CN102956880A - Method for preparing Li4Ti5O12-TiO2 (lithium titanate - titanium oxide) nano composite material and Li4Ti5O12-TiO2 nano composite material thereof - Google Patents

Method for preparing Li4Ti5O12-TiO2 (lithium titanate - titanium oxide) nano composite material and Li4Ti5O12-TiO2 nano composite material thereof Download PDF

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CN102956880A
CN102956880A CN2012104599501A CN201210459950A CN102956880A CN 102956880 A CN102956880 A CN 102956880A CN 2012104599501 A CN2012104599501 A CN 2012104599501A CN 201210459950 A CN201210459950 A CN 201210459950A CN 102956880 A CN102956880 A CN 102956880A
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nano composite
composite material
tio
li4ti5o12
glycerol
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CN102956880B (en
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薛丽红
严有为
张五星
许超
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Huazhong University of 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
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a method for preparing Li4Ti5O12-TiO2 (lithium titanate - titanium oxide) nano composite material. The method comprises the following steps of mixing ammonia and with glycerol, and forming to form a transparent solution; sequentially adding organic titanium polymer and a LiOH (lithium hydroxide) solution into the transparent solution according to certain ratio of usage amounts; carrying out hydrothermal reaction on the obtained mixing solution at the temperature of 120 DEG C to 200 DEG C, and generating to generate a reaction precursor; and carrying out heat treatment on the obtained reaction precursor for 2 to 5 hours at the temperature of 400 DEG C to 800 DEG C, so as to obtain the Li4Ti5O12-TiO2 nano composite material. The invention also discloses a corresponding Li4Ti5O12-TiO2 nano composite material and an application. The method, the nano composite material and the application have the advantages that a Li4Ti5O12-TiO2 nano composite powder product can be obtained in a simple-process and energy-saving way, the quality is conveniently controlled, and the large-scale and batch production is realized; the grain size of the prepared material is small and uniform, and better circulation property and multiplying property and higher specific capacity are realized.

Description

A kind of for the preparation of Li 4Ti 5O 12-TiO 2Method of nano composite material and products thereof
Technical field
The invention belongs to the lithium ion battery electrode material field, more specifically, relate to a kind of for the preparation of Li 4Ti 5O 12-TiO 2Method of nano composite material and products thereof.
Background technology
The Li of spinel structure 4Ti 5O 12Material has the advantages such as " zero strain ", long circulation life and high security, is one of desirable negative material of power-type lithium ion battery of new generation.Yet its theoretical specific capacity is low, and electronic conductivity is low, the corresponding serious high rate capability that restricts this material.Improve at present Li 4Ti 5O 12The method of charge-discharge magnification performance mainly contains: 1. by the doping high volence metal ion or at Li 4Ti 5O 12Particle surface coats charcoal or other high conductivity material, to form the conductive network that connects the active particle material, finishing etc., improves the electron conduction ability; 2. the Li of synthesis nano 4Ti 5O 12Particle, the corresponding contact area that increases electrode material and electrolyte shortens Li +Migration path, increase Li +Mobility, and improve the ionic conduction ability; 3. mutually compound with large capacity negative material, to improve cycle characteristics and the specific capacity of material.
Studies show that TiO 2As a kind of good electrode material, has higher theoretical specific capacity (335mAh/g), suitable embedding lithium current potential (~ 2V vs.Li/Li+) and less cubical expansivity (3% ~ 4%), and TiO 2The Li that mixes 4Ti 5O 12Have better circulation and high rate performance.Therefore, if can prepare Li 4Ti 5O 12-TiO 2Nano composite material, will have important scientific meaning and practical value.
Traditional TiO 2Li doped 4Ti 5O 12The preparation method mostly adopt high-temperature solid phase reaction method or sol-gel process.Yet the existing major defect of these existing preparation methods is: high, the consuming time length of energy consumption, product is inhomogeneous or particle is larger; In addition, its preparation process technique is loaded down with trivial details, and lacks the regulation and control to electrochemical properties, therefore is difficult to realize that extensive explained hereafter satisfies the wilderness demand of energy field.Correspondingly, in association area, exist preparation Li 4Ti 5O 12-TiO 2The method of composite material is made further improved technical need.
