CN102468485B - Lithium titanate composite material, preparation method thereof, and application thereof - Google Patents
Lithium titanate composite material, preparation method thereof, and application thereof Download PDFInfo
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- CN102468485B CN102468485B CN201010531928.4A CN201010531928A CN102468485B CN 102468485 B CN102468485 B CN 102468485B CN 201010531928 A CN201010531928 A CN 201010531928A CN 102468485 B CN102468485 B CN 102468485B
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Abstract
The invention is suitable for the technical field of energy, and provides a lithium titanate composite material, a preparation method thereof, and an application thereof. The lithium titanate composite material comprises graphene and nano-grade lithium titanate particles. Carbon coatings are coated on the nano-grade lithium titanate particles. Graphene is distributed on the outer side of the carbon coatings. The nano-grade lithium titanate particles have a chemical formula of Li4Ti5-xMxO12, wherein x is no smaller than 0.001 and is smaller than 5, and M is a transition metal element. According to the lithium titanate composite material provided by the invention, with the carbon coatings on the surfaces of the nano-grade lithium titanate particles, the metal M is doped in lithium titanate crystal lattices, and graphene is doped in the lithium titanate composite material, such that the conductivity of the lithium titanate composite material is greatly improved, and the charging/discharging rate of the composite material is substantially improved. The preparation method provided by the invention is advantaged in simple operation, low cost and suitability for industrialized productions.
Description
Technical field
The invention belongs to energy and material technical field, relate in particular to a kind of lithium titanate composite material, its preparation method and application.
Background technology
Lithium titanate volume in charge and discharge process changes hardly, good cycle, high (the 1.55V vs.Li/Li of embedding lithium current potential
+) and be difficult for causing that lithium metal is separated out, coulombic efficiency is high, lithium ion diffusion coefficient (is 2 × 10
-8cm2/s), than good characteristics such as the high orders of magnitude of carbon negative pole, the characteristic that therefore charging times is more, charging process is faster, safer, becomes the lithium ion battery negative material of new generation of tool development and application potentiality.But the poorly conductive of prior art lithium titanate material (intrinsic conductivity 10-9S/cm), the low grade of charge-discharge magnification has limited its commercialization.
Summary of the invention
In view of this, the embodiment of the present invention provides a kind of lithium titanate composite material, solves the low technical problem of prior art lithium titanate composite material charge-discharge magnification.
The present invention is achieved in that
A kind of lithium titanate composite material, this lithium titanate composite material comprises Graphene and nanoscale metatitanic acid lithium particulate, and this nanoscale metatitanic acid lithium particulate outer surface has carbon coating layer, and this Graphene is distributed in carbon coating layer outside, and this nanoscale metatitanic acid lithium particulate chemistry consists of Li
4ti
5-xm
xo
12, 0.001≤x < 5, M is transition metal.
The embodiment of the present invention further provides a kind of lithium titanate composite material preparation method, comprises the steps:
Press lithium, titanium and metal M mol ratio 4: 5-x: x the oxide of the source compound of lithium, titanium dioxide and metal M is mixed, grind 1-10 hour, at 400-900 ℃ of temperature, calcine 1-16 hour in air, obtaining chemical composition is Li
4ti
5-xm
xo
12nanoparticle, 0.001≤x < 5, M is transition metal;
The mix and blend reaction in solvent by this nanoparticle and organic carbon source monomer, obtains the coated lithium titanate nanoparticle of organic carbon source monomer;
This organic carbon source monomer clad nano particulate and graphene oxide are mixed in solvent, obtain mixed solution;
Dry this mixed solution, grinding are obtained to precursor;
Precursor, in reducing atmosphere and 400-1000 ℃ of temperature lower calcination 1-24 hour, is obtained to lithium titanate composite material.
The embodiment of the present invention also provides the application of above-mentioned lithium titanate composite material in battery or capacitor.
