CN102945952A - Method for preparing anode material carbon coated lithium titanate for lithium ion power batteries - Google Patents

Method for preparing anode material carbon coated lithium titanate for lithium ion power batteries Download PDF

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Publication number
CN102945952A
CN102945952A CN2012105165957A CN201210516595A CN102945952A CN 102945952 A CN102945952 A CN 102945952A CN 2012105165957 A CN2012105165957 A CN 2012105165957A CN 201210516595 A CN201210516595 A CN 201210516595A CN 102945952 A CN102945952 A CN 102945952A
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lithium
coats
lithium titanate
ion power
preparation
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CN2012105165957A
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鄢俊敏
张新波
孟凡陆
尹彦斌
赵雪
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Jilin University
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Jilin University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a method for preparing anode material carbon coated lithium titanate for lithium ion power batteries, and belongs to the technical field of electrochemical energy materials. According to the invention, titanium dioxides are coated with carbon firstly, and then technological processes of lithiation and calcining are performed, so that a carbon layer coated on the surface of the titanium dioxides both can effectively suppress the size increasing of particles in the process of sintering, and improves the electrical conductivity of lithium titanate materials; and in the process of lithiation, a small amount of lithium oxalate is added in lithium salts, thereby reducing the alkalinity of a solution, and facilitating the melting of TiO2/C. The invention aims to overcome the defects of poor battery rate performance difference and the like caused by the fact that lithium titanate materials prepared by using the traditional solid phase method is large in particle size and poor in electronic conductivity, and provides a method for preparing carbon coated lithium titanate materials which can improve the battery rate performance. The method is simple in process operation, and suitable for large-scale production.

