CN102651470A - Method for preparing whisker shaped lithium titanate (Li4Ti5O12) by low-temperature solid phase method - Google Patents
Method for preparing whisker shaped lithium titanate (Li4Ti5O12) by low-temperature solid phase method Download PDFInfo
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- CN102651470A CN102651470A CN2012100650833A CN201210065083A CN102651470A CN 102651470 A CN102651470 A CN 102651470A CN 2012100650833 A CN2012100650833 A CN 2012100650833A CN 201210065083 A CN201210065083 A CN 201210065083A CN 102651470 A CN102651470 A CN 102651470A
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- lithium titanate
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Abstract
The invention discloses a method for preparing whisker shaped lithium titanate (Li4Ti5O12) by a low-temperature solid phase method. A TiO2(B) whisker and a lithium salt serve as raw materials; after being mixed, the TiO2(B) whisker and the lithium salt are baked twice at the temperature of 200 to 350 DEG C and the temperature of 500 to 650 DEG C respectively; after a product which is formed by baking twice is washed by water and dried, the whisker shaped lithium titanate is obtained. According to the method, the TiO2(B) whisker serves as a titanium source for synthesizing the Li4Ti5O12 for the first time, and the obtained product is the whisker shaped Li4Ti5O12 which is 50 to 500nm in diameter and 5 to 20 in length-diameter ratio and has the characteristics of easy control in size, uniformity in shape and the like. The process has the advantages of low baking temperature, low energy consumption, suitability for industrial application and the like.
Description
Technical field
The invention belongs to the preparation field of Inorganic Non-metallic Materials, be specifically related to the method that a kind of low-temperature solid-phase method prepares whisker shape lithium titanate.
Background technology
Lithium titanate material (Li
4Ti
5O
12) as a kind of negative material of lithium ion battery; Be a kind of " zero strain material "; Compare and business-like material with carbon element; Characteristics with high security, high stability, long-life and environmental protection will be as the negative material of lithium ion battery of new generation and be widely used in new-energy automobile, battery-operated motor cycle and require high security, high stability and macrocyclic application.Bibliographical information, the nanometerization of lithium titanate help to improve its electric capacity under high impulse electricity speed.
We know that the nano material and the performance of different-shape have close ties.International nanometer circle great master Lieber thinks that unidimensional system (like nanotube, nano wire) is the minimum dimension structure that can be used as electronics and photoexcited state transmission; To realizing nano-device functionalization and integrated extremely important; Therefore than two peacekeeping zero-dimensional systems interesting, important many (Hu JT; Odom TW; Lieber CM. Chemistry and physics in one dimension:Synthesis and properties of nanowires and nanotubes. [J] Accounts Chem. Res., 1999,32 (5): 435-445.).Discover to have the Li of one dimension pattern
4Ti
5O
12Demonstrated excellent more performance (L.Cheng, J.Yan and Y.Y. Xia.J. Mater. Chem., 2010,20,595 – 602.) than graininess.Yet, because Li
4Ti
5O
12Belong to cubic system, in its crystal growing process, demonstrate isotropism, therefore be difficult to obtain whisker shape Li
4Ti
5O
12Therefore, nanometer Li
4Ti
5O
12Material rarely has report.People (L.Cheng, J.Yan and Y.Y. Xia.J. Mater. Chem., 2010,20,595 – 602.) such as its ancient name for China utilize the method for C coating cleverly, through the roasting under the 800 degree inert atmospheres, have prepared 1-dimention nano Li
4Ti
5O
12Composite material with C.In addition, the method that patent 200610022477.5 discloses uses high temperature solid-state method can obtain whisker shape lithium titanate, but needs the high-temperature process of 980 degree ~ 1050 degree in the preparation process.The solid phase method of report nearly all relates to the high-temperature roasting about 800 degree at present, needs to consume mass energy consumption.