Summary of the invention
For above defective and the technical need of prior art, the object of the present invention is to provide a kind of for the preparation of Li 4Ti 5O 12-TiO 2Method of nano composite material and products thereof, it is by studying and improve aspects such as key reaction thing and reaction conditions thereof, and is can technique simple, save and can obtain the nanoscale product in the seedbed, and is convenient to control quality and is suitable for large-scale mass production; Prepared Li 4Ti 5O 12-TiO 2The nano composite material crystallite dimension is little, epigranular, and possesses the specific capacity of good cycle performance, high rate performance and Geng Gao.
According to one aspect of the present invention, provide a kind of for the preparation of Li 4Ti 5O 12-TiO 2The method of nano composite material is characterized in that the method comprises the following steps:
(a) ammoniacal liquor and glycerol are mixed with the volume ratio of 1:1 ~ 1:20, and form clear solution;
(b) this clear solution is mixed mutually with the organotitanium polymer that is selected from butyl titanate or isopropyl titanate, wherein in the organotitanium polymer addition of titanium atom and the relation between the glycerol to satisfy be 0.1 ~ 5.0mol titanium atom/L glycerol;
(c) preparation LiOH solution, and join the LiOH solution of respective volume in the formed mixed solution of step (b) and mix according to the ratio of atomic ratio Li:Ti=0.5 ~ 2.0;
(d) mixed solution that step (c) is obtained was carried out hydro-thermal reaction 12 ~ 36 hours under 120 ~ 200 ℃ condition, obtain thus pre-reaction material;
(e) heat treatment 2 ~ 5 hours under 400-800 ℃ condition obtained Li thus after the pre-reaction material that step (d) obtained was processed through cleaning-drying 4Ti 5O 12-TiO 2Nano composite material.
By above design, on the one hand because the solution that adopts glycerol and ammoniacal liquor as reaction dissolvent, can utilize the ring-type chelation of glycerol in order to control the formation of Ti-O-C key, corresponding realization TiO 2With Li 4Ti 5O 12Nano combined, but also can utilize the chelating membrane of grain surface to suppress nuclei growth, thereby be conducive to reduce the size of crystal grain; On the other hand, the LiOH solution by adopting above consumption proportion is as reactant and mineralizer, and what can promote to react fully carries out, and guarantees to generate smoothly required Li 4Ti 5O 12-TiO 2Nanocomposite.
As further preferably, in step (b), it is 0.5 ~ 2.0mol titanium atom/L glycerol that the addition of described titanium atom and the relation between the glycerol satisfy.
By the consumption proportion between titanium atom and the glycerol further specifically is defined as above number range, more contrast test shows, above-mentioned consumption proportion can guarantee that reaction obtains to include simultaneously Li with high efficiency more 4Ti 5O 12And TiO 2Nano composite material, the product that obtains simultaneously shows better aspect cycle performance, high rate performance and specific capacity.
As further preferably, in step (d), adopt hydrothermal reaction kettle to be used as carrying out the container of described hydro-thermal reaction, and the mixed solution that adds account for this hydrothermal reaction kettle volume 50% ~ 80%.
By adopt hydrothermal reaction kettle carry out hydro-thermal reaction and with adding mixed solution volume make above restriction, more contrast test shows, can produce suitable air pressure in hydrothermal reaction process like this, further promotes the carrying out of hydro-thermal reaction; In addition, can also avoid add mixed solution product problem on the low side when very few, corresponding enhancing productivity.
As further preferably, in step (d), the mixed solution that adds account for this hydrothermal reaction kettle volume 55% ~ 65%.
According to another aspect of the present invention, also provide corresponding nano composite material product.
As further preferably, in resulting nano composite material, described Li 4Ti 5O 12Be spinel structure, described TiO 2Be Anatase or Rutile Type.
According to another aspect of the present invention, also provide resulting Li 4Ti 5O 12-TiO 2The purposes of nano composite material aspect the preparation cathode material of lithium-ion power battery.
Description of drawings
Fig. 1 is for the preparation of Li according to the present invention 4Ti 5O 12-TiO 2The process chart of nano composite material;
Fig. 2 a is the X-ray diffraction spectrogram according to the embodiment of the invention 1 resulting 1# sample;
Fig. 2 b is the scanning electron microscope (SEM) photograph according to the embodiment of the invention 1 resulting 1# sample;
Fig. 2 c be to this 1# sample charging under the 1C multiplying power, and respectively with 1C, 2C, 5C, 10C and 20C multiplying power under the charging and discharging curve figure that discharges and obtained;
Fig. 2 d is to the cycle performance curve chart of this 1# sample under the 1C multiplying power;
Fig. 2 e be to this 1# sample charging under the 1C multiplying power, and respectively with 1C, 2C, 5C, 10C and 20C multiplying power under the high rate performance curve chart that discharges, wherein each multiplying power circulation is 20 times.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.In addition, below in each execution mode of described the present invention involved technical characterictic just can mutually not make up as long as consist of each other conflict.
