture in dehydrated alcohol, ball milling 12 ~ 16h, obtain mixture B;
(3) by mixture B vacuum drying at 105-150 DEG C, described silicon-base alloy negative material is obtained;
Wherein, the molar ratio described in step (1) is lithium powder: silica flour: magnesium powder=22:4:(0.1 ~ 1).
2. the preparation method of silicon-base alloy negative material according to claim 1, it is characterised in that the ball milling described in step (2) carries out in blanket of nitrogen.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310568825.9A CN103647061B (en) | 2013-11-15 | 2013-11-15 | The preparation method of silicon-base alloy negative material |
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| CN201310568825.9A CN103647061B (en) | 2013-11-15 | 2013-11-15 | The preparation method of silicon-base alloy negative material |
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| CN103647061A CN103647061A (en) | 2014-03-19 |
| CN103647061B true CN103647061B (en) | 2016-06-08 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105098250B (en) * | 2014-05-08 | 2018-07-31 | 微宏动力***（湖州）有限公司 | A kind of positive plate is free of the lithium ion battery of lithium |
| CN105375012B (en) * | 2015-11-30 | 2020-05-12 | 中国科学院金属研究所 | Silicon-tin composite material for lithium ion battery cathode and preparation method thereof |
| CN112234183B (en) * | 2020-10-14 | 2021-10-26 | 中国计量大学 | Preparation method for in-situ synthesis of conductive metal/silicon/polymer-based negative electrode material |
| CN114050251B (en) * | 2021-11-18 | 2024-01-19 | 兰州城市学院 | Preparation and application of silicon-carbon composite micro-nano structure material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237519A (en) * | 2011-07-11 | 2011-11-09 | 三峡大学 | Fluorine-free preparation method for three-dimensional porous silica powder anode material of lithium ion battery |
| CN103280555A (en) * | 2013-01-21 | 2013-09-04 | 深圳大学 | Lithium ion battery silicon-based alloy cathode material and preparation method thereof and lithium ion battery |
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| US9419272B2 (en) * | 2011-03-07 | 2016-08-16 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery, method of preparing same, and rechargeable lithium battery including same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237519A (en) * | 2011-07-11 | 2011-11-09 | 三峡大学 | Fluorine-free preparation method for three-dimensional porous silica powder anode material of lithium ion battery |
| CN103280555A (en) * | 2013-01-21 | 2013-09-04 | 深圳大学 | Lithium ion battery silicon-based alloy cathode material and preparation method thereof and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| Evaluation of Alloys Synthesized By Mechanical Alloying as Potential Anode Materials for Lithium-Ion Batteries;Mario Wachtler等;《Journal of Metastable and Nanocrystalline Materials》;20040731;第20-21卷;263-268 * |
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