CN101402469B - Method of producing spinel structured lithium titanate - Google Patents
Method of producing spinel structured lithium titanate Download PDFInfo
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- CN101402469B CN101402469B CN2008100738693A CN200810073869A CN101402469B CN 101402469 B CN101402469 B CN 101402469B CN 2008100738693 A CN2008100738693 A CN 2008100738693A CN 200810073869 A CN200810073869 A CN 200810073869A CN 101402469 B CN101402469 B CN 101402469B
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- lithium titanate
- spinel structure
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- carbon black
- raw materials
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Abstract
The invention discloses a method for preparing lithium titanate with a spinel structure. Lithium carbonate, titanium dioxide and carbon black which are low in price and easy to obtain are used as raw materials; the lithium titanate (LiTi2O4) is synthesized by a one-step solid phase reaction method. The raw materials are fully mixed and react for 4 to 36 hours at a temperature between 700 and 1,300 DEG C under an argon atmosphere or a vacuum atmosphere to prepare the lithium titanate (LiTi2O4) with the spinel structure which is pure or contains a little carbon black. A product is ground through a planetary ball mill; the granularity of the product reaches between 0.5 and 5 mu m; and the cycle ratio capacity of the product reaches between 100 and 160 mAh/g. The method has a simple process and low prices of raw materials and is suitable for industrial production; and the product has excellent electrochemical performance and can be used a material for the cathode of a high-performance lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery electrode material, be meant especially and adopt the synthetic lithium titanate with spinel structure (LiTi that can be used as lithium ion battery negative material of raw material one single-step solid phase reaction cheap and easy to get
2O
4) method.
Background technology
Lithium titanate is meant Li-Ti-O series oxygen compound, wherein, and spinel structure
LiTi
2O
4, Li
4Ti
5O
12Li with positive ramsdellite structure (Pbnm)
2Ti
3O
7All have good reversible embedding lithium response characteristic, can be used as lithium ion battery negative material.The LiTi of spinel structure
2O
4Advantage such as have that embedding lithium current potential is low, charge-discharge performance is stable, good conductivity, high-rate performance are good is expected to be used as long lifetime high-power lithium ion battery negative material.But LiTi
2O
4In have the III valency Ti ion of easy oxidation by air, cause its complicated process of preparation.The LiTi that has reported
2O
4The preparation method mainly contains: the suboxide of metallic titanium powder or titanium is (as TiO, Ti
2O
3Deng) with high price titanium (IV valency) oxide compound (as TiO
2, Li
2TiO
3, Li
2Ti
3O
7, Li
2Ti
2O
5Deng) react metallic lithium and TiO
2Under inert atmosphere or vacuum condition, react Li
2CO
3With TiO
2Method such as react in hydrogen.These methods exist that reaction conditions is restive, preparation section is long, the more high shortcoming of raw materials cost.
Summary of the invention
The objective of the invention is that existing lithium titanate synthesising method reacting condition is restive in order to overcome, operation is long, the high deficiency of raw materials cost, providing a kind of is the method for the synthetic lithium titanate of a single-step solid phase reaction of raw material with titanium dioxide, Quilonum Retard and carbon black.
The technical scheme that technical solution problem of the present invention is adopted is: with titanium dioxide cheap and easy to get, Quilonum Retard and carbon black is raw material, and redox reaction at high temperature takes place the three, one-step synthesis lithium titanate with spinel structure (LiTi
2O
5).Its chemical equation is:
Li
2CO
3+4TiO
2+2C＝2LiTi
2O
4+3CO↑
Concrete steps are: by atomic ratio Li: Ti: C=1: 2: (0.50～0.58) takes by weighing analytical pure Quilonum Retard, titanium dioxide and carbon black respectively, with ball mill grinding 0.5h～2h, make the raw material thorough mixing, mixture is contained in porcelain dish or corundum boat, place in tube furnace or the vacuum oven, the control argon flow amount is that 20L/h～200L/h or vacuum tightness are 10
-1Pa at 700 ℃～1300 ℃ reaction 4h～36h, reduces temperature naturally to normal temperature, takes out reaction product (product is a mazarine), grinds 2h under argon shield, and obtaining granularity is the lithium titanate with spinel structure LiTi of 0.5 μ m～5 μ m
2O
4Powder.
Present method adopts carbon black at high temperature to make LiTi
2O
4In 1/2 titanium atom be reduced to III by the IV valency, avoid using the lower valency titanium oxide of difficult preparation, avoid using the more expensive titanium valve of the hydrogen of potential safety hazard and price as reductive agent.Synthetic product is mainly the spinel phase, a small amount of unreacted carbon black is completely only arranged, but carbon black does not influence its chemical property; The chemical property of product is good, and specific storage is 100mAh/g-160mAh/g.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the embodiment of the invention 1 preparation product.
