CN101920988A - Nickel-doped spinel type lithium titanate powdery material and preparation method thereof - Google Patents

Nickel-doped spinel type lithium titanate powdery material and preparation method thereof Download PDF

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Publication number
CN101920988A
CN101920988A CN201010201177XA CN201010201177A CN101920988A CN 101920988 A CN101920988 A CN 101920988A CN 201010201177X A CN201010201177X A CN 201010201177XA CN 201010201177 A CN201010201177 A CN 201010201177A CN 101920988 A CN101920988 A CN 101920988A
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China
Prior art keywords
nickel
lithium
titanate
preparation
spinel type
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CN201010201177XA
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Chinese (zh)
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王丹
汪保国
金彩虹
何丹农
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Priority to CN201010201177XA priority Critical patent/CN101920988A/en
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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 relates to a nickel-doped spinel type lithium titanate powdery material and a preparation method thereof. The material has a chemical formula of Li4Ti5-yNiyO12, wherein y is greater than 0 and less than or equal to 0.5. The method of the invention has the advantages of reduction of reaction temperature, shortening of reaction time, simple preparation process and short preparation period; and the prepared nickel-containing spinel type lithium titanate has high performance and broad market prospect.

Description

A kind of spinel type lithium titanate powdery material of mixing nickel and preparation method thereof
Technical field
The present invention relates to spinel type lithium titanate and preparation method thereof, particularly a kind of spinel type lithium titanate powdery material of mixing nickel and preparation method thereof.
Background technology
Used in the market lithium ion battery, substantially all be to be negative pole with the carbon material, but carbon material is a negative pole also has some weakness that are difficult to overcome in actual applications, for example, the current potential of carbon dioxide process carbon electrode and the current potential of metallic lithium are very approaching, when battery overcharge, and the easy precipitating metal lithium of carbon electrodes, thereby may form Li dendrite and cause short circuit, and then cause battery explosion.In order to solve the safety problem of lithium cell, people have done a large amount of research.
In recent years, spinel type lithium titanate Li 4Ti 5O 12Become the focus of research gradually as the lithium-titanium composite oxide of " zero strain " material.If substitute carbon as lithium ion battery negative material with lithium titanate, because lithium titanate/lithium has higher relatively electropotential (1.55V), suppressed lithium and on negative pole, separated out, fundamentally solved the short circuit problem that the lithium dendrite arm causes, the security that has improved the lithium electricity; Embed at lithium ion that crystalline structure can keep the stability of height in the process of deviating from, and make it have good cycle performance and sparking voltage stably; Li 4Ti 5O 12High 1 order of magnitude of chemical diffusion coefficient ratio carbon negative pole material at normal temperatures, the speed that discharges and recharges is very fast.In a word, substitute carbon as lithium ion battery negative material with lithium titanate, lithium ion battery then can show excellent security energy and high rate performance.
Find that through retrieval the researchist is many to improve and improve lithium titanate (Li by adulterated mode to prior art 4Ti 5O 12) performance.Improve the lithium titanate performance by doped with Al exactly as patent CN101151747A; Patent CN101151746A has introduced a kind of preparation method of the Mg of containing lithium titanate.
Summary of the invention
One of purpose of the present invention is to provide a kind of spinel type lithium titanate powdery material of mixing nickel, as the raw material of preparation high performance lithium ionic cell cathode material.
Two of purpose of the present invention is to provide the preparation method of this lithium titanate.
For achieving the above object, the present invention adopts following technical scheme:
A kind of spinel type lithium titanate powdery material of mixing nickel is characterized in that the chemical formula of this material is: Li 4Ti 5-yNi yO 12, 0<y in the formula≤0.5.
The particle diameter of above-mentioned lithium titanate powdery material is 300nm~500nm.
A kind of method for preparing the above-mentioned spinel type lithium titanate powdery material of mixing nickel is characterized in that the concrete steps of this method are:
A. lithium salts after will pulverizing or lithium alkali and nickel salt or nickel alkali are dispersed in the dispersion agent;
