CN102324511A - Preparation method for lithium ion battery composite cathode material - Google Patents

Preparation method for lithium ion battery composite cathode material Download PDF

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CN102324511A
CN102324511A CN201110303494A CN201110303494A CN102324511A CN 102324511 A CN102324511 A CN 102324511A CN 201110303494 A CN201110303494 A CN 201110303494A CN 201110303494 A CN201110303494 A CN 201110303494A CN 102324511 A CN102324511 A CN 102324511A
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lithium ion
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赵海雷
杨茜
王捷
王静
王春梅
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University of Science and Technology Beijing USTB
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Abstract

The invention discloses a preparation method for a lithium ion battery composite cathode material, and belongs to the field of new materials and electrochemistry, and aims to provide a compound electrode material capable of charging and discharging at a high magnification and an economical and feasible preparation process. The preparation method comprises the following steps of: preparing Li4Ti5O12-TiO2 nano particles by using lithium acetate and tetrabutyl titanate as raw materials and ammonia water as a pH value regulator, and adopting a solvent thermal bonding treatment method; then uniformly coating a carbon source on the surface of the Li4Ti5O12-TiO2 composite particles through a rotary evaporation process; and performing high-temperature pyrolysis to prepare a Li4Ti5O12-TiO2/C composite material. The Li4Ti5O12-TiO2/C composite material prepared by the method is fine in particle and uniform in particle size and composition distribution, has high magnification property and cyclical stability, can bring advantages of Li4Ti5O12, TiO2 and C into play, is an ideal high-magnification lithium ion battery composite cathode material, and can be widely used in the fields of portable electronic equipment, electric vehicles, aerospace and the like.

Description

A kind of preparation method of composite cathode material for lithium ion cell
Technical field
The invention belongs to new material and electrochemical field, but be specifically related to a kind of Li of high power charging-discharging 4Ti 5O 12-TiO 2/ C composite cathode material for lithium ion cell and preparation method thereof.
Background technology
Under the dual-pressure of energy crisis and environmental pollution, each state is all striving to find novel energy, and the forerunner of green energy resource---lithium ion battery is widely used in fields such as portable electric appts, Aero-Space, military affairs.At present, the fashionable whole world of the electric automobile of energy-conserving and environment-protective makes height ratio capacity, high cyclical stability, the excellent motive-power battery of high rate performance become the emphasis of current research.
The graphite-like carbon negative pole material of commercial extensive use exists some drawbacks: the current potential of carbon electrode and the current potential of lithium metal are very near (100 mV vs. Li +/ Li), the surface is prone to the precipitating metal lithium and forms dendrite, has potential safety hazard; Generate the SEI film with the electrolyte reaction in the discharge process first, coulombic efficiency is low first; Lithium ion takes off in the embedding process repeatedly, and material structure is damaged and causes the specific capacity decay, has reduced it and has recycled the life-span.So novel negative material has become the focus of current concern.
Li 4Ti 5O 12Have charge and discharge platform (1.55 V vs. Li stably +/ Li), not with the electrolyte reaction, fail safe reaches coulombic efficiency height first; In the removal lithium embedded process, changes in crystal structure is very little, is called as " zero strain material ", has good cyclical stability, long service life.Li 4Ti 5O 12Have huge using value as the power type negative material, cause its capacity attenuation when high current charge-discharge fast but conductivity is low, high rate performance is relatively poor.At present, improve Li 4Ti 5O 12The key of material power density is to improve its electronic conductivity and ionic conductivity, takes following method usually:
(1) ion doping.In the Li position or the Ti position carry out high-valence cationic to mix, carry out in the O position low price anion doped, according to elrectroneutrality pcharge-neutrality principle, part Ti ion is by Ti 4+To Ti 3+Change, improve Li 4Ti 5O 12The electronic conductivity of material.But it improves Li 4Ti 5O 12The DeGrain of material high rate performance; Simultaneously, doped chemical gets into Li 4Ti 5O 12Lattice can reduce the structural stability of material to a certain extent.The Wen Zhaoyin group of Shanghai silicate research institute is to Li 4Ti 5O 12Carried out the cation doping study on the modification, synthesized Li through solid phase method 3.95M 0.15Ti 4.9O 12(M=Al, Ga, Co) and Li 3.9Mg 0.1Al 0.15Ti 4.85O 12, discover Al 3+Be doped with and be beneficial to the specific capacity that improves material, its stable cycle performance; Doping Ga 3+Specific capacity for material has raising slightly, but cyclical stability reduces slightly; Co 3+And Mg 2+Mix, reduced Li to a certain extent 4Ti 5O 12The chemical property of material (Shahua Huang, Zhaoyin Wen, Xiujian Zhu, Zuxiang Lin. Effects of dopant on the electrochemical performance of Li 4Ti 5O 12As electrode material for lithium ion batteries. J. Power Sources 165 (2007) 408 – 412).
