CN1919736A - Preparation method of spinelle lithium titanate for lithium secondary battery negative electrode material - Google Patents

Preparation method of spinelle lithium titanate for lithium secondary battery negative electrode material Download PDF

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Publication number
CN1919736A
CN1919736A CNA2006101094976A CN200610109497A CN1919736A CN 1919736 A CN1919736 A CN 1919736A CN A2006101094976 A CNA2006101094976 A CN A2006101094976A CN 200610109497 A CN200610109497 A CN 200610109497A CN 1919736 A CN1919736 A CN 1919736A
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lithium
salt
secondary battery
preparation
watery fusion
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CN100450930C (en
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白莹
吴锋
吴川
包丽颖
王国庆
张旻昱
王峰
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NATIONAL HIGH-TECHNOLOGIES GREEN MATERIALS DEVELOPMENT CENTER
Beijing Institute of Technology BIT
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NATIONAL HIGH-TECHNOLOGIES GREEN MATERIALS DEVELOPMENT CENTER
Beijing Institute of Technology BIT
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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 discloses a preparing method of spinel lithium titanate as Li-secondary battery cathode material, which adopts titanium dioxide and inorganic Li salt as raw material to low-temperature fusing salt as synthetic dielectrics to generate the product through solid-phase reaction.

Description

A kind of preparation method who is used for the lithium secondary battery cathode material spinel lithium titanate
Technical field
The present invention relates generally to a kind of preparation method who is used for the lithium secondary battery cathode material spinel lithium titanate, belongs to field of chemical power source, particularly lithium secondary battery critical material and technical field.
Background technology
At present, commercial lithium ion battery negative material adopts carbon material mostly, and there are some shortcomings in it: separating out of Li dendrite arranged in charge and discharge process; First charge-discharge efficiency low (about about 85%); React with electrolytic solution; There is tangible voltage delay.Compare with the carbon negative pole, the alloy type negative material generally has higher specific storage, but cycle performance is relatively poor.Spinel type lithium titanate (Li 4Ti 5O 12) having remarkable advantages: it is a kind of zero strain material, in the embedding of lithium with to deviate from the process volume change of material very little; Good cycle; Good charge and discharge platform is arranged; Theoretical specific capacity is 175mAh/g, and actual specific capacity can reach 165mAh/g, and concentrates on land regions; Do not react with electrolytic solution; Low price.Because above-mentioned advantage is particularly compared Li with commercial carbon negative pole material 4Ti 5O 12Have better chemical property and security, so be expected to become the novel negative material of lithium-ion-power cell.
Li 4Ti 5O 12The preparation method traditional solid reaction process and sol-gel method are arranged.Simple but the raw material of tradition solid reaction process technology needs long ground and mixed and mixes the performance of degree direct influence to product, the reaction velocity of diffusion is slow, and the product size distribution is inhomogeneous, and tap density is low, thermal treatment temp of having relatively high expectations and long heat treatment time, energy consumption is big.Compare with solid state reaction, the product chemical purity height of sol-gel method preparation, good uniformity, thermal treatment temp is lower, and the reaction times is short, but causes cost to rise owing to add organic compound in the building-up process.The present invention absorbs the advantage of conventional solid-state method and gel-sol method, is reaction medium with watery fusion salt, and the velocity of diffusion of reactant in fused salt is apparently higher than in the solid phase environment, this is fast reaction speed effectively, reduce temperature of reaction, shorten the reaction times, save energy.The spinel lithium titanate of the present invention's preparation shows excellent chemical property as the negative pole of lithium secondary battery, is with a wide range of applications.
Summary of the invention
The objective of the invention is to inorganic salt with titanium dioxide and lithium as cheap raw material, adopt the synthetic lithium secondary battery cathode material lithium titanate of watery fusion salt method; Provide a kind of preparation technology simple, the production favorable reproducibility, product is even, and selection that can be by raw material and watery fusion salt is with the preparation method of control product cut size size.
This method is synthesized according to following steps:
(1) with titanium dioxide as the titanium source, the lithium source is selected from a kind of in lithium hydroxide, Quilonum Retard, lithium chloride, the lithium nitrate, titanium dioxide and lithium source are prepared burden according to 5: 4 mol ratio, and mix, add inorganic salt then as watery fusion salt, the mol ratio 1～20 of watery fusion salt and titanium dioxide;
(2) will be ground to the pressed powder that mixes is positioned in the retort furnace and calcines, 500～1200 ℃ of temperature of reaction, 6～16 hours reaction times, naturally cool to room temperature then, after the taking-up of the product after the solid state reaction, wash with distilled water, remove remaining watery fusion salt, put in 80～100 ℃ the vacuum drying oven baking 24 hours, and obtained the spinel lithium titanate material of particle diameter 50nm～100 μ m.