B. according to butyl (tetra) titanate+nickel salt or nickel alkali: lithium salts or lithium alkali are 5: 3.5~5: 4.5 mol ratio, will the solution that joins step a gained with the butyl (tetra) titanate of alcohol dilution in, the TiO that the butyl (tetra) titanate hydrolysis obtains (OH) 2Gel evenly is coated on lithium source and mixed powder surface, nickel source, then with this mixture drying;
C. 700 ℃ again~900 ℃ temperature lower calcinations are 6~10 hours after step b gained mixture being ground, and pulverize grinding after being cooled to room temperature, make the spinel type lithium titanate powdery material of mixing nickel.
Above-mentioned dispersion agent is water or water and the ethanol mixing solutions by 4: 1~1: 4 volume ratio.
Above-mentioned lithium salts or lithium alkali are: Quilonum Retard, lithium hydroxide, lithium oxalate, lithium acetate etc.
Above-mentioned nickel salt or nickel alkali are: nickelous carbonate, nickel hydroxide, nickelous nitrate, single nickel salt etc.
Above-mentioned will be with the method in the solution that joins step a gained of the butyl (tetra) titanate of alcohol dilution disposable adding, dropping or drip earlier with the butyl (tetra) titanate of alcohol dilution 5%~20% after leave standstill 10~30min, allow disposable adding afterwards.
Compare with the preparation method of existing lithium titanate, the inventive method has reduced temperature of reaction, has shortened the reaction times, preparation technology is simple, and preparation cycle is short, and the nickeliferous spinel type lithium titanate that makes has superperformance, and market outlook are wide.
Description of drawings
The spinel type lithium titanate powdery material XRD figure that Fig. 1 mixes nickel for the inventive method preparation.
Fig. 2 mixes the spinel type lithium titanate powdery material sreen analysis figure of nickel for the inventive method preparation.
Fig. 3 mixes the spinel type lithium titanate powdery material charging and discharging curve figure of nickel for the inventive method preparation.
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
1) presses Li 4Ti 5O 12Each raw material of molecular formula weighing, to the dispersion agent of 200ml water and dehydrated alcohol, wherein water and alcoholic acid ratio are 4: 1 (volume ratio) to the method by ultra-sonic dispersion with 2.000g Quilonum Retard homodisperse;
2) according to Ti: Li is that 5: 4 mol ratio is measured butyl (tetra) titanate 20.7ml, after the dilution of 20ml dehydrated alcohol, is added drop-wise in the aqueous ethanolic solution that is dispersed with Quilonum Retard with the speed of 5ml/min; Be added dropwise to complete the back and continue ultra-sonic dispersion 30min, after the dehydration of suction filtration drying and grinding, obtain the surface and be coated with TiO 2The Quilonum Retard powder;
3) with this mixed powder, insert in the retort furnace 900 ℃ of calcinings 6 hours, cool to room temperature with the furnace, mistake 200 mesh sieves obtain final product Li through grinding after 4Ti 5O 12Powder.
Embodiment 2
1) presses Li 4Ti 4.75Ni 0.25O 12Each raw material of molecular formula weighing, to the dispersion agent of 200ml water and dehydrated alcohol, wherein water and alcoholic acid ratio are 3: 1 (volume ratio) to the method by ultra-sonic dispersion with 2.000g Quilonum Retard and 0.282g nickel hydroxide homodisperse;
2) according to Ti+Ni: Li is that 5: 4.2 mol ratio is measured butyl (tetra) titanate 19.7ml, after the dilution of 20ml dehydrated alcohol, is added drop-wise in the aqueous ethanolic solution that is dispersed with Quilonum Retard and nickel hydroxide with the speed of 5ml/min; Be added dropwise to complete the back and continue ultra-sonic dispersion 30min, after the dehydration of suction filtration drying and grinding, obtain the surface and be coated with TiO 2Quilonum Retard and the powder of nickel hydroxide;
3) with this mixed powder, insert in the retort furnace 800 ℃ of calcinings 8 hours, cool to room temperature with the furnace, mistake 200 mesh sieves obtain final product Li through grinding after 4Ti 4.75Ni 0.25O 12Powder.
Embodiment 3
1) presses Li 4Ti 4.5Ni 0.5O 12Each raw material of molecular formula weighing, to the dispersion agent of 200ml water and dehydrated alcohol, wherein water and alcoholic acid ratio are 2: 1 (volume ratio) to the method by ultra-sonic dispersion with 2.000g Quilonum Retard and 0.565g nickel hydroxide homodisperse;
2) according to Ti: Li is that 5: 4.4 mol ratio is measured butyl (tetra) titanate 18.6ml, after the dilution of 20ml dehydrated alcohol, is added drop-wise in the aqueous ethanolic solution that is dispersed with Quilonum Retard and nickel hydroxide with the speed of 5ml/min; Be added dropwise to complete the back and continue ultra-sonic dispersion 30min, after the dehydration of suction filtration drying and grinding, obtain the surface and be coated with TiO 2Quilonum Retard and the powder of nickel hydroxide;
3) with this mixed powder, insert in the retort furnace 700 ℃ of calcinings 10 hours, cool to room temperature with the furnace, mistake 200 mesh sieves obtain final product Li through grinding after 4Ti 4.5Ni 0.5O 12Powder.