Embodiment of the present invention lithium titanate composite material, by the carbon coating layer of nanoscale metatitanic acid lithium microparticle surfaces, the metal adulterating in lithium titanate lattice and in this lithium titanate composite material doped graphene, greatly improve the electric conductivity of lithium titanate composite material, this lithium titanate composite material charge-discharge magnification is significantly improved.
Embodiment of the present invention preparation method, simple to operate, with low cost, be suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention lithium titanate composite material SEM figure;
Fig. 2 is embodiment of the present invention lithium titanate composite material charging and discharging curve figure.
Embodiment
In order to make object 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.
The embodiment of the present invention provides a kind of lithium titanate composite material; this lithium titanate composite material comprises Graphene and nanoscale metatitanic acid lithium particulate; this nanoscale metatitanic acid lithium particulate outer surface has carbon coating layer, and this Graphene is distributed in carbon coating layer outside, and this nanoscale metatitanic acid lithium particulate chemistry consists of Li
4ti
5-xm
xo
12, 0.001≤x < 5, M is transition metal.
Nanoscale metatitanic acid lithium particulate is the basic composition unit of embodiment of the present invention lithium titanate composite material, and this nanoscale metatitanic acid lithium particulate is also nanoscale metatitanic acid lithium particulate.Refer to Fig. 1, as can be known from Fig. 1, this nanoscale metatitanic acid lithium particulate is spherical or class is spherical, and particle diameter is 50 nanometer～100 micron, is preferably 50-200 nanometer.The particle diameter of lithium titanate particulate is nanoscale or micron order, guarantee that this lithium titanate composite material is in charge and discharge process, the distance of lithium ion diffusion is shorter, greatly increases the diffusion rate of lithium ion, thereby has realized the raising greatly of embodiment of the present invention lithium titanate composite material fast charging and discharging performance.
Particularly, this nanoscale metatitanic acid lithium particulate outer surface has carbon coating layer, and this carbon coating layer is to calcine by organic carbon source monomer, carbonization and forming.This carbon coating layer and nanoscale metatitanic acid lithium particulate close contact, because carbon is good electric conducting material, this carbon coating layer improves embodiment of the present invention lithium titanate composite material electric conductivity greatly, has realized the raising greatly of lithium titanate composite material charge-discharge magnification.
Outside at this carbon coating layer is distributed with Graphene, Graphene is entrained between the carbon-coated nano level lithium titanate particulate of lithium titanate composite material, in some specific embodiments, this carbon coating layer is incorporated into Graphene surface, makes nanoscale metatitanic acid lithium particulate be attached to Graphene surface by the annexation of carbon coating layer and Graphene.More preferably, Graphene forms gauffer, forms graphene coated layer at the outer surface of carbon coating layer.
This Graphene is single-layer graphene film or the Graphene aggregation that is made up of the single-layer graphene film of 2-100 layer.Graphene is excellent electric conducting material, by doped graphene in lithium titanate composite material, lithium titanate composite material electric conductivity is greatly improved, and has realized significantly improving of its charge-discharge magnification.
This nanoscale metatitanic acid lithium particulate chemistry consists of Li
4ti
5-xm
xo
12, 0.001≤x < 5, is preferably 0.003≤x≤0.3, M is transition metal, for example, in iron, cobalt, chromium, aluminium, nickel and copper one or more.By doping metals in lithium titanate particulate, greatly improve the electric conductivity of lithium titanate composite material, realize the raising greatly of lithium titanate composite material charge-discharge magnification.
The embodiment of the present invention further provides a kind of lithium titanate composite material preparation method, comprises the steps:
I) press lithium, titanium and metal M mol ratio 4: 5-x: x the oxide of the source compound of lithium, titanium dioxide and metal M is mixed, grind 1-10 hour, at 400-900 ℃ of temperature, calcine 1-16 hour in air, obtaining chemical composition is Li
4ti
5-xm
xo
12nanoparticle, 0.001≤x < 5, M is transition metal;
Ii) the mix and blend reaction in solvent by this nanoparticle and organic carbon source monomer, obtains the coated lithium titanate nanoparticle of organic carbon source monomer;
Iii) this organic carbon source monomer clad nano particulate and graphene oxide are mixed in solvent, obtain mixed solution;
Iv) dry this mixed solution, grinding are obtained to precursor;
V) by precursor in reducing atmosphere and 400-1000 ℃ of temperature lower calcination 1-24 hour, obtain lithium titanate composite material.
