CN102468485A - 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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- CN102468485A CN102468485A CN2010105319284A CN201010531928A CN102468485A CN 102468485 A CN102468485 A CN 102468485A CN 2010105319284 A CN2010105319284 A CN 2010105319284A CN 201010531928 A CN201010531928 A CN 201010531928A CN 102468485 A CN102468485 A CN 102468485A
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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 the 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 high, the lithium ion diffusion coefficient (is 2 * 10
-8Cm2/s) than good characteristics such as the high one magnitude of carbon negative pole, so the characteristic that charging times is more, charging process is faster, safer, make it become 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 limited its commercialization.
Summary of the invention
In view of this, the embodiment of the 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 comprise 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 the 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 a transition metal.
The embodiment of the 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: the x oxide mixing with source compound, titanium dioxide and the metal M of lithium, ground 1-10 hour, under 400-900 ℃ of temperature, calcining is 1-16 hour in air, and obtaining chemical composition is Li
4Ti
5-xM
xO
12Nanoparticle, 0.001≤x＜5, M is a transition metal;
This nanoparticle and organic carbon source monomer are mixed stirring reaction in solvent, obtain the organic carbon source monomer and coat the lithium titanate nanoparticle;
This organic carbon source monomer clad nano particulate and graphene oxide are mixed in solvent, obtain mixed solution;
This mixed solution is dry, grinding obtains precursor;
Precursor in reducing atmosphere and 400-1000 ℃ temperature lower calcination 1-24 hour, is obtained lithium titanate composite material.
The embodiment of the invention also provides the application of above-mentioned lithium titanate composite material in battery or capacitor.
Embodiment of the invention lithium titanate composite material; Carbon coating layer through nanoscale metatitanic acid lithium microparticle surfaces; The metal that in the lithium titanate lattice, mixes reaches doped graphene in this lithium titanate composite material; Improved the electric conductivity of lithium titanate composite material greatly, this lithium titanate composite material charge-discharge magnification is significantly improved.
Embodiment of the invention preparation method, simple to operate, with low cost, be suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is embodiment of the invention lithium titanate composite material SEM figure;
Fig. 2 is embodiment of the invention lithium titanate composite material charging and discharging curve figure.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with accompanying drawing and embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The embodiment of the 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 the 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 a transition metal.
Nanoscale metatitanic acid lithium particulate is the basic composition unit of embodiment of the invention lithium titanate composite material, and this nanoscale metatitanic acid lithium particulate also is a nanoscale metatitanic acid lithium particulate.See also Fig. 1, from Fig. 1, can know, this nanoscale metatitanic acid lithium particulate is spherical or type spherical, and particle diameter is 50 nanometers～100 micron, is preferably the 50-200 nanometer.The particle diameter of lithium titanate particulate is nanoscale or micron order; Guaranteed that this lithium titanate composite material is in charge and discharge process; The distance of lithium ion diffusion is shorter, increases the diffusion rate of lithium ion greatly, thereby has realized the raising greatly of embodiment of the 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 through organic carbon source monomer calcining, carbonization and forming.This carbon coating layer closely contacts with nanoscale metatitanic acid lithium particulate, because carbon is good electric conducting material, this carbon coating layer improves embodiment of the invention lithium titanate composite material electric conductivity greatly, has realized the raising greatly of lithium titanate composite material charge-discharge magnification.
Exterior portions at this carbon coating layer is furnished 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 the Graphene surface, makes nanoscale metatitanic acid lithium particulate surperficial attached to Graphene through the annexation of carbon coating layer and Graphene.More preferably, Graphene forms gauffer, at the outer surface formation Graphene coating layer 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, through doped graphene in lithium titanate composite material, makes the lithium titanate composite material electric conductivity greatly improve, 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 are preferably 0.003≤x≤0.3, M is a transition metal, for example in iron, cobalt, chromium, aluminium, nickel and the copper one or more.Through doping metals in the lithium titanate particulate, improved the electric conductivity of lithium titanate composite material greatly, realized the raising greatly of lithium titanate composite material charge-discharge magnification.