Description

A kind of cathode material for lithium-ion power battery carbon coats the preparation method of lithium titanate
Technical field
The present invention relates to the preparation method that a kind of cathode material for lithium-ion power battery carbon coats lithium titanate, belong to electrochemical energy material technology field.
Background technology
Lithium titanate material is a kind of lithium ion battery negative material that has prospect, and with traditional carbon negative pole material, lithium titanate has obvious advantage: Li as lithium ion battery negative material 4Ti 5O 12Have obvious charge and discharge platform, discharging and recharging when finishing has obvious voltage jump, has good overcharging resisting performance and anti-mistake and puts performance; Voltage platform is positioned at 1.55V (vs.Li/Li +) near, being difficult for causing that lithium metal is separated out or the generation tree dendritic crystal, battery unit does not exist thermal runaway and short circuit yet; In the charge and discharge cycles process, unit cell volume is changed to 0.1%-0.3%, is called as " zero strain " material, and cycle performance is excellent.But Li 4Ti 5O 12The defective that has poorly conductive, capacity attenuation is rapid when high current charge-discharge, and high rate performance is relatively poor.Improve Li 4Ti 5O 12The approach of high rate performance mainly contains the following aspects: (1) preparation nanometer particle size Li 4Ti 5O 12(2) preparation loose structure; (3) improve Li 4Ti 5O 12Conductivity.The main synthetic method of lithium titanate is high temperature solid-state method at present, and solid phase method is fit to large-scale production, and preparation technology is simple.
CN10250280A discloses a kind of preparation method of lithium ionic cell cathode material lithium titanate, and the method is that post-drying is directly mixed in lithium source and titanium source in water, then solid product high-temperature calcination in Muffle furnace is made lithium titanate powder.Although this preparation method's technique is simple, the lithium titanate discharge capacitance that obtains is low, and chemical property is unsatisfactory.
CN102633300A discloses a kind of carbon and has coated lithium titanate anode material and preparation method thereof and its application.The method at first is ground into fine powder with lithium source, titanium source and carbon source, three roasting process of following adopted, although this law has been simplified reinforced operation, technique is simple, and three times roasting process has increased production cost.
Summary of the invention
The lithium titanate material particle diameter that the object of the invention is to overcome the conventional solid-state method preparation reaches more greatly the shortcomings such as battery high rate performance that the electron conduction rate variance causes is poor, provide a kind of and can improve the battery high rate performance, and technological operation is simple, and the carbon of suitable for mass production coats the preparation method of lithium titanate material.
Its technical scheme is: a kind of cathode material for lithium-ion power battery carbon coats the preparation method of lithium titanate, comprises following processing step:
A) take by weighing a certain amount of carbon source and titanium dioxide, its mass ratio is: (3~5): 10, be dissolved in a certain amount of alcohol, and fully stirred for several hour is dried mixture in baking oven;
B) carbon source of drying in the steps A and the mixture of titanium dioxide are carried out sintering under 400~700 ℃ in inert atmosphere, temperature retention time is 5~8 hours, naturally is down to room temperature, obtains the nano titanium oxide that carbon coats;
C) with lithium compound and titanium dioxide, according to Li: Ti=(0.8~1.0): 1 mol ratio is prepared burden, ball milling in uniform dielectric, and oven dry, 600~900 ℃ of lower sintering are 8~10 hours in inert atmosphere, obtain the lithium titanate powder that carbon coats.
Above-mentioned titanium dioxide is Detitanium-ore-type.
Above-mentioned carbon source is sucrose or glucose or its mixture.
Above-mentioned inert atmosphere is a kind of or its mist in argon gas, the nitrogen.
Above-mentioned lithium compound is the mixture of at least a and lithium oxalate in lithium carbonate, the lithium acetate, and the content of lithium oxalate is 1~5%.
Above-mentioned ball-milling medium is acetone or alcohol.
Above-mentioned bake out temperature is 80 ℃.
Above-mentioned heating rate is controlled to be 120~180 ℃/hour.