The cyclic voltammetry curve (scanning speed is 0.5mV/s) of the simulated battery that Fig. 2 is assembled into for the embodiment of the invention 1 preparation product and metallic lithium.
(current density is 2.5mA/cm to the constant current charge-discharge curve of the simulated battery that Fig. 3 is assembled into for the embodiment of the invention 1 preparation product and metallic lithium
2).
Embodiment
Embodiment 1:
(anatase octahedrite is main accurately to take by weighing commercially available analytical reagent titanium dioxide 3.228g, titanium dioxide 〉=99.0%), Quilonum Retard 0.762g (Quilonum Retard 〉=97.0%), carbon black 0.400g (ash content≤0.2%), planetary ball mill 2h in 200mL agate jar, mixture is placed in the 25mL corundum boat, place tube furnace, feeding flow is the commercially available argon gas (Ar 〉=99.996%) of 20L/h, material is at 900 ℃ of reaction 30h, take out after naturally cooling to room temperature, change agate jar and applying argon gas over to, grind 2h with planetary ball mill, promptly get mazarine lithium titanate with spinel structure LiTi
2O
4Powdered product.The x-ray diffractometer measurement result shows that product is mainly spinel structure (seeing accompanying drawing 1); Its simulated battery Li/LiTi
2O
4Cyclic voltammetry curve in one group of redox reversible peak is arranged, reaction potential is 1.36V (seeing accompanying drawing 2); Its specific storage can be 120mAh/g-160mAh/g, charge-discharge performance good (seeing accompanying drawing 3).
Embodiment 2
(anatase octahedrite is main accurately to take by weighing commercially available analytical reagent titanium dioxide 322.800g, titanium dioxide 〉=99.0%), Quilonum Retard 76.200g (Quilonum Retard 〉=97.0%), carbon black 38.000g (ash content≤0.2%), planetary ball mill 2h in batches in 500mL agate jar, mixture is placed the 500mL plumbago crucible, place in the SL63-7B vacuum carbon pipe electric furnace (Shanghai Electric Furnace Factory's production), vacuum tightness is evacuated to 10
-1Pa, heat temperature raising to 900 ℃ reaction 8h takes out after being cooled to room temperature, changes agate jar and applying argon gas over to, grinds 2h with planetary ball mill, promptly gets mazarine lithium titanate with spinel structure LiTi
2O
4Powdered product.Its x-ray diffractometer measurement result and chemical property and embodiment 1 roughly the same, wherein reversible embedding lithium reaction potential is that 1.34V, specific storage are 160mAh/g, charge-discharge performance is good.
Claims (1)
1. the preparation method of a lithium titanate with spinel structure, it is characterized in that concrete steps are: by atomic ratio Li: Ti: C=1: 2: (0.50～0.58) takes by weighing analytical pure Quilonum Retard, titanium dioxide and carbon black respectively, with ball mill grinding 0.5h～2h, make the raw material thorough mixing, mixture is contained in porcelain dish or corundum boat, place in tube furnace or the vacuum oven, the control argon flow amount is that 20L/h～200L/h or vacuum tightness are 10
-1Pa at 700 ℃～1300 ℃ reaction 4h～36h, reduces temperature naturally to normal temperature, takes out reaction product, grinds 2h under argon shield, obtains lithium titanate with spinel structure LiTi
2O
4Powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100738693A CN101402469B (en) | 2008-10-31 | 2008-10-31 | Method of producing spinel structured lithium titanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100738693A CN101402469B (en) | 2008-10-31 | 2008-10-31 | Method of producing spinel structured lithium titanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101402469A CN101402469A (en) | 2009-04-08 |
| CN101402469B true CN101402469B (en) | 2010-08-11 |
Family
ID=40536654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100738693A Expired - Fee Related CN101402469B (en) | 2008-10-31 | 2008-10-31 | Method of producing spinel structured lithium titanate |
Country Status (1)
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408126A (en) * | 2011-08-20 | 2012-04-11 | 桂林理工大学 | Preparation method of spinel structured solid solution Li1+xTi2O4 |
| CN104205469B (en) * | 2012-04-20 | 2018-03-20 | 株式会社Lg 化学 | Electrode for secondary battery and the lithium secondary battery for including the electrode |
| CN104477979A (en) * | 2014-12-17 | 2015-04-01 | 湖南大学 | Method for preparing LiTi204 powder material |
| CN107244693B (en) * | 2017-05-23 | 2022-01-14 | 湖南大学 | Li0.5TiO2Method for preparing powder material |
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2008
- 2008-10-31 CN CN2008100738693A patent/CN101402469B/en not_active Expired - Fee Related
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