Particularly, in step I) in, the source compound of lithium is selected from one or more in lithium carbonate, lithium phosphate, lithium dihydrogen phosphate, lithium nitrate, lithium sulfate, lithium acetate, lithia, lithium hydroxide, lithium chloride, lithium iodide, lithium bromide, lithium fluoride and lithium stearate.M is transition metal, for example, in iron, cobalt, chromium, aluminium, nickel and copper one or more.The titanium dioxide using in this step is sharp ore deposit type titanium dioxide.Wherein, 0.001≤x < 5, is preferably 0.005≤x < 0.3.In grinding steps, need to add alcohol as solvent, this alcohol does not limit, such as ethanol, methyl alcohol, propyl alcohol, butanols etc.Ginding process does not limit, preferably ball grinding method, and when ball milling, rotating speed is 250 revs/min.In this step, metal M element, through grinding and calcining, is doped in lithium titanate nanometer lattice, has greatly improved the electric conductivity of lithium titanate composite material.The lithium titanate nanoparticle of preparing doping metals in this step by solid phase method, simple to operate, with low cost, equipment requirement is low.
Step I i) in, organic carbon source monomer refers to and can, at the organic substance of the polymerization of lithium titanate nano-particle surface and carbonization at 400-1000 ℃ of temperature, specifically comprise thiophene monomer or derivative, pyrrole monomer or derivatives thereof, aniline monomer or derivatives thereof.This step is that organic carbon source monomer is coated on to step I) the middle lithium titanate nano-particle surface of preparing, meanwhile, there is polymerization in the functional group of this organic carbon source monomer self, therefore, forms organic carbon source monomer coating layer at lithium titanate nano-particle surface.In some specific embodiments, also add the initator of hydrogen peroxide as this step reaction.The solvent using in this step does not limit, and can be various solvents, is preferably water.In this step, the stirring reaction time is 20 minutes～2 hours.By the reaction of this step, the lithium titanate nanoparticle that above-mentioned steps i) is prepared is coated by organic monomer, then passes through the high-temperature calcination of following step, and this organic carbon source monomer is decomposed, carbonization, thereby forms carbon coating layer at lithium titanate nano-particle surface.
At step I ii) in, the preparation of graphene oxide is restriction not, the method that the embodiment of the present invention is used is for according to improved hummers method (J.Am.Chem.Soc., 1958,80 (6), 1339-1339, Preparation of Graphitic Oxide) (Chinese name " American Chemical Society's meeting will ").The solvent that this step is used does not limit, and is preferably water.The coated lithium titanate nanoparticle of organic carbon source monomer and graphene oxide that step I i) is prepared mix in solvent, the functional group on the functional group of organic carbon source monomer and graphene oxide surface reacts, and above-mentioned organic carbon source monomer coating layer and graphene oxide are combined closely.In this step, the stirring reaction time is 20 minutes～2 hours, and the addition (quality) of graphene oxide is the 0.1-99% of the lithium titanate nanoparticle quality that adds.
V) dry this mixed solution, grinding are obtained to precursor in step I, in this step, drying means does not limit, and can make in all sorts of ways.After dry, by the solid abrasive powdered obtaining, this powder particle particle diameter is 200-500nm, obtains lithium titanate composite material precursor.
Step v) in, programming rate is 2-10 ℃/min, the atmosphere that this step is used is reducing atmosphere, this reducing atmosphere is not specifically limited, and can be the volume ratio carbon monoxide of 90: 10 and nitrogen atmosphere, hydrogen and the helium etc. of 80: 20.The embodiment of the present invention also provides the application of above-mentioned lithium titanate composite material in battery or capacitor.Embodiment of the present invention lithium titanate composite material uses as negative material in battery or capacitor.
