CN102299333A - Preparation method of carbon coated Li4Ti5O12 nano cathode material - Google Patents

Preparation method of carbon coated Li4Ti5O12 nano cathode material Download PDF

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CN102299333A
CN102299333A CN2011101965395A CN201110196539A CN102299333A CN 102299333 A CN102299333 A CN 102299333A CN 2011101965395 A CN2011101965395 A CN 2011101965395A CN 201110196539 A CN201110196539 A CN 201110196539A CN 102299333 A CN102299333 A CN 102299333A
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lithium
carbon
preparation
negative material
cladded type
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徐云龙
郑少伟
钱秀珍
赵崇军
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WEINA TECH Co Ltd SHANGHAI
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WEINA TECH Co Ltd SHANGHAI
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a preparation method of a carbon coated Li4Ti5O12 lithium ion battery nano cathode material with high multiplying performance, comprising the following steps: using a proper amount of organo-lithium compound as lithium source and carbon source, fully mixing the lithium source, organo-lithium compound and titanium source in a mixer according to a certain molar ratio, and then putting the mixture in a sintering furnace for sintering under inert atmosphere. The method has the advantages of simple process, little energy consumption, short preparation period and easy control. According to the invention, the prepared Li4Ti5O12 nano cathode material has high crystallinity, a compact and uniform carbon film with the thickness of about 1 nm is coated on the surface of the material, the average particle size is about 30 nm, the high-rate electrochemical performance is excellent, the discharge capacity at 10C rate is 136.7 mAh/g, the discharge capacity at 20C rate is 121.1 mAh/g, and the cycle performance is good.