Watery fusion salt of the present invention is selected from a kind of or any 2～3 kinds of mixing in lithium chloride, Quilonum Retard, Lithium Sulphate, lithium nitrate, Repone K, salt of wormwood, vitriolate of tartar, saltpetre, sodium-chlor, yellow soda ash, sodium sulfate, the SODIUMNITRATE.
Positively effect of the present invention has:
1, used watery fusion salt wide material sources;
2, raw material in heat-processed by watery fusion salt as medium, can realize uniform mixing, thereby not need to resemble and raw material or intermediate are ground repeatedly traditional solid state reaction, can realize the quick preparation of material;
3, the preparation process of material is simple, expands the scale of production easily.
Description of drawings
Fig. 1 is for pressing embodiment 3 described spinel Li 4Ti 5O 12The SEM electromicroscopic photograph;
Fig. 2 is Li 4Ti 5O 12XRD spectra,
Wherein (a) presses embodiment 3 described spinel Li 4Ti 5O 12XRD spectra, (b) spinel Li 4Ti 5O 12Standard powdery diffractometry XRD spectra;
Fig. 3 is for pressing embodiment 3 described spinel Li 4Ti 5O 12In current density is 0.07mA/cm 2Under preceding 50 all charging and discharging curves.
Embodiment
Describe the present invention in detail below by specific embodiment:
Embodiment 1
With TiO 2, LiOHH 2Be transferred in the crucible after 1.25: 1: 1.25 in molar ratio mixed of O and LiCl is even, place retort furnace, under air atmosphere, calcined 16 hours for 1200 ℃, naturally cool to room temperature with stove then, take out sample.Remove unnecessary Cl with the distilled water repetitive scrubbing -And Li +, until splashing into AgNO 3Solution does not precipitate to separate out and gets final product.Sample after the washing is placed on 100 ℃ interior the baking 24 hours of vacuum drying oven, obtains the lithium titanate powder.Observing the product pattern through field emission scanning electron microscope (SEM) is octahedral structure, and particle diameter is 90～100 μ m, detects with X-ray powder art diffraction (XRD) to be pure phase spinel Li 4Ti 5O 12
The Li that will synthesize 4Ti 5O 12, acetylene black and binding agent mix by mass ratio at 8: 1: 1, be coated on the aluminium foil.After 24 hours, take out compressing tablet 55 ℃ of vacuum oven, be cut into the pole piece of 7 * 7mm, weigh.With Li 4Ti 5O 12Be working electrode, metallic lithium is a counter electrode, and electrolytic solution adopts 1M LiPF 6-EC/DMC (volume ratio 1: 1) is assembled into Experimental cell in the argon gas glove box, survey its chemical property.Adopt the battery performance test instrument that Experimental cell is carried out the test of charge and discharge cycles, the charging stopping potential is to 2.5V, and discharge cut-off voltage is to 1.2V, current density 0.07mA/cm 2First charge-discharge efficiency and specific discharge capacity are respectively 91% and 152mAh/g.
Embodiment 2
With TiO 2, LiOHH 2Be transferred in the crucible after 1.25: 1: 25 in molar ratio mixed of O and LiCl is even, place retort furnace, under air atmosphere, calcined 6 hours for 500 ℃, naturally cool to room temperature with stove then, take out sample.Remove unnecessary Cl with the distilled water repetitive scrubbing -And Li +, until splashing into AgNO 3Solution does not precipitate to separate out and gets final product.Sample after the washing is placed in 80 ℃ the vacuum drying oven baking 24 hours, obtains the lithium titanate powder.Observing the product pattern through field emission scanning electron microscope is octahedral structure, and particle diameter is 50-60nm, and detecting with the X-ray powder diffraction is pure phase spinel Li 4Ti 5O 12
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1.Current density is 0.07mA/cm 2, the first charge-discharge efficiency of sample and specific discharge capacity are respectively 94% and 168mAh/g; Current density is 0.14mA/cm 2, the first charge-discharge efficiency of sample and specific discharge capacity are respectively 91% and 156mAh/g.
Embodiment 3
With TiO 2, LiOHH 2Be transferred in the crucible after O and 1.25: 1: 10 in molar ratio mixed of binary watery fusion salt 0.59LiCl-0.41KCl are even, place retort furnace, under air atmosphere, calcined 8 hours for 800 ℃, naturally cool to room temperature with stove then, take out sample.Remove unnecessary Cl with the distilled water repetitive scrubbing -And Li +, until splashing into AgNO 3Solution does not precipitate to separate out and gets final product.Sample after the washing is placed on 100 ℃ interior the baking 24 hours of vacuum drying oven, obtains the lithium titanate powder.Observing the product pattern through field emission scanning electron microscope is octahedral structure, and particle diameter is 1～3 μ m, as shown in Figure 1.Detecting with the X-ray powder diffraction is pure phase spinel Li 4Ti 5O 12, see Fig. 2.
The preparation of pole piece, the assembling of Experimental cell and electrochemical property test are with embodiment 1.Fig. 3 is Li 4Ti 5O 12Charging and discharging curve.When current density is 0.07mA/cm 2, the first charge-discharge efficiency of sample and specific discharge capacity difference 92% and 163mAh/g, the 50 all capability retentions that circulate are 90%; When current density is 0.14mA/cm 2, the first charge-discharge efficiency of sample and specific discharge capacity are respectively 90% and 147mAh/g.