Fig. 1 is for the preparation of Li according to the present invention 4Ti 5O 12-TiO 2The process chart of nano composite material.As shown in fig. 1, in order to prepare required nanoscale Li 4Ti 5O 12-TiO 2Composite material at first, mixes ammoniacal liquor and glycerol with the volume ratio of 1:1～1:20, and forms clear solution; This clear solution is mixed mutually with the organotitanium polymer that is selected from butyl titanate or isopropyl titanate, wherein in the organotitanium polymer addition of titanium atom and the relation between the glycerol to satisfy be 0.1～5.0mol titanium atom/L glycerol, be preferably 0.5～2.0mol titanium atom/L glycerol.
Then, preparation LiOH solution, and add the LiOH solution of respective volume in the formed mixed solution and mix according to the ratio of atomic ratio Li:Ti=0.5 ~ 2.0; The mixed solution that obtains for example is contained in the hydrothermal reaction kettle, the mixed solution that adds account for this hydrothermal reaction kettle volume 50% ~ 80%, preferred 55% ~ 65%, and under 120 ~ 200 ℃ condition, carried out hydro-thermal reaction 12 ~ 36 hours, obtain thus pre-reaction material.
At last, after the pre-reaction material process cleaning-drying processing that obtains, heat treatment is 2 ~ 5 hours under 400-800 ℃ condition, obtains thus Li 4Ti 5O 12-TiO 2Nano composite material.
Embodiment 1
5mL ammoniacal liquor is evenly mixed with the 20mL glycerol, add successively again the LiOH solution of 10mmol butyl titanate and 40mL 0.225mol/L and mix.Above-mentioned mixed solution is transferred in the hydrothermal reaction kettle of Teflon liner, wherein adding the 55%(that mixed solution accounts for the hydrothermal reaction kettle volume is that the volume filling rate is 65%), and at 150 ℃ of lower hydrothermal treatment consists 24h.React after complete that also to be pre-reaction material with the sediment that generates clean and dry processing with deionized water and ethanol, then at 400 ℃ of lower heat treatment 2h, obtain the 1# sample.
Fig. 2 a is the X-ray diffraction spectrogram according to the embodiment of the invention 1 resulting 1# sample.As can be seen from the figure, the characteristic diffraction peak of this 1# sample is except meeting spinel-type Li 4Ti 5O 12Outside the standard spectrogram, Detitanium-ore-type TiO has also appearred 2Diffraction maximum, 1# sample of this explanation embodiment 1 preparation is by Li 4Ti 5O 12With Detitanium-ore-type TiO 2Be composited.
Fig. 2 b is the scanning electron microscope (SEM) photograph of embodiment 1 resulting 1# sample.As can be seen from the figure, the particle diameter of this 1# sample distributes comparatively even, and particle size is less, and average grain diameter is about 20nm, and grain surface is smooth, and pattern is rule, and crystallinity is better.
Fig. 2 c is the charging and discharging curve of embodiment 1 resulting 1# sample.Sample a little charging platform also occurs at the 2.14V place when discharging and recharging except a pair of stably charging/discharging voltage platform is arranged about 1.5V, and this is corresponding to Detitanium-ore-type TiO 2Embedding lithium current potential.Sample is 159.6mAh/g in the discharge capacity of 1C multiplying power, and the discharge capacity during 20C is still up to 151.3mAh/g; Along with discharge-rate increases to 20C from 1C, its discharge platform voltage only drops to 1.43V from 1.54V simultaneously, and as seen the polarization of this material is less, is the ideal electrode material of doing electrokinetic cell.
Fig. 2 d is the cycle performance curve demonstration to embodiment 1 resulting 1# sample, the first discharge specific capacity of this 1# sample under the 1C multiplying power is 184.7mAh/g, the enclosed pasture efficient be under 89.1%, the 1C multiplying power through 100 times the circulation after specific discharge capacity be 151.7mAh/g, capability retention is 82.1%.