The embodiment of the 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: the x oxide mixing with source compound, titanium dioxide and the metal M of lithium, ground 1-10 hour, under 400-900 ℃ of temperature, calcining is 1-16 hour in air, and obtaining chemical composition is Li
4Ti
5-xM
xO
12Nanoparticle, 0.001≤x＜5, M is a transition metal;
Ii) this nanoparticle and organic carbon source monomer are mixed stirring reaction in solvent, obtain the organic carbon source monomer and coat the lithium titanate nanoparticle;
Iii) this organic carbon source monomer clad nano particulate and graphene oxide are mixed in solvent, obtain mixed solution;
Iv) that this mixed solution is dry, grinding obtains precursor;
V) with precursor in reducing atmosphere and 400-1000 ℃ 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 the lithium stearate.M is a transition metal, for example in iron, cobalt, chromium, aluminium, nickel and the copper one or more.The titanium dioxide that uses in this step is sharp ore deposit type titanium dioxide.Wherein, 0.001≤x＜5 are preferably 0.005≤x＜0.3.In grinding steps, need to add alcohol as solvent, this alcohol is restriction not, for example ethanol, methyl alcohol, propyl alcohol, butanols etc.Ginding process is restriction not, preferred ball grinding method, and rotating speed is 250 rev/mins during ball milling.In this step, the metal M element is doped in the lithium titanate nanometer lattice through grinding and calcining, has improved the electric conductivity of lithium titanate composite material greatly.Prepare the lithium titanate nanoparticle of doping metals in this step through solid phase method, simple to operate, with low cost, equipment requirements is low.
At step I i) in, the organic carbon source monomer is meant and can specifically comprises thiophene monomer or derivative, pyrrole monomer or derivatives thereof, aniline monomer or derivatives thereof at the organic substance of polymerization of lithium titanate nano-particle surface and carbonization under 400-1000 ℃ of temperature.This step is that the organic carbon source monomer is coated on step I) the middle lithium titanate nano-particle surface for preparing, simultaneously, polymerization takes place in the functional group of this organic carbon source monomer self, therefore, forms organic carbon source monomer coating layer at the lithium titanate nano-particle surface.In some specific embodiments, also add the initator of hydrogen peroxide solution as this step reaction.The solvent that uses in this step is restriction not, can be all kinds of solvents, is preferably water.In this step, the stirring reaction time is 20 minutes～2 hours.Through the reaction of this step, above-mentioned steps i) the lithium titanate nanoparticle of preparation coated by organic monomer, passes through the high-temperature calcination of following step again, and this organic carbon source monomer is decomposed, carbonization, thereby forms carbon coating layer at the lithium titanate nano-particle surface.
Step I ii) in; The preparation of graphene oxide is restriction not; The employed method of the embodiment of the invention is 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 is restriction not, is preferably water.With step I i) the organic carbon source monomer of preparation coats the lithium titanate nanoparticle and graphene oxide mixes 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 of graphene oxide (quality) is the 0.1-99% of the lithium titanate nanoparticle quality of adding.
, grinding v) that this mixed solution is dry in step I obtains precursor, and not restriction of drying means can make in all sorts of ways in this step.After the drying, with the solid abrasive powdered that obtains, this powder particle particle diameter is 200-500nm, obtains the lithium titanate composite material precursor.
Step v) in, programming rate is 2-10 ℃/minute, the atmosphere that this step is used is reducing atmosphere, the not concrete restriction of this reducing atmosphere can be 90: 10 carbon monoxide of volume ratio and nitrogen atmosphere, 80: 20 hydrogen and helium etc.The embodiment of the invention also provides the application of above-mentioned lithium titanate composite material in battery or capacitor.Embodiment of the invention lithium titanate composite material uses as negative material in battery or capacitor.
Embodiment of the invention lithium titanate composite material through the carbon coating layer of nanoscale metatitanic acid lithium microparticle surfaces, has improved the electric conductivity of lithium titanate composite material greatly, has realized changing significantly improving of composite material charge-discharge magnification.
