CN1705150A - Method for making negative electrode material of lithium ion cell - Google Patents

Method for making negative electrode material of lithium ion cell Download PDF

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Publication number
CN1705150A
CN1705150A CNA2004100426509A CN200410042650A CN1705150A CN 1705150 A CN1705150 A CN 1705150A CN A2004100426509 A CNA2004100426509 A CN A2004100426509A CN 200410042650 A CN200410042650 A CN 200410042650A CN 1705150 A CN1705150 A CN 1705150A
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lithium ion
silicon
negative material
ion battery
manufacture method
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CN100352084C (en
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潘树明
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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

A method for preparing negative pole material of lithium cell, which contains putting silicon, carbon, doped 0.01 % rareearth oxide La2O5 and Nd2O5 in high power ball mill, protected by Ar or N2 for preventing oxidation, the C : Si = 3 :1 -5 : 1, checking the abrading grain size every 20 hr until to 50-100nm to obtain high specific capacity and fine safety nano negative pole material.

Description

The manufacture method of lithium ion battery negative material
Technical field
The invention belongs to energy technology field, especially relate to the preparation method of lithium ion battery negative material.
Background technology
At present, the negative material of known lithium ion has hard carbon, native graphite, mesophase-carbon micro-beads.Different material with carbon elements there are differences in many-sides such as microscopic pattern, surface functional group, porosity granularity, degree of crystallinity, impurity, the relation of its chemical property, electrochemical behavior, architectural feature has all been carried out extensively and in depth research, consider that from the dynamics angle raising of rhombus content of graphite has promoted the embedding of lithium ion.Lithium ion can occupy the irregular position of boundary, owing to embed with extremely slow speed, electrochemistry capacitance can be greater than the theoretical capacity 372mAh/g of graphite.The electrode potential of desirable negative material should be approaching with lithium metal, the black electrode of stone by the position from 0.4 to zero (with respect to Li +/ change between Li), be proper negative material.Material with carbon element has good structural stability, chemical stability and thermal stability.Degree of graphitization material with carbon element cyclicity low and that kinetic property is good is better.
In order to improve the performance of lithium ion battery negative material, to adopt and introduce metallic element, the nonmetal modification of carrying out is introduced in surface treatment.
At present with carbon, native graphite do negative material have problems be the problem of poor stability and reversible capacity is lower and with the problem of electrolyte compatibility.
Summary of the invention
The present invention has overcome some shortcomings that exist in the prior art, provides a kind of and can improve security performance, improves compatible better with the electrolyte again negative material manufacture method of reversible capacity.
Technical scheme of the present invention:
1. material:
1. amorphous silicon: to be that shortrange order and long-range are unordered have very unique physical property to its architectural feature, is easy to form heterojunction, and very low interfacial state is arranged, and is easy to realize that high concentration is controllable doped.
2. polysilicon: purity reaches the semiconductor grade multicrystal silicon materials that are, and that form is divided into is bar-shaped, bulk and graininess, is the raw material of making monocrystalline silicon, grey metal gloss, hard and crisp.
3. silicon single crystal is the semiconductor silicon material of monocrystal, good thermal conductivity and mechanical behavior under high temperature, and excellent semiconductor property has czochralski silicon monocrystal, zone-melted silicon single crystal, magnetic to draw silicon single crystal.
4. material with carbon element is hard carbon, native graphite.
2. the equipment that synthesizes negative material:
In high energy vibration formula ball mill, carry out, with high-purity Ar gas or high-purity N 2Gas shiled is adorned a cylindrical abrading block in the ball grinder, and rotating speed 400-1500 rev/min, adopt on request at certain hour and choose an amount of sample for analyzing usefulness, can pack in high oscillatory type ball mill on demand yard a brain ball or a Ceramic Balls rise and stir and abrasive action.
3. detect: sample thief comes out to test nano-silicon size: 40-110nm.