(2) introduce high conductive phase, the method for taking carbon to coat usually.Carbon is dispersed in Li 4Ti 5O 12Particle surface has bridging action, has strengthened the electron conduction ability between the particle, has improved the high rate performance of material.Simultaneously, carbon does not get into Li 4Ti 5O 12Lattice does not influence the structural stability of material.The Deng Zhenghua of the Chinese Academy of Sciences etc. are lithium source and carbon source with PAALi, TiO 2For having synthesized Li in the titanium source 4Ti 5O 12/ C negative material, particle size are about 200 nm, at 8.60 mA/cm 2Current density under discharge and recharge, specific capacity reaches 130.0 mAh/g first, cyclical stability good (Ziji Lin, Xuebu Hu, Yongjian Huai, Li Liu, Zhenghua Deng, Jishuan Suo. One-step synthesis of Li 4Ti 5O 12/ C anode material with high performance for lithiumion batteries. Solid State Ionics 181 (2010) 412 – 415).The Yu Zuolong of the Chinese Academy of Sciences etc. has synthesized Li through solid phase method 4Ti 5O 12/ GCNTs composite material; It has height ratio capacity and good high rate performance, and under the current density of 10 C, discharge capacity reaches 143 mAh/g first; Circulate after 100 times; Specific capacity is 132 mAh/g (Xing Li, Meizhen Qu, Zuolong Yu. Preparation and electrochemical performance of Li 4Ti 5O 12/ graphitized carbon nanotubes composite. Solid State Ionics 181 (2010) 635 – 639).The Gao Lijun of CANADIAN SOLAR INC., has synthesized Li through sol-gel process 4Ti 5O 12/ C composite material, its high rate performance is good, when stable cycle performance and lithium metal are formed half-cell; Under 60 C discharging conditions; Specific capacity is 108.9 mAh/g first, and after 2000 circulations, capability retention is 75.9%; When forming lithium ion battery with spinel lithium manganate, 85% the when discharge capacity under 1 A/g current density is 60 mA/g (CN 101867036 A).The carbon coating type lithium titanate material of preparations such as the Xu Nin of Tianjin Bamo Technology Co has good high rate performance, and reversible capacity is 150.1 mAh/g during 10 C, 90.3% of capacity (CN 101378119A) when being 0.1 C.
(3) the preparation nano-scale particle shortens the lithium ion the evolving path, improves the ionic conductivity of material.The Zhang Naiqing of Harbin Institute of Technology etc. has synthesized nanometer Li through sol-gel process 4Ti 5O 12Particle, particle size are about 100 nm, under 40 C current densities; The tool specific capacity is up to 108 mAh/g, and material has excellent cyclical stability and capacity restoration property (Naiqing Zhang; Zhimin Liu, Tongyong Yang, Chenglong Liao; Zhijun Wang, Kening Sun. Facile preparation of nanocrystalline Li 4Ti 5O 12And its high electrochemical performance as anode material for lithium-ion batteries. Electrochem. Commun. 13 (2011) 654 – 656).The Yang Li of Shanghai Communications University etc. are through the synthetic Li of hydro thermal method 4Ti 5O 12Negative material, under the current density condition of 20 C, specific discharge capacity is 125 mAh/g, stable circulation, high-rate charge-discharge capability good (CN 101409341A).
TiO 2Theoretical specific capacity be 335 mAh/g, have suitable embedding lithium current potential (~ 2 V vs. Li +/ Li), cubical expansivity low (3 ~ 4%), be introduced into Li 4Ti 5O 12In, can improve the specific capacity of material.The alkaline molten salt growth methods of employing such as Australia M.M. Rahman have been synthesized nanometer Li 4Ti 5O 12-TiO 2Negative material, under 1 C current density condition, first discharge specific capacity is 146 mAh/g; Circulate after 100 times, capability retention is 95% (M.M. Rahman, Jia-Zhao Wang; Mohd Faiz Hassan; Shulei Chou, David Wexler, Hua-Kun Liu. Basic molten salt process-A new route for synthesis of nanocrystalline Li 4Ti 5O 12-TiO 2Anode material for Li-ion batteries using eutectic mixture of LiNO 3– LiOH – Li 2O 2. J. Power Sources 195 (2010) 4297 – 4303).