Titanium oxide is that solid phase method prepares Li
4Ti
5O
12Main titanium source, common have four kinds of crystal formations, is respectively anatase titanium dioxide, rutile-type, plate titanium type and TiO
2(B) type, wherein, TiO
2(B) has loose relatively Open architecture.The present invention aims to provide a kind of under relative low temperature (550 degree-650 degree) condition, with TiO
2(B) whisker and lithium salts are as the method for feedstock production whisker shape lithium titanate.With TiO
2(B) prepare lithium titanate Li as the titanium source
4Ti
5O
12Material still belongs to the first.
Summary of the invention
The objective of the invention is on the basis of existing technology, provide a kind of low-temperature solid-phase method to prepare whisker shape Li
4Ti
5O
12Method.The product that the inventive method obtains is that diameter is 50 ~ 500nm, and draw ratio is 5 ~ 20 whisker shape lithium titanate, and resulting lithium titanate has size and is prone to control, the equal first-class advantage of pattern, and this technology sintering temperature is low, has advantages such as low, the suitable industrial applications of energy consumption.
Realize that the object of the invention adopts following technical scheme:
A kind of low-temperature solid-phase method prepares whisker shape lithium titanate (Li
4Ti
5O
12) method, it is characterized in that, with TiO
2(B) whisker and lithium salts may further comprise the steps as raw material:
1) raw material is pressed TiO
2/ Li
2O=0.9 ~ 1.25:1 (mol ratio) mixes;
2) with mixed raw material 200 ~ 350 ℃ of following roastings 0.5 ~ 5 hour, obtain the bakes to burn the article product;
3) with the bakes to burn the article product 500 ~ 650 ℃ of following roastings 2 ~ 10 hours, obtain the after baking product;
4) with the washing of after baking product process, the oven dry back obtains whisker shape lithium titanate.
In the step 1), can be after the raw materials mix earlier 60 ~ 100 ℃ of vacuum dehydrations 0.5 ~ 2 hour, and dehydrated raw material carried out granulation.
Described lithium salts is one or more in lithium nitrate, lithium hydroxide, lithium acetate or its hydrate preferably.
Described TiO
2(B) whisker, preferred diameter is 50 ~ 500nm, draw ratio is 5 ~ 20.
According to the inventive method, the whisker shape Li that makes
4Ti
5O
12The diameter of material is 50 ~ 500nm, and draw ratio is 5 ~ 20.
Beneficial effect of the present invention comprises:
1, selects loose Open architecture TiO for use
2(B) whisker is beneficial to the embedding of Li ion as the titanium source, thereby has reduced sintering temperature, has practiced thrift energy consumption, helps large-scale production.
2, the Li of the resulting whisker shape of the inventive method
4Ti
5O
12Has the advantage that size is prone to control, the easy control of pattern.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with embodiment, but is limited claim.
Description of drawings
Fig. 1 is the Li of the prepared whisker shape of embodiment 1
4Ti
5O
12SEM (a) and XRD (b) figure.
Fig. 2 is the Li of the prepared whisker shape of embodiment 2
4Ti
5O
12SEM (a) and XRD (b) figure.
Fig. 3 is the prepared Li of Comparative Examples 4
4Ti
5O
12SEM (a) and XRD (b) figure.
Embodiment
According to the method for the invention, with TiO
2(B) whisker prepares lithium titanate as the titanium source through low-temperature solid-phase method, and the product that this method obtains is that diameter is 50 ~ 500nm, and draw ratio is 5 ~ 20 whisker shape Li
4Ti
5O
12, and resulting whisker shape lithium titanate has, and size is prone to control, the equal first-class advantage of pattern.