4. proportioning: the ratio that weighs carbon raw material and silicon, carbon and silicon is C: Si=3: 1～5: 1.
5. the batching of aforementioned proportion is inserted in the high energy vibration formula ball mill.
6. add the rare earth oxide that accounts for whole weight 0.01-0.03%: La 2O 3, Nd 2O 3
7. above-mentioned batch (was added high-purity Ar or N in mixed grinding 10-150 hour in high energy vibration formula ball mill 2Protection).
8. take out and measure: granularity is at 30-100nm.
9. above-mentioned material is carried out electric performance test.
Test experiments:
1. material and electrolyte
A. material: above-mentioned synthetic lithium ion battery negative material
B. electrolyte: mixed solvent 1mol/L, LiClO 4/ EC+DEC (1: 1).
2. experimental procedure:
Make negative plate, positive plate LiCoO 2Material is assembled into simulated battery.
A. charge-discharge performance test:
Constant current charge-discharge experiment: adopt galvanostatic method to carry out charge and discharge, current strength is that to be controlled at precision be 1mA to the potential range in the 15.0mA/g cyclic process;
B. powder microelectrode cyclic voltammetry experiment: used electrolytic cell is two electrode systems, and work electrode is a powder microelectrode, and auxiliary electrode is a battery utmost point lithium sheet, and sweep limits is 0.0～2.0V, and sweep speed is 1mV/S, begins to sweep from 2.0V.
Initial reversible capacity reaches 1850mAh/g, and capacity also can reach more than the 1725mah/g for the 10th time.
The present invention compared with prior art has following advantage:
1. the inventor finds doing pilot study when experiment, with the synthetic negative material of high energy vibration formula ball mill the time without Ar or N 2During gas shiled, oxidative phenomena takes place, with argon gas (Ar), nitrogen (N 2) gas shiled, prevented oxidation, guaranteed quality, have effective advantage.
2. the lithium among the present invention has high reversible specific capacity (greater than 1000mah/g) and good circulating and reversible performance from the battery carbon negative pole material.
3. select the hard carbon that arrives cheap and easy to get, modifying natural graphite for use, reduced cost, have good economic benefit and industrial prospect.
4. to compare with other synthetic methods be simple method to the method for this mechanical alloying, is being subjected to numerous colleagues' attention, and it is good not only to have reduced cost but also fail safe.
Embodiment
Embodiment 1: insert the high energy ball mill that cleans up with 1000g amorphous silicon (purity 99.99%); it is anti-oxidation to fill into high-purity (greater than 99.99%) argon (Ar) gas shiled; in the high speed ball mill of 650 rev/mins of rotating speeds, grind, shut down sampling in per 20 hours to survey granularity, when being ground to 80nm till.Again hard carbon is inserted in following ratio: C 0.82Si 0.18Add percentage 0.01%La (0.1g) by weight again; add in the high energy ball mill; fill high-purity argon (Ar) gas and got sample inspection granularity in per 10 hours one time; shut down when reaching 80nm; the good negative material of taking-up mill is made negative plate and is made simulated battery, tests initial reversible capacity and reaches 1156mAh/g, also can reach 950mAh/g after 20 circulations.
Embodiment 2: insert the clean high energy ball mill of cleaning with 1000g polysilicon (purity 99.99%), as follows embodiment 1 records initial reversible capacity and reaches 1245mAh/g, also can reach 980mAg/g after 20 circulations.
Embodiment 3: insert the high energy ball mill that cleans the capable person with 1000g monocrystalline silicon (purity 99.99%), as follows embodiment 1 records initial reversible capacity and reaches 1280mAh/g, and 20 circulations are afterwards indefinite also can to reach 1056mAh/g.
Embodiment 4: change the hard carbon among the embodiment 1 into native graphite, other are surveyed initial reversible capacity and reach 1315mAh/g with embodiment 1, after 20 circulations, also can reach 1085mAh/g.
Embodiment 5: with 1000g amorphous silicon (purity 99.99%), add percetage by weight 0.01%Nd 2O 3Pack in the high energy ball mill, fill high-purity argon (Ar) gas, got a sample and check granularity in per 10 hours; shut down when reaching 80nm, good negative material is made negative plate to take out mill, makes simulated battery; the initial capacity of test reaches 1768mAh/g, and capacity also can reach 1756mAh/g at the 10th time.
Embodiment 6: will add weight percentage 0.01%Nd among the embodiment 5 2O 3Change 0.01%La into 2O 3, other make simulated battery with embodiment 5, and the test initial capacity reaches 1724mAh/g, and capacity also can reach 1695mAh/g at the 10th time.