Its technique effect is: the present invention adopts the synthetic carbon of high temperature solid-state method to coat lithium titanate material, at first coat uniform carbon-coating at titanium dioxide surface, the nano titanium oxide and the lithium-containing compound mixing and ball milling that again carbon are coated, sintering under inert atmosphere, the carbon that makes coats lithium titanate material, overcome the large shortcoming of conventional solid-state method resulting materials particle diameter, the carbon-coating of coating has suppressed the particle in the sintering process and has increased phenomenon, has also improved electronic conductivity simultaneously.In addition, lithium salts of the present invention adopts the mixture of lithium carbonate and lithium oxalate, and the effect of lithium oxalate is to regulate on the one hand the pH value of mixture, because basicity is unfavorable for greatly TiO 2The melting of/C, residual oxalate is conducive to the pore-creating in the sintering process on the other hand, improves the power performance of lithium ion migration, thereby improves current density and the power density of battery.
Description of drawings
Fig. 1 is the spinelle Li of the embodiment of the invention one preparation 4Ti 5O 12The XRD collection of illustrative plates;
Fig. 2 is that the carbon of the embodiment of the invention two preparations coats lithium titanate material first charge-discharge curve chart;
Fig. 3 is that the carbon of the embodiment of the invention two preparations coats lithium titanate material charge-discharge performance figure under different multiplying.
Fig. 4 is that the carbon of the embodiment of the invention three preparations coats the cycle performance figure of lithium titanate material under 5C.
Embodiment
Embodiment one: take by weighing respectively 3.0g sucrose and 6.0g titanium dioxide, place the 250mL beaker, add the 80mL absolute ethyl alcohol, stir 6h, be placed in 80 ℃ of baking ovens and dry; The sucrose of oven dry and the mixture of titanium dioxide carry out sintering under 600 ℃ in nitrogen, temperature retention time is 5 hours, naturally is down to room temperature, obtain the nano titanium oxide that carbon coats; Mixture (mass fraction of lithium oxalate is 1%) and titanium dioxide with lithium carbonate and lithium oxalate, according to Li: Ti=0.8: 1 mol ratio is prepared burden, ball milling in medium-acetone, oven dry, 800 ℃ of lower sintering are 10 hours in nitrogen, obtain the lithium titanate powder that carbon coats.
Embodiment two: take by weighing respectively 0.6g sucrose and 2.0g titanium dioxide, place the 250mL beaker, add the 80mL absolute ethyl alcohol, stir 6h, be placed in 80 ℃ of baking ovens and dry; The sucrose of oven dry and the mixture of titanium dioxide carry out sintering under 600 ℃ in nitrogen, temperature retention time is 5 hours, naturally is down to room temperature, obtain the nano titanium oxide that carbon coats; Mixture (mass fraction of lithium oxalate is 1%) and titanium dioxide with lithium carbonate and lithium oxalate, according to Li: Ti=0.8: 1 mol ratio is prepared burden, ball milling in medium-acetone, oven dry, 800 ℃ of lower sintering are 10 hours in nitrogen, obtain the lithium titanate powder that carbon coats.
Embodiment three: take by weighing respectively 2.0g glucose and 4.0g titanium dioxide, place the 150mL beaker, add the 60mL absolute ethyl alcohol, stir 6h, be placed in 80 ℃ of baking ovens and dry; The glucose of oven dry and the mixture of titanium dioxide carry out sintering under 600 ℃ in nitrogen, temperature retention time is 5 hours, naturally is down to room temperature, obtain the nano titanium oxide that carbon coats; Mixture (mass fraction of lithium oxalate is 1%) and titanium dioxide with lithium acetate and lithium oxalate, according to Li: Ti=0.8: 1 mol ratio is prepared burden, ball milling in medium-acetone, oven dry, 800 ℃ of lower sintering are 10 hours in nitrogen, obtain the lithium titanate powder that carbon coats.
Embodiment four: take by weighing respectively 2.0g glucose and 4.0g titanium dioxide, place the 150mL beaker, add the 60mL absolute ethyl alcohol, stir 6h, be placed in 80 ℃ of baking ovens and dry; The glucose of oven dry and the mixture of titanium dioxide carry out sintering under 600 ℃ in nitrogen, temperature retention time is 5 hours, naturally is down to room temperature, obtain the nano titanium oxide that carbon coats; Mixture (mass fraction of lithium oxalate is 2%) and titanium dioxide with lithium carbonate and lithium oxalate, according to Li: Ti=0.8: 1 mol ratio is prepared burden, ball milling in medium-acetone, oven dry, 800 ℃ of lower sintering are 10 hours in nitrogen, obtain the lithium titanate powder that carbon coats.

