CN101847712A - Method for depositing TiO2 on surface of multiwall carbon nano-tube for improving memory property of lithium ion - Google Patents

Method for depositing TiO2 on surface of multiwall carbon nano-tube for improving memory property of lithium ion Download PDF

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Publication number
CN101847712A
CN101847712A CN201010126715A CN201010126715A CN101847712A CN 101847712 A CN101847712 A CN 101847712A CN 201010126715 A CN201010126715 A CN 201010126715A CN 201010126715 A CN201010126715 A CN 201010126715A CN 101847712 A CN101847712 A CN 101847712A
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carbon nano
mwcnts
lithium ion
toluene
tubes
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CN101847712B (en
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潘登余
晏秀妹
吴明红
李珍
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a method for depositing TiO2 on the surface of a multiwall carbon nano-tube for improving the memory property of a lithium ion, which belongs to the technical field of the preparation technology of anode materials for lithium ion batteries. The method is characterized by comprising the following steps of: preparing a precursor by mixing oleic acid and tetrabutyl titanate in the weight ratio of 4 to 1, and then adding proper catalyst triethylamine into the precursor; weighting a certain amount of multiwall carbon nano-tubes (MWCNTs), adding the multiwall carbon nano-tubes into a mixed solvent of ethanol and toluene, then carrying out ultrasonic mixing on the obtained mixture and adding the mixture into the precursor; stirring and mixing the mixture, and moving the mixture to a Teflon high pressure reactor, and then putting the high pressure reactor in a baking oven at the temperature of 150 DEG C so as to make the mixture in the high pressure reactor react completely; washing reaction products by using the ethanol and the toluene, and then carrying out centrifugal separation on the reaction products so as to obtain an MWCNTs-TiO2 composite. The composite is easy to be dispersed in the toluene, and can be coated on a copper foil by the spin coating process so as to prepare the anode materials for thin film type lithium ion batteries.