Description

A kind of carbon cladded type Li＜sub〉4＜/sub〉Ti＜sub〉5＜/sub〉O＜sub〉12＜/sub〉preparation method of nanometer negative material
Technical field
The invention belongs to the energy and material technical field, particularly carbon modification lithium-ion battery Li 4Ti 5O 12The nanometer cathode material preparation method.
Background technology
Li 4Ti 5O 12As a kind of novel negative material, many good characteristics are arranged: at Li +Embed and deviate from the process, the crystal structure of material does not change substantially, promptly so-called " zero strain " material, and this specific character makes Li 4Ti 5O 12Have good structural stability and excellent cycle performance; Li 4Ti 5O 12Has higher embedding lithium current potential (1.55V vs.Li/Li +), can the precipitating metal lithium in the charge and discharge process, this current potential is higher than the reduction potential of most of organic electrolytes, so the security performance height.
At present, hinder Li 4Ti 5O 12Business-like major obstacle is that (intrinsic conductivity is 10 to its poorly conductive -9S/cm), thereby cause its high-rate charge-discharge capability relatively poor, therefore, need be by its modification be improved Li 4Ti 5O 12Conductivity to improve its high rate capability.
At the problems referred to above, present main method of modifying has: (1) preparation nanometer Li 4Ti 5O 12, reduce grain diameter, with the evolving path of shortening lithium ion in material, thereby improve the diffusion rate of lithium ion in material; (2) carry out cation and anion doped, in crystal structure, introduce defective, be unlikely to influence simultaneously the stability of material structure again, can reduce the migration resistance of lithium ion in material like this, thereby improve its high rate capability; (3) introduce conductive phase, wherein the most frequently used is material with carbon element.
At present, Li 4Ti 5O 12The preparation method mainly contains sol-gel process and conventional solid-state method.Wherein, the sol-gel process reaction temperature is low, obtains nano particle easily, but degree of crystallinity is not high, causes cycle performance relatively poor.And conventional high-temperature solid phase method reaction temperature is higher, product degree of crystallinity height, but high temperature makes grain diameter bigger.
Chinese patent CN101378119A is with Li 2CO 3Be lithium source, TiO 2Be the titanium source, water is dispersant, carries out ball milling and mixes, and oven dry obtains presoma, places 900 ℃ of following roasting 14h of Muffle furnace then, makes Li 4Ti 5O 12Powder with lithium titanate joins in the ethanolic solution of phenolic resins then, stirs to make the ethanol evaporate to dryness, and sintering obtains carbon and coats lithium titanate then.What this patent adopted is the conventional high-temperature solid phase method, and product degree of crystallinity is higher, but because earlier synthetic lithium titanate, carbon coated again, and technology is comparatively complicated, and the product particle diameter is difficult to control, Li 4Ti 5O 12Average grain diameter is about 16 μ m.
Chinese patent CN101877405A, prepare lithium titanate with anhydrous lithium acetate and butyl titanate, prepare graphite oxide with natural flake graphite and sodium nitrate then, the lithium titanate powdery and the graphite oxide that prepare are mixed by a certain percentage, 1000 ℃ of sintering 3min prepare lithium titanate-graphene combination electrode material under nitrogen atmosphere.This method is with low cost, but complicated process of preparation, and Graphene is difficult to play the effect of control lithium titanate particle diameter.
Chinese patent CN101944590A, with lithium chloride, titanium dioxide is raw material, with the capric acid is carbon source, is scattered in the distilled water, is heated to 60 ℃ and vigorous stirring dispersion 5h, then the suspension-turbid liquid that obtains is transferred to and is heated to 220 ℃ in the closed reactor, insulation 12h, after reaction finished, washing, drying obtained predecessor, with predecessor under nitrogen atmosphere 800 ℃ cure 10h, obtain the lithium titanate that carbon coats.The Li of this invention preparation 4Ti 5O 12Particle surface has coated the layer of even carbon film, but has added the carbon source phase, and batch mixing is inhomogeneous, and preparation process is loaded down with trivial details, in addition, uses lithium chloride as the lithium source, has problems such as equipment corrosion and muriatic recycling.
The present invention is directed to the synthetic Li of above-mentioned technology 4Ti 5O 12The existing problem of negative material uses organo-lithium compound simultaneously as lithium source and carbon source, has reduced reacting phase (not having additional carbon), and synthetic in position carbon the time, by control of process parameters, realizes that carbon is to Li 4Ti 5O 12Effective coating and particle diameter control.
Summary of the invention
The object of the invention provides a kind of preparation carbon and coats Li 4Ti 5O 12The method of/C nano composite anode material: with titanium dioxide is the titanium source, replace the part lithium carbonate with organo-lithium compound, organo-lithium compound carbon skeleton pyrolysis product is a carbon source, by solid phase reaction make that degree of crystallinity height, particle diameter are little, carbon coats the especially good carbon cladded type Li of high rate capability of fine and close, chemical property 4Ti 5O 12The nanometer negative material.
Carbon cladded type Li of the present invention 4Ti 5O 12The preparation of nanometer negative material comprises the steps:
Organo-lithium compound, lithium carbonate, titanium dioxide and low amounts of water are put into the ball grinder ball milling mix, obtain slurry, obtain presoma behind the slurry drying, the synthetic carbon cladded type Li that obtains of presoma solid phase reaction under the argon gas atmosphere protection 4Ti 5O 12The nanometer negative material.Lithium mole in the raw material wherein: titanium mole=0.8～1.1, the lithium mole in the organo-lithium compound: lithium mole=0.2～0.8 in the lithium carbonate, optimal proportion are 0.4～0.6; The ball milling incorporation time is 1～6 hour, and best mixing time is 2～4 hours; The slurry drying temperature is 80 ℃～150 ℃, and the optimum drying temperature is 100 ℃～120 ℃, and the slurry drying time is 10～25 hours, and the optimum drying time is 15～20 hours; The solid phase reaction temperature is 600 ℃～1000 ℃, and optimal reaction temperature is 700 ℃～900 ℃; The solid phase reaction time is 6～20 hours, and optimum reacting time is 8～14 hours.
Wherein, described organo-lithium compound thing is one or both the mixture in lithium citrate, the butyl lithium; Titanium dioxide is anatase crystal, and particle diameter is 10～30nm.
Adopt the carbon cladded type Li of preparation method's preparation of the present invention 4Ti 5O 12The nanometer negative material is a black powder, and carbon content is 4.0%～8.0%.
Adopt the carbon cladded type Li of preparation method's preparation of the present invention 4Ti 5O 12The nanometer negative material has excellent chemical property, charging and discharging capacity 〉=170mAh/g under 0.2C, charging and discharging capacity 〉=120mAh/g under the 20C.
Advantage of the present invention:
(1) use organo-lithium compound as lithium source and carbon source, do not have additional carbon, reduced reacting phase, mixing of materials is more even.
(2) organo-lithium compound can evenly be wrapped in surface, titanium source, and also as carbon source, sintering can form tight, uniform chemical carbon coating film to improve Li later in the time of as the lithium source 4Ti 5O 12The conductivity of material.
(3) can control carbon cladded type Li by the ratio of control lithium carbonate, organo-lithium compound 4Ti 5O 12Carbon content in the nanometer negative material.
(4) the use conventional solid-state method can make the carbon with high-crystallinity, nanometer particle size and coat Li 4Ti 5O 12
(5) the carbon cladded type Li that makes of this method 4Ti 5O 12The nanometer negative material has good high-rate charge-discharge capability.
Description of drawings
Fig. 1 is the carbon cladded type Li that embodiment 1 makes 4Ti 5O 12The XRD figure of nanometer negative material.
Fig. 2 is the carbon cladded type Li that makes with embodiment 1 4Ti 5O 12The SEM figure of nanometer negative material.
Fig. 3 is the carbon cladded type Li that makes with embodiment 1 4Ti 5O 12The TEM figure of nanometer negative material.
Fig. 4 is the carbon cladded type Li that makes with embodiment 1 4Ti 5O 12The nanometer negative material is the charging and discharging curve figure of lithium ion battery under 0.2C, 0.5C, 1C, 5C, 8C, 10C and 20C of electrode material assembling.
Fig. 5 is the carbon cladded type Li that makes with embodiment 1 4Ti 5O 12The nanometer negative material is the cycle characteristics figure of the lithium ion battery of electrode material assembling.
Embodiment
Below by EXPERIMENTAL EXAMPLE the present invention is specifically described; it is important to point out that present embodiment only is used for that the present invention will be further described; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
Take by weighing 1.47g lithium citrate, 0.78g lithium carbonate and 4g Detitanium-ore-type TiO 2, add the 5ml deionized water, the three is put into ball grinder ball milling 2h, after the drying with it at 800 ℃ of sintering 12h, naturally cool to room temperature then and promptly make carbon cladded type Li 4Ti 5O 12The nanometer negative material.The content that records carbon in this carbon coating lithium titanate material is 6.7%, and the particle average grain diameter is 30nm, and specific area is 50.7m 2/ g, first discharge specific capacity is 121.1mAh/g during 20C, 100 times the circulation back is 106.1mAh/g.
Embodiment 2
Take by weighing 2.21g lithium citrate, 0.39g lithium carbonate and 4g Detitanium-ore-type TiO 2, add the 5ml deionized water, the three is put into ball grinder ball milling 2h, after the drying with it at 800 ℃ of sintering 12h, naturally cool to room temperature then and promptly make carbon cladded type Li 4Ti 5O 12The nanometer negative material.The content that records carbon in this carbon coating lithium titanate material is 8.0%, and the particle average grain diameter is 25nm, and specific area is 80.2m 2/ g, first discharge specific capacity is 110.5mAh/g during 20C, 100 times the circulation back is 82.6mAh/g.
Embodiment 3
Take by weighing 1.34g butyl lithium, 0.78g lithium carbonate and 4g Detitanium-ore-type TiO 2, add the 5ml deionized water, the three is put into ball grinder ball milling 2h, after the drying with it at 800 ℃ of sintering 12h, naturally cool to room temperature then and promptly make carbon cladded type Li 4Ti 5O 12The nanometer negative material.The content that records carbon in this carbon coating lithium titanate material is 4.0%, and the particle average grain diameter is 60nm, and specific area is 36.7m 2/ g, first discharge specific capacity is 98.2mAh/g during 20C, 100 times the circulation back is 43.5mAh/g.
Embodiment 4
Take by weighing 2.02g butyl lithium, 0.39g lithium carbonate and 4g Detitanium-ore-type TiO 2, add the 5ml deionized water, the three is put into ball grinder ball milling 2h, after the drying with it at 800 ℃ of sintering 12h, naturally cool to room temperature then and promptly make carbon cladded type Li 4Ti 5O 12The nanometer negative material.The content that records carbon in this carbon coating lithium titanate material is 5.7%, and the particle average grain diameter is 45nm, and specific area is 87m 2/ g, first discharge specific capacity is 101.5mAh/g during 20C, 100 times the circulation back is 76.2mAh/g.