Summary of the invention
The object of the present invention is to provide that a kind of particle is tiny, particle size distribution is even, pattern is regular, under the high power charging-discharging condition, have the higher relatively specific capacity and the Li of cyclical stability 4Ti 5O 12-TiO 2/ C composite cathode material for lithium ion cell.
A kind of preparation method of composite cathode material for lithium ion cell is characterized in that: it is by Li 4Ti 5O 12, TiO 2, three kinds of components of C constitute.
Its concrete steps are:
(1) configuration solution: select for use and analyze pure butyl titanate as the titanium source, mix with organic solvent, stir, process clear solution, wherein the addition of titanium is at 0.0001 ~ 0.1 mol/100 ml solvent;
Select for use and analyze pure lithium acetate, prepare, it is joined in the settled solution, stir according to atomic ratio Li/Ti=0.8 ~ 1.6 as the lithium source;
Select for use and analyze pure ammoniacal liquor (quality percentage composition 25 ~ 28%) as pH value conditioning agent, dropwise join in the solution, wherein the addition of ammoniacal liquor is at 1 ~ 8 ml/100 ml solvent;
(2) above-mentioned solution is placed autoclave, carry out solvent thermal reaction, synthesis condition is: 140 ~ 180 oC insulation 12 ~ 48 hours;
(3) with the product of step (2) gained with absolute ethanol washing, filter after, place baking oven 80 ~ 120 oThe C oven dry obtains Li 4Ti 5O 12-TiO 2Presoma;
(4) under the air atmosphere, the presoma of step (3) gained is warming up to 450 ~ 650 oC insulation 1.5 ~ 4 hours cools to room temperature with the furnace and makes Li 4Ti 5O 12-TiO 2Powder;
(5) Li that step (4) is made 4Ti 5O 12-TiO 2Mix in solvent with carbon source, be stirred to evenly, through rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface;
(6) under the inertia protective atmosphere, the powder of step (5) gained is warming up to 550 ~ 650 oC insulation 1 ~ 5 hour cools to room temperature then with the furnace, makes Li 4Ti 5O 12-TiO 2/ C composite negative pole material.
The described organic solvent of step (1) is a unary alcohol, and described ammoniacal liquor can disposablely fast join in the solution, also can slowly dropwise join in the solution.
The described carbon source of step (5) is one or more among sucrose, glucose, starch, epoxy resin, fructose, the PVdF.
The described inertia protective atmosphere of step (6) is one or both in nitrogen, the argon gas.
TiO 2At Li 4Ti 5O 12-TiO 2Quality percentage composition in the powder is 5 ~ 50%, and C is at Li 4Ti 5O 12-TiO 2Quality percentage composition in the/C composite negative pole material is 1 ~ 10%, and carbon source does not get into basis material Li 4Ti 5O 12-TiO 2Lattice.
TiO 2At Li 4Ti 5O 12-TiO 2Content in the powder is preferably 15 ~ 40%, and this is because if TiO 2Content is low excessively, then synthetic Li 4Ti 5O 12-TiO 2Grain diameter is bigger, and is not obvious to the improvement of material ionic conductivity; TiO 2Too high levels, then synthetic Li 4Ti 5O 12-TiO 2The too small easy reunion of particle is unfavorable for improving the chemical property of material.
Take into account consideration from capacity and conductivity, C is at Li 4Ti 5O 12-TiO 2Content in the/C composite negative pole material is preferably 2 ~ 4%, and this is because if carbon content is low excessively, then can't fundamentally improve the electron conduction of material, and carbon content is too high, then can reduce the specific capacity of material.
Li 4Ti 5O 12Material has good cyclical stability as " zero strain material "; TiO 2But the material removal lithium embedded, and when heat treatment, because space steric effect has suppressed Li 4Ti 5O 12The growth of particle obtains nanometer Li 4Ti 5O 12-TiO 2Particle has shortened the lithium ion the evolving path, has improved the ionic conductivity of material; Carbon is dispersed between the particle or is coated on particle surface, has good bridging action, improved material electron conduction, bringing into play three's advantage separately.