Embodiment of the present invention lithium titanate composite material, by the carbon coating layer of nanoscale metatitanic acid lithium microparticle surfaces, has improved the electric conductivity of lithium titanate composite material greatly, has realized and has changed significantly improving of composite material charge-discharge magnification.
Embodiment of the present invention lithium titanate composite material, by doped graphene in lithium titanate micrograined texture, greatly improve the electric conductivity of lithium titanate composite material, greatly improve its charge-discharge magnification, nanoscale metatitanic acid lithium particulate is attached to Graphene surface, further improve the electric conductivity of lithium titanate composite material, further realized significantly improving of its charge-discharge magnification.Meanwhile, doping metals M in lithium titanate micrograined texture, has improved the electric conductivity of lithium titanate composite material greatly, has greatly improved the charge-discharge magnification of lithium titanate composite material.
In embodiment of the present invention lithium titanate composite material, lithium ion has higher diffusion rate, makes to use the battery of lithium titanate composite material or capacitor to have fast charging and discharging performance.
Embodiment of the present invention preparation method, simple to operate, with low cost, be suitable for suitability for industrialized production.
Below in conjunction with specific embodiment, the present invention will be described in detail.
Embodiment mono-
Embodiment of the present invention lithium titanate composite material preparation method, comprises the steps:
I) ratio that is 4: 4.7: 0.3 by lithium carbonate, titanium dioxide and ferrous oxide according to elemental lithium, titanium elements, ferro element mol ratio joins in ball grinder, add ethanolic solution, on ball mill with the rotating speed ball milling of 250r/min after 3 hours, again the mixture after ball milling is put into crucible, be placed in again Muffle furnace, in 900 ℃ of air, calcine 16h, naturally cooling after, obtaining chemical composition is Li
4ti
4.7fe
0.3o
12nanoparticle;
II) under the condition stirring by step I) nanoparticle that obtains joins in the aniline solution that concentration is 1.72mol/L, then adds 10g H
2o
2, stirring reaction is after 2 hours, gets precipitation after centrifugal, and it is Li that washing obtains polyaniline-coated chemical composition
4ti
4.7fe
0.3o
12nano particle.
III) preparation graphene oxide solution, the preparation method of graphene oxide is according to improved hummers method, (J.Am.Chem.Soc., 1958,80 (6), 1339-1339, Preparation of Graphitic Oxide), then 10g is dissolved in the water of 10mL, to form concentration be 1g/mL graphite oxide aqueous solution, obtains the solution system of brown;
IV) get above-mentioned steps III) the polyaniline-coated chemical composition that obtains is Li
4ti
4.7fe
0.3o
12nanoparticle 0.1mol, graphite oxide aqueous solution (wherein containing graphene oxide 5g) evenly mix, and obtain mixed liquor;
V) by step IV) mixed liquor that obtains stirs and is warming up to 70 ℃, until system becomes after muddy, puts into 80 ℃ of air dry ovens and continues dryly more than 1 hour, obtains lithium titanate composite material precursor;
VI) by step V) the lithium titanate composite material precursor that obtains puts into Muffle furnace, in carbon monoxide atmosphere, rises to 800 ℃ and be incubated 12h from room temperature, and programming rate is 5 ℃/min, naturally cooling, grinds after sieving and obtains lithium titanate composite material.
VII) battery assembling and performance test: get respectively lithium titanate composite material provided by the invention, acetylene black, polyvinylidene fluoride (PVDF) and carry out proportioning in the ratio of 84: 8: 8, after evenly mixing, be coated on and on Copper Foil, make positive plate, next take lithium metal as negative pole, polypropylene film is barrier film, the LiPF of 1mol/L
6ethylene carbonate (EC) and the mixed liquor of dimethyl carbonate (DMC) (volume ratio 1: 1) be electrolyte, in the glove box of argon gas atmosphere, in the time that moisture is less than 1.0ppm, be assembled in order button cell, leave standstill to be tested after 12 hours.