Fig. 2 e is the high rate performance curve chart to embodiment 1 resulting 1# sample.Can find out among the figure, this 1# sample high rate performance is very good, and along with the raising of multiplying power, the discharge capacity of test battery decays to some extent, but it is very little to decay, and capacity is respectively 157.5,156.1,154.9 and 150.3mAh/g when 1C, 2C, 5C, 10C, 20C multiplying power discharging.
Embodiment 2
5mL ammoniacal liquor is evenly mixed with the 20mL glycerol, add again the LiOH solution of 15mmol butyl titanate and 30mL1.0mol/L.Said mixture is transferred in the hydrothermal reaction kettle of Teflon liner, the volume filling rate is 55%, at 200 ℃ of lower hydrothermal treatment consists 36h.React and sediment is cleaned and drying with deionized water and ethanol after complete, then at 500 ℃ of lower heat treatment 5h, obtain the 2# sample.
X-ray diffraction spectrogram and Li with embodiment 2 resulting 2# samples 4Ti 5O 12, Detitanium-ore-type TiO 2, rutile TiO 2The contrast of standard spectrogram is found: the characteristic diffraction peak of this 2# sample is except meeting spinel-type Li 4Ti 5O 12Outside the standard spectrogram, Detitanium-ore-type TiO has also appearred 2Diffraction maximum, this interpret sample is by Li 4Ti 5O 12With Detitanium-ore-type TiO 2Be composited.
Embodiment 3
1mL ammoniacal liquor is evenly mixed with the 20mL glycerol, add again the LiOH solution of 40mmol butyl titanate and 60mL0.67mol/L.Said mixture is transferred in the hydrothermal reaction kettle of Teflon liner, the volume filling rate is 80%, at 120 ℃ of lower hydrothermal treatment consists 36h.React and sediment is cleaned and drying with deionized water and ethanol after complete, then at 800 ℃ of lower heat treatment 2h, obtain the 3# sample.
X-ray diffraction spectrogram and Li with embodiment 3 resulting 3# samples 4Ti 5O 12, Detitanium-ore-type TiO 2, rutile TiO 2The contrast of standard spectrogram is found: the characteristic diffraction peak of this 3# sample is except meeting spinel-type Li 4Ti 5O 12Outside the standard spectrogram, the diffraction maximum of rutile TiO 2 also occurred, this interpret sample is composited by Li4Ti5O12 and rutile TiO 2.
Embodiment 4
10mL ammoniacal liquor is evenly mixed with the 10mL glycerol, add again the LiOH solution of 50mmol butyl titanate and 30mL0.83mol/L.Said mixture is transferred in the hydrothermal reaction kettle of Teflon liner, the volume filling rate is 50%, at 180 ℃ of lower hydrothermal treatment consists 12h.React and sediment is cleaned and drying with deionized water and ethanol after complete, then at 600 ℃ of lower heat treatment 2.5h, obtain the 4# sample.
X-ray diffraction spectrogram and Li4Ti5O12, anatase type tio2, the contrast of rutile TiO 2 standard spectrograms of embodiment 4 resulting 4# samples are found: the characteristic diffraction peak of this 2# sample is except meeting spinel-type Li4Ti5O12 standard spectrogram, the diffraction maximum that rutile TiO 2 also occurs, this interpret sample is composited by Li4Ti5O12 and rutile TiO 2.
Those skilled in the art will readily understand; the above only is preferred embodiment of the present invention; not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.

Claims (7)

1. one kind for the preparation of Li 4Ti 5O 12-TiO 2The method of nano composite material is characterized in that the method comprises the following steps:
(a) ammoniacal liquor and glycerol are mixed with the volume ratio of 1:1 ~ 1:20, and form clear solution;
(b) this clear solution is mixed mutually with the organotitanium polymer that is selected from butyl titanate or isopropyl titanate, wherein in the organotitanium polymer addition of titanium atom and the relation between the glycerol to satisfy be 0.1 ~ 5.0mol titanium atom/L glycerol;
(c) preparation LiOH solution, and join the LiOH solution of respective volume in the formed mixed solution of step (b) and mix according to the ratio of atomic ratio Li:Ti=0.5 ~ 2.0;
(d) mixed solution that step (c) is obtained was carried out hydro-thermal reaction 12 ~ 36 hours under 120 ~ 200 ℃ condition, obtain thus pre-reaction material;
(e) heat treatment 2 ~ 5 hours under 400-800 ℃ condition obtained Li thus after the pre-reaction material that step (d) obtained was processed through cleaning-drying 4Ti 5O 12-TiO 2Nano composite material.