Adopt the negative material of this method preparation to have the following advantages:
(1) particle is tiny, and particle size distribution is even, and pattern is regular;
(2) carbon source does not get into basis material Li 4Ti 5O 12-TiO 2Lattice, help keeping the structural stability of material;
(3) under the high power charging-discharging condition, have higher relatively specific capacity and cyclical stability;
(4) each component can be brought into play advantage separately.
The present invention utilizes space steric effect, original position synthesis of nano Li through solvent-thermal method 4Ti 5O 12-TiO 2Composite material, and utilize rotary evaporation technology evenly to coat one deck carbon at particle surface, preparation Li 4Ti 5O 12-TiO 2/ C composite negative pole material.TiO 2Existence, capacity is provided on the one hand, stop particle to be grown up on the one hand, realize the nanometerization of active powder; The nano active particle has good ionic conductivity; Carbon coats the electron conduction that material is improved in the back.The three is bringing into play advantage separately.Under the high current charge-discharge condition, Li 4Ti 5O 12-TiO 2/ C material have height ratio capacity, high cyclical stability and a high security, be a kind of well behaved lithium ion battery negative material.
The invention has the advantages that in the building-up process of material, flexible operation, simple, reaction condition is gentle, and thing formation mutually, size and particle shape are easy to control.
Li 4Ti 5O 12-TiO 2/ C composite material is a kind of well behaved composite cathode material for lithium ion cell, and this material and preparation method thereof is not seen document and patent report as yet.
Description of drawings
Fig. 1 is the Li of embodiment 1 4Ti 5O 12-TiO 2The charging and discharging curve figure of/C.
Embodiment
Below in conjunction with embodiment the present invention is further specified, but is not limited to protection scope of the present invention:
Embodiment 1:
Take by weighing 2.383 g and analyze pure butyl titanate (purity>=99.0%) and be dissolved in the 50 ml absolute ethyl alcohols, stir, process clear solution; According to atomic ratio Li/Ti=1.4, take by weighing 1.000 g lithium acetates (purity>=99.0%), join in the settled solution, continue to stir until forming homogeneous solution; Dropwise add 2 ml ammoniacal liquor to solution, after mixing mixed liquor is transferred in the 100 ml autoclaves, and places baking oven, 180 oC insulation 24 hours is cooled to room temperature, the product of gained with absolute ethanol washing, filtration after, place baking oven 80 oThe C oven dry obtains Li 4Ti 5O 12-TiO 2Presoma; Under the air atmosphere, the presoma of gained is warming up to 600 oC insulation 2 hours cools to room temperature with the furnace and makes Li 4Ti 5O 12-TiO 2Powder, wherein, TiO 2At Li 4Ti 5O 12-TiO 2Content in the powder is about 23%; Take by weighing 0.450 g Li 4Ti 5O 12-TiO 2Powder, 0.027 g sucrose mix both in absolute ethyl alcohol, be stirred to evenly, and through rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface; Under the high pure nitrogen protective atmosphere, powder is warming up to 600 oC insulation 1 hour cools to room temperature then with the furnace, makes Li 4Ti 5O 12-TiO 2/ C composite negative pole material, C is at Li 4Ti 5O 12-TiO 2Content in the/C composite negative pole material is about 2%.
With the Li that makes 4Ti 5O 12-TiO 2The PVdF of the acetylene black of/C composite negative pole material, 10 wt%, 5 wt% mixes, and processes slurry, evenly is coated on the Copper Foil, is stamped into the circular electrode pole piece behind the vacuum drying, is to electrode with lithium metal, 1 mol/L LiPF 6/ EMC+DC+EC (volume ratio is 1:1:1) is an electrolyte, and Celgard 2400 is a barrier film, forms test cell.Battery is carried out the constant current charge-discharge test, and current density is 5 C (1 C=175 mA/g), and the charging/discharging voltage scope is 1.0 ~ 2.5 V.The result shows that its maximum reversible specific capacity reaches 167.7 mAh/g, and after 100 circulations, specific capacity remains on about 150 mAh/g.