The system that discharges and recharges of battery is: when charging, set charging and discharging currents by the specific capacity size of battery and charge-discharge magnification, carry out constant current charge-discharge, after cell voltage reaches 2.5V, system is had a rest 10 minutes.Embodiment of the present invention charging 0.2C, discharging current is 1C, when electric discharge, in the time that cell voltage drops to 1.0V, circuit stops electric discharge (1C=175mA/g) automatically, then enters next circulation.
Refer to Fig. 2, Fig. 2 is embodiment of the present invention lithium titanate composite material first charge-discharge test curve figure.1 is charging curve, and 2 for putting point curve, and as seen from the figure, the material of synthesized has excellent discharge platform and higher reversible capacity, and discharge capacity can reach 162mAh/g first, puts a platform more smooth, demonstrates good embedding lithium performance.
Embodiment bis-
Embodiment of the present invention lithium titanate composite material preparation method, comprises the steps:
I) ratio that is 4: 4.8: 0.2 by lithium acetate, titanium dioxide and nickel protoxide according to elemental lithium, titanium elements, nickel element mol ratio joins in ball grinder, add ethanolic solution, on ball mill with the rotating speed ball milling of 250r/min after 1 hour, again the mixture after ball milling is put into crucible, be placed in Muffle furnace, in air ambient, 400 ℃ of calcining 1h, naturally, after cooling, obtaining chemical composition is Li
4ti
4.8ni
0.2o
12nanoparticle;
II) under the condition stirring by step I) nanoparticle that obtains joins in pyrroles's solution that concentration is 1.72mol/L, then adds 15gH
2o
2, stirring reaction is after 2 hours, gets precipitation after centrifugal, and it is Li that washing obtains polyaniline-coated chemical composition
4ti
4.8ni
0.2o
12nano particle.
III) preparation graphene oxide solution, the preparation method of graphene oxide is according to improved hummers method, (J.Am.Chem.Soc., 1958,80 (6), 1339-1339, Preparation of Graphitic Oxide), then 10g is dissolved in the water of 10mL, to form concentration be 1g/mL graphite oxide aqueous solution, obtains the solution system of brown;
IV) get above-mentioned steps III) the polyaniline-coated chemical composition that obtains is Li
4ti
4.8ni
0.2o
12nanoparticle 0.1mol, graphite oxide aqueous solution (wherein containing graphene oxide 5g) evenly mix, and obtain mixed liquor;
V) by step IV) mixed liquor that obtains stirs and is warming up to 70 ℃, until system becomes after muddy, puts into 80 ℃ of air dry ovens and continues dryly more than 5 hours, obtains lithium titanate composite material precursor;
VI) by step V) the lithium titanate composite material precursor that obtains puts into Muffle furnace, in hydrogen atmosphere, rises to 400 ℃ and be incubated 24h from room temperature, and programming rate is 5 ℃/min, naturally cooling, grinds after sieving and obtains lithium titanate composite material.
Embodiment tri-
Embodiment of the present invention lithium titanate composite material preparation method, comprises the steps:
I) ratio that is 4: 4.8: 0.2 by lithium nitrate, titanium dioxide and chromium oxide according to elemental lithium, titanium elements, chromium element mol ratio joins in ball grinder, add ethanolic solution, on ball mill with the rotating speed ball milling of 250r/min after 3 hours, again the mixture after ball milling is put into crucible, be placed in Muffle furnace, 600 ℃ calcining 12h, naturally cooling after, obtaining chemical composition is Li
4ti
4.8cr
0.2o
12nanoparticle;
II) under the condition stirring by step I) nanoparticle that obtains joins in the aniline solution that concentration is 1.72mol/L, then adds 20gH
2o
2, stirring reaction is after 2 hours, gets precipitation after centrifugal, and it is Li that washing obtains polyaniline-coated chemical composition
4ti
4.8cr
0.2o
12nano particle.