Claims (6)

1. carbon cladded type Li 4Ti 5O 12The preparation method of nanometer negative material is characterized in that comprising the steps:
(1) presses the lithium mole: titanium mole=0.8～1.1, lithium mole in the organo-lithium compound: the ratio of lithium mole=0.2～0.8 in the lithium carbonate, organo-lithium compound, lithium carbonate, titanium dioxide and low amounts of water are put into the ball grinder wet ball grinding mixed 1～6 hour, obtain finely dispersed slurry; Wherein used organo-lithium compound is one or both the mixture in lithium citrate, the butyl lithium;
(2) obtain presoma behind the slurry drying, then presoma was carried out solid phase reaction 6～20 hours under 600 ℃～1000 ℃ argon gas atmosphere protections, make carbon cladded type Li 4Ti 5O 12The nanometer negative material.
2. according to the described carbon cladded type of claim 1 Li 4Ti 5O 12The preparation method of nanometer negative material is characterized in that the described titanium dioxide of step (1) is anatase crystal, and particle diameter is 10～30nm.
3. according to the described carbon cladded type of claim 1 Li 4Ti 5O 12The preparation method of nanometer negative material is characterized in that the lithium mole in the described organo-lithium compound of step (1): the lithium mole in the lithium carbonate=0.4: 0.6.
4. according to the described carbon cladded type of claim 1 Li 4Ti 5O 12The preparation method of nanometer negative material is characterized in that the described ball milling incorporation time of step (1) is 2～4 hours.
5. according to the described carbon cladded type of claim 1 Li 4Ti 5O 12The preparation method of nanometer negative material is characterized in that the described reaction temperature of step (2) is 700 ℃～900 ℃, and the reaction time is 8～14 hours.
6. each described preparation carbon cladded type Li of claim 1-5 4Ti 5O 12The carbon cladded type Li that the method for nanometer negative material prepares 4Ti 5O 12The nanometer negative material is characterized in that carbon content is 4.0%～8.0%.
CN2011101965395A 2011-07-14 2011-07-14 Preparation method of carbon coated Li4Ti5O12 nano cathode material Pending CN102299333A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103560227A (en) * 2013-11-13 2014-02-05 重庆理工大学 Preparation method of Li4Ti5O12/C composite material
CN103730647A (en) * 2012-10-10 2014-04-16 中国科学院物理研究所 Rhombic manganese ore material and preparation method, cathode and lithium battery
CN104022257A (en) * 2014-06-16 2014-09-03 深圳市贝特瑞新能源材料股份有限公司 Silicon dioxide composite anode material for lithium ion battery, as well as preparation method and application of silicon dioxide composite anode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101071853A (en) * 2007-06-01 2007-11-14 河南大学 Nano lithium titanate for Negative electrode material of cell or electrochemical vessel, and its and titanium dioxide composite preparing method
CN101431154A (en) * 2008-12-25 2009-05-13 成都中科来方能源科技有限公司 Lithium titanate/C composite electrode material and method for producing the same
CN101759227A (en) * 2008-12-24 2010-06-30 比亚迪股份有限公司 Lithium titanate composite material and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101071853A (en) * 2007-06-01 2007-11-14 河南大学 Nano lithium titanate for Negative electrode material of cell or electrochemical vessel, and its and titanium dioxide composite preparing method
CN101759227A (en) * 2008-12-24 2010-06-30 比亚迪股份有限公司 Lithium titanate composite material and preparation method thereof
CN101431154A (en) * 2008-12-25 2009-05-13 成都中科来方能源科技有限公司 Lithium titanate/C composite electrode material and method for producing the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103730647A (en) * 2012-10-10 2014-04-16 中国科学院物理研究所 Rhombic manganese ore material and preparation method, cathode and lithium battery
CN103730647B (en) * 2012-10-10 2016-04-13 中国科学院物理研究所 Rhombic manganese ore material and preparation method thereof, negative pole and lithium battery
CN103560227A (en) * 2013-11-13 2014-02-05 重庆理工大学 Preparation method of Li4Ti5O12/C composite material
CN103560227B (en) * 2013-11-13 2016-03-09 重庆理工大学 A kind of Li 4ti 5o 12the preparation method of/C composite
CN104022257A (en) * 2014-06-16 2014-09-03 深圳市贝特瑞新能源材料股份有限公司 Silicon dioxide composite anode material for lithium ion battery, as well as preparation method and application of silicon dioxide composite anode material

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Application publication date: 20111228