Description

At multi-walled carbon nano-tubes surface deposition nano-TiO 2Improve the method for lithium ion memory property
Technical field
The present invention relates to a kind of at multi-walled carbon nano-tubes surface deposition nano-TiO 2Improve the method for lithium ion memory property, belong to lithium ion battery negative material fabricating technology field.
Background technology
In exploring new type lithium ion battery negative material process, it is found that the charge/discharge capacity of carbon nano-tube can surpass more than a times of graphite lithium intercalation compound, make the research of carbon nano-tube lithium cell cathode material become focus.Yet, easily form irreversible SEI film (solid electrolyte interface film) in the carbon nano-tube first charge-discharge process at electrode and electrolyte interface, thereby cause carbon nano-tube problem such as enclosed pasture efficient very low (＜40%) and cyclical stability extreme difference first, hindered its industrialized development.
MWCNT-TiO 2Compound is that people study more carbon back heterojunction composite in recent years, and its research is inquired on the one hand is to utilize the right separation in the light induced electron hole of carbon nano-tube aided nano titanium dioxide to improve the efficient of optically catalytic TiO 2; Then be to utilize the carbon nano tube modified nano titanium oxide of tool satisfactory electrical conductivity on the other hand to improve titanium dioxide lithium ion memory property.Yet, the influence of the lithium ion memory property of carbon nano-tube is never studied at the nano titanium oxide of this composite surface deposition.
Summary of the invention
The object of the present invention is to provide a kind of multi-walled carbon nano-tubes surface deposition nano-TiO 2Improve the method for lithium ion memory property.
The present invention is a kind of at multi-walled carbon nano-tubes surface deposition nano-TiO 2Improve the method for lithium ion memory property, it is characterized in that having following technical process and step:
A. measure the butyl titanate and the oleic acid of certain volume, the preparing titanium dioxide predecessor; The volume ratio of butyl titanate and oleic acid is 1: 4; Oleic acid is heated to 55～65 ℃, in stirring, adds butyl titanate, get bright brown precursor liquid; It is standby to be cooled to room temperature;
B. get a certain amount of above-mentioned predecessor liquid, in stirring, add proper catalyst triethylamine; The addition of triethylamine is 6～7% of a described predecessor liquid volume amount;
C. taking by weighing a certain amount of multi-walled carbon nano-tubes (MWCNTs) joins in the mixed solvent of a certain amount of ethanol and toluene; The volume ratio of ethanol and toluene is 1: 1.5～1: 3 in the mixed solvent; Multi-walled carbon nano-tubes (MWCNTs) is 2.5～4.0mg/ml with the ratio that cooperates of described mixed solvent by the mass volume ratio suffering, the multi-walled carbon nano-tubes (MWCNTs) that promptly per 1 milliliter of mixed solvent configuration is 2.5～4.0 milligrams; Ultrasonic mixing 15～20 minutes;
D. join then in the above-mentioned precursor fluid that is added with triethylamine, continue to stir 2～3 hours, make to mix; Then this mixture is moved in the Teflon autoclave, and be positioned in 120～150 ℃ of baking ovens, reacted 12～15 hours; Obtain the black mixed liquor;
E. be 10000 rev/mins centrifugal separator centrifugation sedimentation with above-mentioned black mixed liquor rotating speed, obtain black precipitate; Then with ethanol washing once to remove excessive oleic acid, again with toluene wash 1～2 time to remove free titanium dioxide nano-particle; Through centrifugation, promptly obtain MWCNTs-TiO again 2Compound.
The characteristics of the inventive method are: pass through TiO 2Self assembly and the growth in situ of nano particle on carbon nano-tube makes MWCNTs-TiO 2Compound.TiO 2Deposition at the multi-wall carbon nano-tube tube-surface can be used as protective layer, can suppress electrode surface effectively and produce irreversible solid electrolyte interface film (SEI film), thereby improve the lithium ion memory property.
Adopted the catalysis triethylamine among the present invention, but catalysis predecessor aminolysis forms nano titanium oxide.
The MWCNTs-TiO that the inventive method makes 2Compound very easily is dispersed in the toluene, can directly be coated on making film lithium ion battery negative material on the Copper Foil by the method such as the spin coating proceeding of solution-operated.
Description of drawings
Fig. 1 is the prepared MWCNTs-TiO of the inventive method 2The transmission electron microscope of compound (TEM) photo figure.
Fig. 2 is (a) original MWCNTs, (b) TiO among the present invention 2Nano particle, (c) MWCNTs-TiO 2The X-ray diffraction analysis of compound (XRD) collection of illustrative plates.
Fig. 3 is (a) former carbon nano-tube, (b) MWCNTs-TiO 2Specific capacity-the voltage curve of compound.
Fig. 4 is the MWCNTs-TiO of the inventive method gained 2Compound enclosed pasture efficiency curve diagram.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
The step of present embodiment is as described below:
(1), get oleic acid and be heated to about 60 ℃, add butyl titanate in the stirring and obtain bright brown predecessor (oleic acid and butyl titanate volume ratio are 4: 1), it is standby to be cooled to room temperature.
(2), get adding 0.2ml triethylamine in the stirring of 3mL predecessor.
(3), take by weighing 20mg MWCNTS and add in the mixed liquor of 2ml ethanol and 5ml toluene, add behind the ultrasonic 15min and mix with predecessor; Move to teflon autoclave (the reactor volume is 30mL) after continuing to stir 2h, and be positioned in 150 ℃ of electric dry ovens, keep constant temperature 15h, make abundant reaction.
(4), the product that obtains removes unnecessary oleic acid one time with the ethanol washing, again with toluene wash 1-2 all over removing free titanium dioxide nano-particle, obtain the MWCNTs-TiO2 compound after the centrifugation.This sample energy stable dispersion is in toluene.
Detection and test to the present embodiment products therefrom
(1), transmission electron microscope (TEM) detects
MWCNTs-TiO 2The testing result of compound is seen Fig. 1.
(2), X-ray diffractometer (XRD) analyzing and testing
Referring to Fig. 2, among Fig. 2, a is original carbon nano-tube XRD diffracting spectrum, and b is pure anatase-type nanometer titanium dioxide diffracting spectrum, and c is MWCNTs-TiO 2The compound diffracting spectrum, the diffraction maximum of carbon nano-tube is penetrated but also comprised to the diffraction that it had not only comprised titanium dioxide.Though (101 peaks of titanium dioxide overlap with carbon nano-tube (002) peak among the figure, and (101) peak of carbon nano-tube shows in compound existing carbon nano-tube in the compound is described.)
(3), the measurement of lithium ion memory property (cyclic voltammetry)
The making of negative pole:
The ion cathode material lithium preparation method is in this experiment: with MWCNTs-TiO 2It is to get rid of film on the 14mm copper sheet that toluene solution drops in diameter, and 200 ℃ of annealing 1min repeat twice, and it is of poor quality that the active material quality is the copper sheet that gets rid of the film front and back, is 0.0006g in this example, tests as negative pole;
As a comparison, the storage characteristics of original carbon nano-tube is done contrast test, specific practice is: with carbon nano-tube and 4: 1 mixed pressuring plates of PTFE (20%) mass ratio as battery cathode.
Referring to Fig. 3 and Fig. 4.
Among Fig. 3, (a) and (b) are respectively the specific capacity-voltage curve of original carbon nano-tube and preceding 20 circulations of example gained composite sample, in 0.005～2.5 potential range, compare their lithium ion memory property.From (a) as can be known: the discharge capacity first of original carbon nano-tube is～750 MAH/grams, and charging capacity is～175 MAH/grams, and enclosed pasture efficient only is～23% first; From (b) as can be known: and the discharge first of the composite sample that makes is sung～320 MAH/grams, charging capacity still is～298 MAH/grams, enclosed pasture efficient reaches 93% first.The compound of this explanation carbon nano-tube and titanium dioxide is compared the carbon nano-tube reversible capacity and is significantly increased, and promptly enclosed pasture efficient is improved significantly.
Among Fig. 4, the enclosed pasture efficiency curve of the 20th～100 circulation of composite sample is stabilized between 95～97%, illustrates that the composite sample charge-discharge performance is superior.