Embodiment 1
With TiO
2(B) whisker and LiOH press TiO
2/ Li
2O=0.9 (mol ratio) preparation, TiO
2(B) diameter of whisker is 50nm ~ 100nm, and draw ratio is 5 ~ 10, mixes with homogenizer; With mixed raw material TiO
2(B) and LiOH place 60 ~ 100 ℃ vacuum drying chamber to carry out 0.5 ~ 2 hour dehydration, dehydrated raw material is carried out granulation; Raw material after the granulation places Muffle furnace, 200 ℃ of following roastings 5 hours, gets the bakes to burn the article product; Then, temperature is increased to 650 ℃ with 5 ℃/minute heating rate, roasting 2 hours, the after baking product of white loose; Through washing, oven dry back obtains diameter and is about 50nm ~ 100nm with the after baking product, and draw ratio is the Li of 5 ~ 10 whisker shape
4Ti
5O
12
With TiO
2(B) whisker is the titanium source, TiO
2(B) diameter of whisker is 300 ~ 500nm, and is long straight than 15 ~ 20; With the acetate dihydrate lithium is the lithium source, and by preparing lithium titanate with embodiment 1 essentially identical method, actual conditions and product characteristic are seen table 1.
Comparative Examples 1
With TiO
2(B) whisker is the titanium source, TiO
2(B) diameter of whisker is 300 ~ 500nm, and is long straight than 15 ~ 20; With the lithium hydroxide is the lithium source, and by preparing lithium titanate with embodiment 1 essentially identical method, difference is that roasting condition is that prepared product shape characteristic was seen table 1 750 ℃ of following roastings 2 hours for the second time.
Comparative Examples 2～4
With anatase titanium dioxide TiO
2Whisker is the titanium source, and the diameter of whisker is 300 ~ 500nm, and is long straight than 15 ~ 20; With the lithium hydroxide is the lithium source, and by preparing lithium titanate with embodiment 1 essentially identical method, actual conditions and product characteristic are seen table 1.
The condition of other embodiment of table 1 and Comparative Examples and product characteristic
Can find out that with Comparative Examples 1 too high sintering temperature can't obtain the Li of whisker shape by embodiment 1
4Ti
5O
12Can find out that with Comparative Examples 2～4 when being the titanium source with the anatase-type titanium oxide whisker, (650 ℃/750 ℃) can't obtain the Li of pure phase under the low temperature by embodiment 1
4Ti
5O
12, (850 ℃) can only obtain granular lithium titanate under the high temperature.
Can find out by embodiment and comparative example, the invention provides a kind of low-temperature solid-phase method and prepare whisker shape Li
4Ti
5O
12Method.Among the present invention, TiO
2(B) whisker is that low temperature (500 ~ 650 ℃) obtains pure phase Li as the lithium source
4Ti
5O
12Key factor.Because it is simple and with low cost that the solid sintering technology that has adopted suitable industrialization to amplify, technology of the present invention have preparation technology, the Li that obtains
4Ti
5O
12Advantages such as whisker lithium electrical property excellence.
Claims (5)
1. a low-temperature solid-phase method prepares whisker shape lithium titanate (Li
4Ti
5O
12) method, it is characterized in that, with TiO
2(B) whisker and lithium salts may further comprise the steps as raw material:
1) raw material is pressed TiO
2/ Li
2O mol ratio=0.9 ~ 1.25:1 mixes;
2) with mixed raw material 200 ~ 350 ℃ of following roastings 0.5 ~ 5 hour, obtain the bakes to burn the article product;
3) with the bakes to burn the article product 500 ~ 650 ℃ of following roastings 2 ~ 10 hours, obtain the after baking product;
4) with the washing of after baking product, the oven dry back obtains whisker shape lithium titanate.
2. preparation whisker shape lithium titanate (Li according to claim 1
4Ti
5O
12) method, it is characterized in that described lithium salts is selected from one or more in lithium nitrate, lithium hydroxide, lithium acetate or its hydrate.
3. preparation whisker shape lithium titanate (Li according to claim 1
4Ti
5O
12) method, it is characterized in that described TiO
2(B) diameter of whisker is 50 ~ 500nm, and draw ratio is 5 ~ 20.