III) preparation graphene oxide solution, the preparation method of graphene oxide is according to improved hummers method, (J.Am.Chem.Soc., 1958,80 (6), 1339-1339, Preparation of Graphitic Oxide), then 10g is dissolved in the water of 10mL, to form concentration be 1g/mL graphite oxide aqueous solution, obtains the solution system of brown;
IV) get above-mentioned steps III) the polyaniline-coated chemical composition that obtains is Li
4ti
4.8cr
0.2o
12nanoparticle 0.1mol, graphite oxide aqueous solution (wherein containing graphene oxide 5g) evenly mix, and obtain mixed liquor;
V) by step IV) mixed liquor that obtains stirs and is warming up to 70 ℃, until system becomes after muddy, puts into 80 ℃ of air dry ovens and continues dryly more than 1 hour, obtains lithium titanate composite material precursor;
VI) by step V) the lithium titanate composite material precursor that obtains puts into Muffle furnace, in 10% hydrogen and 90% argon gas atmosphere, rise to 1000 ℃ and be incubated 5h from room temperature, programming rate is 5 ℃/min, naturally cooling, grinding obtains lithium titanate composite material after sieving.
The foregoing is only preferred embodiment of the present invention, not in order to limit 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., within all should being included in protection scope of the present invention.
Claims (6)
1. a lithium titanate composite material preparation method, comprises the steps:
Press lithium, titanium and metal M mol ratio 4:5-x:x the oxide of the source compound of lithium, titanium dioxide and metal M is mixed, grind 1-10 hour, at 400-900 ℃ of temperature, calcine 1-16 hour in air, obtaining chemical composition is Li
4ti
5-xm
xo
12nanoparticle, 0.001≤x < 5, M is transition metal, in described transition metal chosen from Fe, cobalt, chromium, nickel, copper more than one;
By described nanoparticle and organic carbon source monomer, mix and blend in solvent reacts 20 minutes-2 hours, obtains the coated lithium titanate nanoparticle of organic carbon source monomer;
Described organic carbon source monomer clad nano particulate and graphene oxide are mixed in solvent, and stirring reaction obtains mixed solution;
Dry described mixed solution, grinding are obtained to lithium titanate composite material precursor;
Described lithium titanate composite material precursor, in reducing atmosphere and 400-1000 ℃ of temperature lower calcination 1-24 hour, is obtained to lithium titanate composite material, and wherein, the programming rate that rises to 400-1000 ℃ is 2-10 ℃/min; Described lithium titanate composite material comprises Graphene and nanoscale metatitanic acid lithium particulate, and described nanoscale metatitanic acid lithium particulate outer surface has Graphene described in carbon coating layer to be distributed in described carbon coating layer outside.
2. lithium titanate composite material preparation method as claimed in claim 1, is characterized in that, described organic carbon source monomer be in pyrrole monomer or derivatives thereof, aniline monomer or derivatives thereof and thiophene monomer or derivatives thereof more than one.
3. lithium titanate composite material preparation method as claimed in claim 1, is characterized in that, described carbon coating layer is incorporated into Graphene surface.
4. lithium titanate composite material preparation method as claimed in claim 1, is characterized in that, described nanoscale metatitanic acid lithium diameter of particle is 50 nanometer～100 micron.
5. lithium titanate composite material preparation method as claimed in claim 1, is characterized in that, described Graphene is the aggregation that the single-layer graphene film of single-layer graphene film or 2-100 layer forms.
6. lithium titanate composite material preparation method as claimed in claim 1, is characterized in that, described x scope is 0.003≤x < 0.3.
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| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene composite electrode material |
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| CN101237036A (en) * | 2008-01-21 | 2008-08-06 | 湘潭大学 | Making method for positive material LiFePO4 of poly-aniline coated lithium ion battery |
| CN101562248A (en) * | 2009-06-03 | 2009-10-21 | 龚思源 | Graphite composite lithium ion battery anode material lithium iron phosphate and preparation method thereof |
| CN101702431A (en) * | 2009-10-30 | 2010-05-05 | 南京工业大学 | A kind of preparation method of lithium titanate negative electrode composite material for lithium ion battery |
| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene composite electrode material |
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