Claims (5)

1. the manufacture method of a lithium ion battery negative material; it is characterized in that; with silicon materials or silicon and material with carbon element and mix a small amount of rare earth oxide and insert in the high energy ball mill, anti-oxidation with argon gas or nitrogen protection, be ground to 50-100nm and obtain specific capacity height, nanometer negative material that fail safe is good.
2. the manufacture method of lithium ion battery negative material according to claim 1 is characterized in that, silicon materials are amorphous silicon and crystalline silicon material.
3. the manufacture method of lithium ion battery negative material according to claim 1 is characterized in that, material with carbon element is hard carbon or native graphite.
4. the manufacture method of lithium ion battery negative material according to claim 1 is characterized in that, mixes a small amount of rare earth oxide La 2O 3And Nd 2O 3
5. the manufacture method of lithium ion battery negative material according to claim 1 is characterized in that, adds the ratio of carbon and silicon: be 3: 1 to 5: 1.
CNB2004100426509A 2004-05-31 2004-05-31 Method for making negative electrode material of lithium ion cell Expired - Fee Related CN100352084C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101442124B (en) * 2007-11-19 2011-09-07 比亚迪股份有限公司 Method for preparing composite material of lithium ion battery cathode, and cathode and battery
CN102110806B (en) * 2009-12-23 2013-07-24 上海杉杉科技有限公司 Negative electrode material of lithium ion battery and preparation method thereof
US20130244087A1 (en) * 2010-11-30 2013-09-19 Shenzhen BYD Auto R&D Company Limited and BYD Company Limited Negative active material, method for preparing the same and lithium ion battery comprising the same
US20130252031A1 (en) * 2010-11-30 2013-09-26 Shenzhen BYD Auto R&D Company Limited and BYD Company Limited Negative active material, method of preparing negative active material and lithium ion battery comprising the same
EP2678891A1 (en) * 2011-02-23 2014-01-01 Evonik Litarion GmbH Electrode material having high capacitance
CN106784721A (en) * 2017-01-11 2017-05-31 安徽工业大学 A kind of YC2@onions shape carbon/amorphous carbon nano-complex and its preparation method and application
WO2019041341A1 (en) * 2017-09-04 2019-03-07 超能高新材料股份有限公司 Negative electrode material for lithium-ion battery

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0853729A (en) * 1994-08-09 1996-02-27 Mitsubishi Materials Corp Nickel based alloy
JP4137350B2 (en) * 2000-06-16 2008-08-20 三星エスディアイ株式会社 Negative electrode material for lithium secondary battery, electrode for lithium secondary battery, lithium secondary battery, and method for producing negative electrode material for lithium secondary battery
CN1199300C (en) * 2002-06-21 2005-04-27 中国科学院上海微***与信息技术研究所 High specific capacity Si-C composite material for cathode of Li ion cell, and mfg. method thereof
CN1242502C (en) * 2003-03-28 2006-02-15 中国科学院上海微***与信息技术研究所 Silicon aluminium alloy/carbon composite material used for lithium ion battery negative electrode and its preparation method
CN1252846C (en) * 2003-09-10 2006-04-19 武汉大学 Silicon alloy and carbon base material composition and its preparing method and use

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101442124B (en) * 2007-11-19 2011-09-07 比亚迪股份有限公司 Method for preparing composite material of lithium ion battery cathode, and cathode and battery
CN102110806B (en) * 2009-12-23 2013-07-24 上海杉杉科技有限公司 Negative electrode material of lithium ion battery and preparation method thereof
US20130244087A1 (en) * 2010-11-30 2013-09-19 Shenzhen BYD Auto R&D Company Limited and BYD Company Limited Negative active material, method for preparing the same and lithium ion battery comprising the same
US20130252031A1 (en) * 2010-11-30 2013-09-26 Shenzhen BYD Auto R&D Company Limited and BYD Company Limited Negative active material, method of preparing negative active material and lithium ion battery comprising the same
US9005812B2 (en) * 2010-11-30 2015-04-14 Shenzhen Byd Auto R&D Company Limited Negative active material, method of preparing negative active material and lithium ion battery comprising the same
US9029020B2 (en) * 2010-11-30 2015-05-12 Shenzhen Byd Auto R&D Company Limited Negative active material, method for preparing the same and lithium ion battery comprising the same
EP2678891A1 (en) * 2011-02-23 2014-01-01 Evonik Litarion GmbH Electrode material having high capacitance
CN103518275A (en) * 2011-02-23 2014-01-15 赢创利塔里安有限责任公司 Electrode material having high capacitance
CN106784721A (en) * 2017-01-11 2017-05-31 安徽工业大学 A kind of YC2@onions shape carbon/amorphous carbon nano-complex and its preparation method and application
WO2019041341A1 (en) * 2017-09-04 2019-03-07 超能高新材料股份有限公司 Negative electrode material for lithium-ion battery
CN109792042A (en) * 2017-09-04 2019-05-21 超能高新材料股份有限公司 Lithium ion battery negative material

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