4. preparation whisker shape lithium titanate (Li according to claim 1
4Ti
5O
12) method, it is characterized in that, in the step 1), after the raw materials mix 60 ~ 100 ℃ of vacuum dehydrations 0.5 ~ 2 hour, and with the dehydrated raw material granulation.
5. preparation whisker shape lithium titanate (Li according to claim 1
4Ti
5O
12) method, it is characterized in that the diameter of described whisker shape lithium titanate is 50 ~ 500nm, draw ratio is 5 ~ 20.
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|---|---|---|---|
| CN201210065083.3A CN102651470B (en) | 2012-03-14 | 2012-03-14 | Method for preparing whisker shaped lithium titanate (Li4Ti5O12) by low-temperature solid phase method |
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|---|---|---|---|
| CN201210065083.3A CN102651470B (en) | 2012-03-14 | 2012-03-14 | Method for preparing whisker shaped lithium titanate (Li4Ti5O12) by low-temperature solid phase method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752707A (en) * | 2015-03-03 | 2015-07-01 | 深圳市翔丰华科技有限公司 | Titanium dioxide (B) negative electrode material and preparation method thereof |
| CN106169577A (en) * | 2015-05-19 | 2016-11-30 | 三星Sdi株式会社 | Negative electrode active material and lithium rechargeable battery for lithium rechargeable battery |
| CN108658123A (en) * | 2018-05-28 | 2018-10-16 | 姚文俊 | A kind of preparation method and applications of porous titanate |
| CN112250461A (en) * | 2020-10-15 | 2021-01-22 | 广东欧文莱陶瓷有限公司 | High-strength transparent ceramic and preparation method thereof |
| EP4318644A3 (en) * | 2022-08-05 | 2024-02-28 | Samsung SDI Co., Ltd. | Negative electrode for rechargeable lithium battery and rechargeable lithium battery including same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995490A (en) * | 2006-12-12 | 2007-07-11 | 成都理工大学 | Process for preparing lithium titanate crystal whisker |
| CN101777645A (en) * | 2010-02-10 | 2010-07-14 | 赵县强能电源有限公司 | Preparation method of carbon-modified lithium titanate |
| US20100178560A1 (en) * | 2009-01-15 | 2010-07-15 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
-
2012
- 2012-03-14 CN CN201210065083.3A patent/CN102651470B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995490A (en) * | 2006-12-12 | 2007-07-11 | 成都理工大学 | Process for preparing lithium titanate crystal whisker |
| US20100178560A1 (en) * | 2009-01-15 | 2010-07-15 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN101777645A (en) * | 2010-02-10 | 2010-07-14 | 赵县强能电源有限公司 | Preparation method of carbon-modified lithium titanate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752707A (en) * | 2015-03-03 | 2015-07-01 | 深圳市翔丰华科技有限公司 | Titanium dioxide (B) negative electrode material and preparation method thereof |
| CN106169577A (en) * | 2015-05-19 | 2016-11-30 | 三星Sdi株式会社 | Negative electrode active material and lithium rechargeable battery for lithium rechargeable battery |
| US10847793B2 (en) | 2015-05-19 | 2020-11-24 | Samsung Sdi Co., Ltd. | Negative active material for rechargeable lithium battery and rechargeable lithium battery comprising same |
| CN108658123A (en) * | 2018-05-28 | 2018-10-16 | 姚文俊 | A kind of preparation method and applications of porous titanate |
| CN112250461A (en) * | 2020-10-15 | 2021-01-22 | 广东欧文莱陶瓷有限公司 | High-strength transparent ceramic and preparation method thereof |
| EP4318644A3 (en) * | 2022-08-05 | 2024-02-28 | Samsung SDI Co., Ltd. | Negative electrode for rechargeable lithium battery and rechargeable lithium battery including same |
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| CN102651470B (en) | 2014-04-02 |
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