2. the method for claim 1 is characterized in that, in step (b), it is 0.5 ~ 2.0mol titanium atom/L glycerol that the addition of described titanium atom and the relation between the glycerol satisfy.
3. method as claimed in claim 1 or 2 is characterized in that, in step (d), for example adopts hydrothermal reaction kettle to be used as carrying out the container of described hydro-thermal reaction, and the mixed solution that adds account for this hydrothermal reaction kettle volume 50% ~ 80%.
4. such as the described method of claim 1-3 any one, it is characterized in that, in step (d), the mixed solution that adds account for this hydrothermal reaction kettle volume 55% ~ 65%.
5. one kind according to such as the prepared Li of the described method of claim 1-4 any one 4Ti 5O 12-TiO 2The nano composite material product.
6. Li as claimed in claim 5 4Ti 5O 12-TiO 2The nano composite material product is characterized in that, at Li described in the resulting nano composite material 4Ti 5O 12Be spinel structure, described TiO 2Be Anatase or Rutile Type.
7. such as claim 5 or 6 described Li 4Ti 5O 12-TiO 2The purposes of nano composite material product aspect the preparation cathode material of lithium-ion power battery.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103346298A (en) * 2013-06-06 2013-10-09 吉林大学 Preparation method for lithium titanate-titanium oxide composite electrode material
CN104201344A (en) * 2014-09-05 2014-12-10 南开大学 Preparation method of copper-doped Li4Ti5O12-TiO2 regulation and control composite material
CN104993107A (en) * 2015-05-27 2015-10-21 辽宁大学 Lithium ion battery cathode material Li4Ti5O12/rutile-TiO2 and preparation method thereof
CN105206815A (en) * 2015-09-28 2015-12-30 清华大学 Carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite and preparation and application thereof
CN106887574A (en) * 2017-03-10 2017-06-23 辽宁大学 A kind of preparation method of regular octahedron pattern lithium ion battery negative material
CN108666557A (en) * 2018-05-29 2018-10-16 陕西动力越源科技有限公司 A kind of lithium ion battery Li4Ti5O12With TiO2Composite electrode material and preparation method thereof
CN108933252A (en) * 2018-09-04 2018-12-04 江南大学 Lithium ion battery lithium titanate and composite titania material and preparation method thereof
CN109546102A (en) * 2018-10-18 2019-03-29 北京航空航天大学 A kind of lithium titanate anode material and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102386385A (en) * 2011-10-09 2012-03-21 北京科技大学 Preparation method of Li4Ti5O12-TiO2 composite electrode material
CN102610824A (en) * 2012-03-26 2012-07-25 上海大学 Preparation method of lithium titanate (Li4Ti5O12)/Ag composite lithium-ion negative electrode materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102386385A (en) * 2011-10-09 2012-03-21 北京科技大学 Preparation method of Li4Ti5O12-TiO2 composite electrode material
CN102610824A (en) * 2012-03-26 2012-07-25 上海大学 Preparation method of lithium titanate (Li4Ti5O12)/Ag composite lithium-ion negative electrode materials

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103346298A (en) * 2013-06-06 2013-10-09 吉林大学 Preparation method for lithium titanate-titanium oxide composite electrode material
CN104201344A (en) * 2014-09-05 2014-12-10 南开大学 Preparation method of copper-doped Li4Ti5O12-TiO2 regulation and control composite material
CN104993107A (en) * 2015-05-27 2015-10-21 辽宁大学 Lithium ion battery cathode material Li4Ti5O12/rutile-TiO2 and preparation method thereof
CN105206815A (en) * 2015-09-28 2015-12-30 清华大学 Carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite and preparation and application thereof
CN106887574A (en) * 2017-03-10 2017-06-23 辽宁大学 A kind of preparation method of regular octahedron pattern lithium ion battery negative material
CN108666557A (en) * 2018-05-29 2018-10-16 陕西动力越源科技有限公司 A kind of lithium ion battery Li4Ti5O12With TiO2Composite electrode material and preparation method thereof
CN108933252A (en) * 2018-09-04 2018-12-04 江南大学 Lithium ion battery lithium titanate and composite titania material and preparation method thereof
CN109546102A (en) * 2018-10-18 2019-03-29 北京航空航天大学 A kind of lithium titanate anode material and preparation method thereof

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