Claims (7)

1. a spinel type lithium titanate powdery material of mixing nickel is characterized in that the chemical formula of this material is: Li 4Ti 5-yNi yO 12, 0<y in the formula≤0.5.
2. the spinel type lithium titanate powdery material of mixing nickel according to claim 1, the particle diameter that it is characterized in that described lithium titanate powdery material is 300nm~500nm.
3. one kind prepares method of mixing the spinel type lithium titanate powdery material of nickel according to claim 1, it is characterized in that the concrete steps of this method are:
A. lithium salts after will pulverizing or lithium alkali and nickel salt or nickel alkali are dispersed in the dispersion agent;
B. according to butyl (tetra) titanate+nickel salt or nickel alkali: lithium salts or lithium alkali are 5: 3.5~5: 4.5 mol ratio, will the solution that joins step a gained with the butyl (tetra) titanate of alcohol dilution in, and the TiO (OH) that the butyl (tetra) titanate hydrolysis is obtained 2Gel evenly is coated on lithium source and mixed powder surface, nickel source, then with this mixture drying;
C. 700 ℃ again~900 ℃ temperature lower calcinations are 6~10 hours after step b gained mixture being ground, and pulverize grinding after being cooled to room temperature, make the spinel type lithium titanate powdery material of mixing nickel.
4. preparation method according to claim 3 is characterized in that described dispersion agent is water or water and the ethanol mixing solutions by 4: 1~1: 4 volume ratio.
5. preparation method according to claim 3 is characterized in that described lithium salts or lithium alkali are: Quilonum Retard, lithium hydroxide, lithium oxalate, lithium acetate etc.
6. preparation method according to claim 3 is characterized in that described nickel salt or nickel alkali are: nickelous carbonate, nickel hydroxide, nickelous nitrate, single nickel salt etc.
7. preparation method according to claim 3, it is characterized in that described will be with the method in the solution that joins step a gained of the butyl (tetra) titanate of alcohol dilution disposable adding, dropping or drip earlier with the butyl (tetra) titanate of alcohol dilution 5%~20% after leave standstill 10~30min, disposable then adding.
CN201010201177XA 2010-06-12 2010-06-12 Nickel-doped spinel type lithium titanate powdery material and preparation method thereof Pending CN101920988A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102983319A (en) * 2012-12-18 2013-03-20 上海纳米技术及应用国家工程研究中心有限公司 Modified lithium titanate material and preparation method thereof
CN103579600A (en) * 2012-07-24 2014-02-12 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of transition-metal-modified lithium titanate material
CN103594694A (en) * 2013-11-28 2014-02-19 扬州大学 Preparation method of spherical lithium titanate ion battery cathode material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101656310A (en) * 2009-09-10 2010-02-24 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing spinel-type lithium titanate as negative electrode material of lithium-ion battery
CN101702431A (en) * 2009-10-30 2010-05-05 南京工业大学 Preparation method of lithium titanium negative electrode composite material for lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101656310A (en) * 2009-09-10 2010-02-24 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing spinel-type lithium titanate as negative electrode material of lithium-ion battery
CN101702431A (en) * 2009-10-30 2010-05-05 南京工业大学 Preparation method of lithium titanium negative electrode composite material for lithium ion battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103579600A (en) * 2012-07-24 2014-02-12 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of transition-metal-modified lithium titanate material
CN102983319A (en) * 2012-12-18 2013-03-20 上海纳米技术及应用国家工程研究中心有限公司 Modified lithium titanate material and preparation method thereof
CN103594694A (en) * 2013-11-28 2014-02-19 扬州大学 Preparation method of spherical lithium titanate ion battery cathode material

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Open date: 20101222