Claims (1)

1. one kind at multi-walled carbon nano-tubes surface deposition nano-TiO 2Improve the method for lithium ion memory property, it is characterized in that having following technical process and step:
A. measure the butyl titanate and the oleic acid of certain volume, the preparing titanium dioxide predecessor; The volume ratio of butyl titanate and oleic acid is 1: 4; Oleic acid is heated to 55～65 ℃, in stirring, adds butyl titanate, get bright brown precursor liquid; It is standby to be cooled to room temperature;
B. get a certain amount of above-mentioned predecessor liquid, in stirring, add proper catalyst triethylamine; The addition of triethylamine is 6～7% of a described predecessor liquid volume amount;
C. taking by weighing a certain amount of multi-walled carbon nano-tubes (MWCNTs) joins in the mixed solvent of a certain amount of ethanol and toluene; The volume ratio of ethanol and toluene is 1: 1.5～1: 3 in the mixed solvent; Multi-walled carbon nano-tubes (MWCNTs) is 2.5～4.0mg/ml with the ratio that cooperates of described mixed solvent by the mass volume ratio suffering, the multi-walled carbon nano-tubes (MWCNTs) that promptly per 1 milliliter of mixed solvent configuration is 2.5～4.0 milligrams; Ultrasonic mixing 15～20 minutes;
D. join then in the above-mentioned precursor fluid that is added with triethylamine, continue to stir 2～3 hours, make to mix; Then this mixture is moved in the Teflon autoclave, and be positioned in 120～150 ℃ of baking ovens, reacted 12～15 hours; Obtain the black mixed liquor;
E. be 10000 rev/mins centrifugal separator centrifugation sedimentation with above-mentioned black mixed liquor rotating speed, obtain black precipitate; Then with ethanol washing once to remove excessive oleic acid, again with toluene wash 1～2 time to remove free titanium dioxide nano-particle; Through centrifugation, promptly obtain MWCNTs-TiO again 2Compound.
CN2010101267153A 2010-03-17 2010-03-17 Method for depositing TiO2 on surface of multiwall carbon nano-tube for improving memory property of lithium ion Expired - Fee Related CN101847712B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102931401A (en) * 2012-10-12 2013-02-13 中航锂电（洛阳）有限公司 Method for preparing lithium iron phosphate composite material
CN103187572A (en) * 2011-12-28 2013-07-03 清华大学 Thin-film lithium-ion battery
CN105527773A (en) * 2015-12-29 2016-04-27 江苏大学 Titanium dioxide functionalization multiwalled carbon nanotube nano composite optical limiting material and preparation method thereof
CN107210430A (en) * 2014-11-20 2017-09-26 魁北克电力公司 By the stable nano-sized anatase lattice of cation vacancy, its production method and application thereof
CN107221636A (en) * 2017-05-12 2017-09-29 哈尔滨工业大学 A kind of high performance three-dimensional classification hybrid structure lithium ion battery negative material and preparation method thereof
CN108735979A (en) * 2017-04-24 2018-11-02 清华大学 The preparation method of negative electrode of lithium ion battery
CN110880589A (en) * 2019-11-25 2020-03-13 浙江理工大学 Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof

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CN1868589A (en) * 2006-06-22 2006-11-29 厦门大学 Method for preparing carbon nanometer tube/titanium dioxide composite photocatalyst
CN101157521A (en) * 2007-09-20 2008-04-09 复旦大学 Visible light active nano titania coextruded film material and preparation method thereof
US20090175757A1 (en) * 2007-05-14 2009-07-09 Northwestern University Titanium dioxide, single-walled carbon nanotube composites
US20090191458A1 (en) * 2007-07-23 2009-07-30 Matsushita Electric Industrial Co., Ltd. Porous network negative electrodes for non-aqueous electrolyte secondary battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1868589A (en) * 2006-06-22 2006-11-29 厦门大学 Method for preparing carbon nanometer tube/titanium dioxide composite photocatalyst
US20090175757A1 (en) * 2007-05-14 2009-07-09 Northwestern University Titanium dioxide, single-walled carbon nanotube composites
US20090191458A1 (en) * 2007-07-23 2009-07-30 Matsushita Electric Industrial Co., Ltd. Porous network negative electrodes for non-aqueous electrolyte secondary battery
CN101157521A (en) * 2007-09-20 2008-04-09 复旦大学 Visible light active nano titania coextruded film material and preparation method thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103187572A (en) * 2011-12-28 2013-07-03 清华大学 Thin-film lithium-ion battery
CN103187572B (en) * 2011-12-28 2016-01-20 清华大学 Film lithium ion battery
CN102931401A (en) * 2012-10-12 2013-02-13 中航锂电（洛阳）有限公司 Method for preparing lithium iron phosphate composite material
CN102931401B (en) * 2012-10-12 2015-12-02 中航锂电（洛阳）有限公司 A kind of preparation method of composite ferric lithium phosphate material
CN107210430A (en) * 2014-11-20 2017-09-26 魁北克电力公司 By the stable nano-sized anatase lattice of cation vacancy, its production method and application thereof
CN107210430B (en) * 2014-11-20 2020-12-15 魁北克电力公司 Nanoscale anatase lattices stabilized by cationic vacancies, method for the production thereof and use thereof
CN105527773A (en) * 2015-12-29 2016-04-27 江苏大学 Titanium dioxide functionalization multiwalled carbon nanotube nano composite optical limiting material and preparation method thereof
CN108735979A (en) * 2017-04-24 2018-11-02 清华大学 The preparation method of negative electrode of lithium ion battery
CN108735979B (en) * 2017-04-24 2020-12-04 清华大学 Preparation method of lithium ion battery cathode
CN107221636A (en) * 2017-05-12 2017-09-29 哈尔滨工业大学 A kind of high performance three-dimensional classification hybrid structure lithium ion battery negative material and preparation method thereof
CN110880589A (en) * 2019-11-25 2020-03-13 浙江理工大学 Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof
CN110880589B (en) * 2019-11-25 2021-04-06 浙江理工大学 Carbon nanotube @ titanium dioxide nanocrystal @ carbon composite material and preparation method and application thereof

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