Claims (2)

1. preparation method who is used for the lithium secondary battery cathode material spinel lithium titanate, it is characterized in that: this method is synthesized according to following steps:
(1) with titanium dioxide as the titanium source, the lithium source is selected from a kind of in lithium hydroxide, Quilonum Retard, lithium chloride, the lithium nitrate, titanium dioxide and lithium source are prepared burden according to 5: 4 mol ratio, and mix, add inorganic salt then as watery fusion salt, the mol ratio 1～20 of watery fusion salt and titanium dioxide;
(2) will be ground to the pressed powder that mixes is positioned in the retort furnace and calcines, 500～1200 ℃ of temperature of reaction, 6～16 hours reaction times, naturally cool to room temperature then, after the taking-up of the product after the solid state reaction, wash with distilled water, remove remaining watery fusion salt, put in 80～100 ℃ the vacuum drying oven baking 24 hours, and obtained the spinel lithium titanate material of particle diameter 50nm～100 μ m.
2. the described preparation method who is used for the lithium secondary battery cathode material spinel lithium titanate of claim 1, it is characterized in that: described watery fusion salt is selected from a kind of or any 2～3 kinds of mixing in lithium chloride, Quilonum Retard, Lithium Sulphate, lithium nitrate, Repone K, salt of wormwood, vitriolate of tartar, saltpetre, sodium-chlor, yellow soda ash, sodium sulfate, the SODIUMNITRATE.
CNB2006101094976A 2006-08-17 2006-08-17 Preparation method of spinelle lithium titanate for lithium secondary battery negative electrode material Expired - Fee Related CN100450930C (en)