Claims (8)

1. a cathode material for lithium-ion power battery carbon coats the preparation method of lithium titanate, comprises following processing step:
A) take by weighing a certain amount of carbon source and titanium dioxide, its mass ratio is: (3~5): 10, be dissolved in a certain amount of alcohol, and fully stirred for several hour is dried mixture in baking oven;
B) carbon source of drying in the steps A and the mixture of titanium dioxide are carried out sintering under 400~700 ℃ in inert atmosphere, temperature retention time is 5~8 hours, naturally is down to room temperature, obtains the nano titanium oxide that carbon coats;
C) with lithium compound and titanium dioxide, according to Li: Ti=(0.8~1.0): 1 mol ratio is prepared burden, ball milling in uniform dielectric, and oven dry, 600~900 ℃ of lower sintering are 8~10 hours in inert atmosphere, obtain the lithium titanate powder that carbon coats.
2. a kind of cathode material for lithium-ion power battery carbon according to claim 1 coats the preparation method of lithium titanate, and it is characterized in that: described carbon source is sucrose or glucose or its mixture.
3. a kind of cathode material for lithium-ion power battery carbon according to claim 1 coats the preparation method of lithium titanate, and it is characterized in that: described titanium dioxide is Detitanium-ore-type.
4. a kind of cathode material for lithium-ion power battery carbon according to claim 1 coats the preparation method of lithium titanate, and it is characterized in that: described inert atmosphere is a kind of or its mist in argon gas, the nitrogen.
5. a kind of cathode material for lithium-ion power battery carbon according to claim 1 coats the preparation method of lithium titanate, it is characterized in that: described lithium compound is the mixture of at least a and lithium oxalate in lithium carbonate, the lithium acetate, and the content of lithium oxalate is 1~5%.
6. a kind of cathode material for lithium-ion power battery carbon according to claim 1 coats the preparation method of lithium titanate, and it is characterized in that: described ball-milling medium is acetone or alcohol.
7. a kind of cathode material for lithium-ion power battery carbon according to claim 1 coats the preparation method of lithium titanate, and it is characterized in that: described bake out temperature is 80 ℃.
8. a kind of cathode material for lithium-ion power battery carbon according to claim 1 coats the preparation method of lithium titanate, and it is characterized in that: described heating rate is controlled to be 120~180 ℃/hour.
CN2012105165957A 2012-12-05 2012-12-05 Method for preparing anode material carbon coated lithium titanate for lithium ion power batteries Pending CN102945952A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103682278A (en) * 2013-12-26 2014-03-26 山东精工电子科技有限公司 Preparation method of nanocarbon coated lithium titanate cathode material
CN105609321A (en) * 2016-03-25 2016-05-25 陕西煤业化工技术研究院有限责任公司 Lithium ion capacitor cathode composite material and preparation method thereof
WO2016202162A1 (en) * 2015-06-16 2016-12-22 田东 Method for synthesizing lithium-ion negative-electrode material li4ti5o12/c
CN106486662A (en) * 2016-12-09 2017-03-08 江南大学 The preparation method of carbon-coated lithium ion battery negative material
CN107170975A (en) * 2017-06-01 2017-09-15 江汉大学 A kind of method and lithium titanate for lifting lithium titanate electrical conductivity
CN107528057A (en) * 2017-08-31 2017-12-29 北方奥钛纳米技术有限公司 The preparation method of carbon coating lithium titanate and carbon coating lithium titanate and application
CN111969189A (en) * 2020-08-21 2020-11-20 贵州梅岭电源有限公司 Lithium ion battery composite negative electrode material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101391806A (en) * 2007-09-20 2009-03-25 北京有色金属研究总院 Method for manufacturing spinelle lithium titanate for lithium ionic cell cathode material
CN101777644A (en) * 2010-02-05 2010-07-14 中国科学院新疆理化技术研究所 Method for preparing carbon-encapsulated magnesium-doped lithium ion battery cathode material lithium titanate
CN102148351A (en) * 2010-02-06 2011-08-10 清华大学 Preparation method for electrode material of lithium battery
CN102496707A (en) * 2011-12-30 2012-06-13 天津力神电池股份有限公司 Preparation method of nano-grade-carbon-clad spinel lithium titanate battery cathode material
CN102522536A (en) * 2011-12-17 2012-06-27 合肥国轩高科动力能源有限公司 Template synthesis method for lithium-ion anode material lithium titanate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101391806A (en) * 2007-09-20 2009-03-25 北京有色金属研究总院 Method for manufacturing spinelle lithium titanate for lithium ionic cell cathode material
CN101777644A (en) * 2010-02-05 2010-07-14 中国科学院新疆理化技术研究所 Method for preparing carbon-encapsulated magnesium-doped lithium ion battery cathode material lithium titanate
CN102148351A (en) * 2010-02-06 2011-08-10 清华大学 Preparation method for electrode material of lithium battery
CN102522536A (en) * 2011-12-17 2012-06-27 合肥国轩高科动力能源有限公司 Template synthesis method for lithium-ion anode material lithium titanate
CN102496707A (en) * 2011-12-30 2012-06-13 天津力神电池股份有限公司 Preparation method of nano-grade-carbon-clad spinel lithium titanate battery cathode material

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103682278A (en) * 2013-12-26 2014-03-26 山东精工电子科技有限公司 Preparation method of nanocarbon coated lithium titanate cathode material
CN103682278B (en) * 2013-12-26 2016-05-11 山东精工电子科技有限公司 The preparation method of the coated lithium titanate anode material of a kind of nanometer carbon
WO2016202162A1 (en) * 2015-06-16 2016-12-22 田东 Method for synthesizing lithium-ion negative-electrode material li4ti5o12/c
CN105609321A (en) * 2016-03-25 2016-05-25 陕西煤业化工技术研究院有限责任公司 Lithium ion capacitor cathode composite material and preparation method thereof
CN105609321B (en) * 2016-03-25 2018-07-31 陕西煤业化工技术研究院有限责任公司 A kind of lithium-ion capacitor anode material and preparation method thereof
CN106486662A (en) * 2016-12-09 2017-03-08 江南大学 The preparation method of carbon-coated lithium ion battery negative material
CN107170975A (en) * 2017-06-01 2017-09-15 江汉大学 A kind of method and lithium titanate for lifting lithium titanate electrical conductivity
CN107528057A (en) * 2017-08-31 2017-12-29 北方奥钛纳米技术有限公司 The preparation method of carbon coating lithium titanate and carbon coating lithium titanate and application
CN111969189A (en) * 2020-08-21 2020-11-20 贵州梅岭电源有限公司 Lithium ion battery composite negative electrode material and preparation method thereof
CN111969189B (en) * 2020-08-21 2021-10-26 贵州梅岭电源有限公司 Lithium ion battery composite negative electrode material and preparation method thereof

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Application publication date: 20130227