 
Embodiment 2:
Take by weighing 2.383 g and analyze pure butyl titanate (purity>=99.0%) and be dissolved in the 50 ml absolute ethyl alcohols, stir, process clear solution; According to atomic ratio Li/Ti=1.4, take by weighing 1.000 g lithium acetates (purity>=99.0%), join in the settled solution, continue to stir until forming homogeneous solution; Dropwise add 1 ml ammoniacal liquor to solution, after mixing mixed liquor is transferred in the 100 ml autoclaves, and places baking oven, 180 oC insulation 24 hours is cooled to room temperature, the product of gained with absolute ethanol washing, filtration after, place baking oven 80 oThe C oven dry obtains Li 4Ti 5O 12-TiO 2Presoma; Under the air atmosphere, the presoma of gained is warming up to 600 oC insulation 2 hours cools to room temperature with the furnace and makes Li 4Ti 5O 12-TiO 2Powder, wherein, TiO 2At Li 4Ti 5O 12-TiO 2Content in the powder is about 19%; Take by weighing 0.450 g Li 4Ti 5O 12-TiO 2Powder, 0.026 g starch mix both in absolute ethyl alcohol, be stirred to evenly, and through rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface; Under the high pure nitrogen protective atmosphere, powder is warming up to 600 oC insulation 1 hour cools to room temperature then with the furnace, makes Li 4Ti 5O 12-TiO 2/ C composite negative pole material, C is at Li 4Ti 5O 12-TiO 2Content in the/C composite negative pole material is about 2%.
Electrochemical property test is identical with embodiment 1.The result shows that its maximum reversible specific capacity reaches 165.5 mAh/g, and after 100 circulations, capacity remains on about 150 mAh/g.
 
Embodiment 3:
Take by weighing 2.383 g and analyze pure butyl titanate (purity>=99.0%) and be dissolved in the 50 ml absolute ethyl alcohols, stir, process clear solution; According to atomic ratio Li/Ti=1.2, take by weighing 0.857 g lithium acetate (purity>=99.0%), join in the settled solution, continue to stir until forming homogeneous solution; Dropwise add 2 ml ammoniacal liquor to solution, after mixing mixed liquor is transferred in the 100 ml autoclaves, and places baking oven, 180 oC insulation 24 hours is cooled to room temperature, the product of gained with absolute ethanol washing, filtration after, place baking oven 80 oThe C oven dry obtains Li 4Ti 5O 12-TiO 2Presoma; Under the air atmosphere, the presoma of gained is warming up to 600 oC insulation 2 hours cools to room temperature with the furnace and makes Li 4Ti 5O 12-TiO 2Powder, wherein, TiO 2At Li 4Ti 5O 12-TiO 2Content in the powder is about 25%; Take by weighing 0.450 g Li 4Ti 5O 12-TiO 2Powder, 0.044 g glucose mix both in absolute ethyl alcohol, be stirred to evenly, and through rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface; Under the high pure nitrogen protective atmosphere, powder is warming up to 600 oC insulation 1 hour cools to room temperature then with the furnace, makes Li 4Ti 5O 12-TiO 2/ C composite negative pole material, C is at Li 4Ti 5O 12-TiO 2Content in the/C composite negative pole material is about 2%.
Electrochemical property test is identical with embodiment 1.The result shows that its maximum reversible specific capacity reaches 131.4 mAh/g, and after 100 circulations, capacity remains on about 115 mAh/g.

Claims (8)

1. the preparation method of a composite cathode material for lithium ion cell, it is characterized in that: it is by Li 4Ti 5O 12, TiO 2, three kinds of components of C constitute, processing step is: (1) configuration solution: select for use and analyze pure butyl titanate as the titanium source, mix with organic solvent, stir, process clear solution, wherein the addition of titanium is at 0.0001 ~ 0.1 mol/100 ml solvent;
Select for use and analyze pure lithium acetate, prepare, it is joined in the settled solution, stir according to atomic ratio Li/Ti=0.8 ~ 1.6 as the lithium source;
The pure ammoniacal liquor of analysis of selecting weight percentage 25 ~ 28% for use dropwise joins in the solution as pH value conditioning agent, and wherein the addition of ammoniacal liquor is at 1 ~ 8 ml/100 ml solvent;
(2) above-mentioned solution is placed autoclave, carry out solvent thermal reaction, synthesis condition is: 140 ~ 180 oC insulation 12 ~ 48 hours;
(3) with the product of step (2) gained with absolute ethanol washing, filter after, place baking oven 80 ~ 120 oThe C oven dry obtains Li 4Ti 5O 12-TiO 2Presoma;
(4) under the air atmosphere, the presoma of step (3) gained is warming up to 450 ~ 650 oC insulation 1.5 ~ 4 hours cools to room temperature with the furnace and makes Li 4Ti 5O 12-TiO 2Powder;
(5) Li that step (4) is made 4Ti 5O 12-TiO 2Mix in solvent with carbon source, be stirred to evenly, through rotary evaporation, carbon source evenly is coated on Li 4Ti 5O 12-TiO 2Particle surface;
(6) under the inertia protective atmosphere, the powder of step (5) gained is warming up to 550 ~ 650 oC insulation 1 ~ 5 hour cools to room temperature then with the furnace, makes Li 4Ti 5O 12-TiO 2/ C composite negative pole material.
2. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: the described organic solvent of step (1) is a unary alcohol.
3. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: the described ammoniacal liquor of step (1) can disposablely fast join in the solution, also can slowly dropwise join in the solution.
4. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: the described carbon source of step (5) is one or more among sucrose, glucose, starch, epoxy resin, fructose, the PVdF.
5. the preparation method of composite cathode material for lithium ion cell according to claim 1, it is characterized in that: the described inertia protective atmosphere of step (6) is one or both in nitrogen, the argon gas.
6. the preparation method of composite cathode material for lithium ion cell according to claim 1 is characterized in that: TiO 2At Li 4Ti 5O 12-TiO 2Quality percentage composition in the powder is 5 ~ 50%, and C is at Li 4Ti 5O 12-TiO 2Quality percentage composition in the/C composite negative pole material is 1 ~ 10%, and carbon source does not get into basis material Li 4Ti 5O 12-TiO 2Lattice.
7. the preparation method of composite cathode material for lithium ion cell according to claim 6 is characterized in that: TiO 2At Li 4Ti 5O 12-TiO 2Quality percentage composition in the powder is 15 ~ 40%.
8. the preparation method of composite cathode material for lithium ion cell according to claim 6, it is characterized in that: C is at Li 4Ti 5O 12-TiO 2Quality percentage composition in the/C composite negative pole material is 2 ~ 4%.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544468A (en) * 2012-02-10 2012-07-04 中国科学院福建物质结构研究所 Carbon-coated mesoporous lithium titanate anode material of lithium ion battery and method for preparing carbon-coated mesoporous lithium titanate anode material
CN102891289A (en) * 2012-10-23 2013-01-23 中国科学院过程工程研究所 Multi-dimensional LTO/C nano composite material, preparation method and application thereof
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CN105789583A (en) * 2016-03-28 2016-07-20 辽宁大学 Lithium ion battery anode material Li4Ti5O12/TiO2/Ag and preparation method thereof
CN105845901A (en) * 2016-03-28 2016-08-10 辽宁大学 Lithium ion battery negative material Li4Ti5O12 / TiO2 / RGO and preparation method thereof
CN105932238A (en) * 2016-05-11 2016-09-07 新疆大学 Preparation method of lithium ion battery negative electrode material lithium titanate coated by spherical rare earth metal oxide
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CN109319830A (en) * 2018-11-13 2019-02-12 北方奥钛纳米技术有限公司 Lithium titanate material and preparation method thereof, negative electrode tab, battery
CN109904439A (en) * 2017-12-11 2019-06-18 中信国安盟固利动力科技有限公司 A kind of low temperature preparation method of novel titanium base material
CN112736236A (en) * 2021-01-15 2021-04-30 辽宁大学 Novel biomass carbon-coated biphase Li serving as lithium ion battery negative electrode material4Ti5O12-TiO2And uses thereof
CN114702065A (en) * 2022-03-25 2022-07-05 扬州大学 Oxygen-enriched defective TiO2Carbon composite material, preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010031401A1 (en) * 1999-02-16 2001-10-18 Tetsuya Yamawaki Process for producing lithium titanate and lithium ion battery and negative electrode therein
CN101378119A (en) * 2008-10-06 2009-03-04 天津巴莫科技股份有限公司 Method for preparing carbon-coating type lithium titanate for lithium ion battery
CN101944591A (en) * 2010-09-14 2011-01-12 耿世达 Lithium titanate anode material for lithium ion batteries and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010031401A1 (en) * 1999-02-16 2001-10-18 Tetsuya Yamawaki Process for producing lithium titanate and lithium ion battery and negative electrode therein
CN101378119A (en) * 2008-10-06 2009-03-04 天津巴莫科技股份有限公司 Method for preparing carbon-coating type lithium titanate for lithium ion battery
CN101944591A (en) * 2010-09-14 2011-01-12 耿世达 Lithium titanate anode material for lithium ion batteries and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
单宇 等: "溶胶_凝胶法制备Li4Ti5O12/C复合负极材料及性能研究", 《电源技术》 *

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