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CN102050483A (en) * 2010-07-22 2011-05-11 中信国安盟固利动力科技有限公司 Industrial synthesis method for lithium titanate
CN102315427A (en) * 2010-06-29 2012-01-11 比亚迪股份有限公司 Cathode active substance for lithium ion secondary battery, preparation method and lithium ion secondary battery
CN102332574A (en) * 2011-08-18 2012-01-25 青岛瀚博电子科技有限公司 Modified lithium titanate material used for lithium ion battery and manufacturing method thereof
CN103058269A (en) * 2012-12-25 2013-04-24 河北师范大学 Method of preparing of lithium titanate
CN103117381A (en) * 2013-01-25 2013-05-22 合肥国轩高科动力能源股份公司 Method for preparing nano lithium titanate material through low-energy-consumption solid-phase method
CN103947019A (en) * 2011-11-29 2014-07-23 松下电器产业株式会社 Negative electrode active material, electrical storage device, and method for producing negative electrode active material
CN104319383A (en) * 2009-05-26 2015-01-28 石原产业株式会社 Lithium titanate, process for production of same, and electrode active material and electricity storage device each comprising same
CN104617285A (en) * 2014-12-16 2015-05-13 天津大学 Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method
CN104617297A (en) * 2015-02-09 2015-05-13 湖南科技大学 Method for preparing lithium ion battery anode material LiMnBO3 by using molten salt method
CN106602007A (en) * 2016-11-25 2017-04-26 清华大学深圳研究生院 Preparation method of lithium titanate material with adjustable surface
US9705129B2 (en) 2012-05-23 2017-07-11 Robert Bosch Gmbh Process for producing an electrode for an electrochemical energy storage means and electrode

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JP4073868B2 (en) * 2001-07-20 2008-04-09 アルテアナノ インコーポレイテッド Method for producing lithium titanate
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CN104319383A (en) * 2009-05-26 2015-01-28 石原产业株式会社 Lithium titanate, process for production of same, and electrode active material and electricity storage device each comprising same
CN104319383B (en) * 2009-05-26 2018-04-17 石原产业株式会社 Lithium titanate, the method for producing lithium titanate and the electrode active material and electrical storage device for respectively containing lithium titanate
CN102315427A (en) * 2010-06-29 2012-01-11 比亚迪股份有限公司 Cathode active substance for lithium ion secondary battery, preparation method and lithium ion secondary battery
CN102050483A (en) * 2010-07-22 2011-05-11 中信国安盟固利动力科技有限公司 Industrial synthesis method for lithium titanate
CN102332574A (en) * 2011-08-18 2012-01-25 青岛瀚博电子科技有限公司 Modified lithium titanate material used for lithium ion battery and manufacturing method thereof
US9287562B2 (en) 2011-11-29 2016-03-15 Panasonic Intellectual Property Management Corporation Co., Ltd. Negative electrode active material comprising spinel lithium titanate, electrical storage device, and method for producing negative electrode active material
CN103947019A (en) * 2011-11-29 2014-07-23 松下电器产业株式会社 Negative electrode active material, electrical storage device, and method for producing negative electrode active material
CN103947019B (en) * 2011-11-29 2016-06-08 松下知识产权经营株式会社 The manufacture method of negative electrode active material, Electrical storage devices and negative electrode active material
CN104813508B (en) * 2012-05-23 2018-03-27 罗伯特·博世有限公司 For the method and electrode of the electrode for manufacturing electrochemical energy accumulator
US9705129B2 (en) 2012-05-23 2017-07-11 Robert Bosch Gmbh Process for producing an electrode for an electrochemical energy storage means and electrode
CN103058269A (en) * 2012-12-25 2013-04-24 河北师范大学 Method of preparing of lithium titanate
CN103117381A (en) * 2013-01-25 2013-05-22 合肥国轩高科动力能源股份公司 Method for preparing nano lithium titanate material through low-energy-consumption solid-phase method
CN103117381B (en) * 2013-01-25 2016-08-03 合肥国轩高科动力能源有限公司 A kind of method of low energy consumption solid-phase method for preparing nano-sized lithium titanate material
CN104617285B (en) * 2014-12-16 2017-02-22 天津大学 Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method
CN104617285A (en) * 2014-12-16 2015-05-13 天津大学 Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method
CN104617297A (en) * 2015-02-09 2015-05-13 湖南科技大学 Method for preparing lithium ion battery anode material LiMnBO3 by using molten salt method
CN106602007A (en) * 2016-11-25 2017-04-26 清华大学深圳研究生院 Preparation method of lithium titanate material with adjustable surface
CN106602007B (en) * 2016-11-25 2019-03-08 清华大学深圳研究生院 A kind of preparation method of the regulatable lithium titanate material in surface

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