Embodiment of the invention lithium titanate composite material; Through doped graphene in the lithium titanate micrograined texture; Improved the electric conductivity of lithium titanate composite material greatly, improved its charge-discharge magnification greatly, nanoscale metatitanic acid lithium particulate is attached to the Graphene surface; Further improve the electric conductivity of lithium titanate composite material, further realized significantly improving of its charge-discharge magnification.Simultaneously, doping metals M in the lithium titanate micrograined texture has improved the electric conductivity of lithium titanate composite material greatly, has improved the charge-discharge magnification of lithium titanate composite material greatly.
In the embodiment of the invention lithium titanate composite material, lithium ion has higher diffusion rate, makes to use the battery or the capacitor of lithium titanate composite material to have fast charging and discharging performance.
Embodiment of the 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 is set forth in detail.
Embodiment one
Embodiment of the invention lithium titanate composite material preparation method comprises the steps:
I) be that 4: 4.7: 0.3 ratio joins in the ball grinder with lithium carbonate, titanium dioxide and ferrous oxide according to elemental lithium, titanium elements, ferro element mol ratio; Add ethanolic solution, after 3 hours, again the mixture behind the ball milling is being put into crucible with the rotating speed ball milling of 250r/min on the ball mill; Place Muffle furnace again; Calcine 16h in 900 ℃ of air, behind the natural cooling, obtaining chemical composition is Li
4Ti
4.7Fe
0.3O
12Nanoparticle;
II) under stirring condition with step I) nanoparticle that obtains joins in the aniline solution that concentration is 1.72mol/L, adds 10g H then
2O
2, stirring reaction is after 2 hours, gets deposition after centrifugal, and washing obtains polyaniline, and to coat chemical composition be Li
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, forming concentration is the graphite oxide aqueous solution of 1g/mL, obtains the solution system of brown;
IV) get above-mentioned steps III) to coat chemical composition be Li for the polyaniline that obtains
4Ti
4.7Fe
0.3O
12Nanoparticle 0.1mol, graphite oxide aqueous solution (wherein containing graphene oxide 5g) evenly mix, and obtain mixed liquor;
V) with step IV) resulting mixed liquor stirs and is warming up to 70 ℃, after system becomes muddy, puts into 80 ℃ of air dry ovens and continues dryly more than 1 hour, obtains the lithium titanate composite material precursor;
VI) with 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, and natural cooling grinds and promptly obtains lithium titanate composite material after sieving.
VII) battery assembling and performance test: get lithium titanate composite material provided by the invention, acetylene black, polyvinylidene fluoride (PVDF) respectively and carry out proportioning in 84: 8: 8 ratio; Be coated on after evenly mixing and process positive plate on the Copper Foil; Next with the lithium metal negative pole; Polypropylene film is a 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, be assembled into button cell in order during less than 1.0ppm in moisture, leave standstill after 12 hours to be tested.
The system of discharging and recharging of battery is: during charging, press specific capacity size and the charge-discharge magnification of battery and set charging and discharging currents, carry out constant current charge-discharge, treat that cell voltage reaches 2.5V after, system had a rest 10 minutes.Embodiment of the invention charging 0.2C, discharging current is 1C, when treating during discharge that cell voltage drops to 1.0V, circuit stops discharge (1C=175mA/g) automatically, gets into next circulation then.
See also Fig. 2, Fig. 2 is embodiment of the invention lithium titanate composite material first charge-discharge test curve figure.1 is charging curve, and 2 for putting point curve, and visible by figure, the material that is synthesized has excellent discharge platform and higher reversible capacity, and discharge capacity can reach 162mAh/g first, and it is more smooth to put a platform, demonstrates and embeds the lithium performance preferably.
Embodiment two
Embodiment of the invention lithium titanate composite material preparation method comprises the steps:
I) be that 4: 4.8: 0.2 ratio joins in the ball grinder with lithium acetate, titanium dioxide and nickel protoxide according to elemental lithium, titanium elements, nickel element mol ratio, add ethanolic solution, on the ball mill with the rotating speed ball milling of 250r/min after 1 hour; Again the mixture behind the ball milling is put into crucible; Place Muffle furnace, in air ambient, 400 ℃ of calcining 1h; Behind the natural cooling, obtaining chemical composition is Li
4Ti
4.8Ni
0.2O
12Nanoparticle;
II) under stirring condition with step I) nanoparticle that obtains joins in pyrroles's solution that concentration is 1.72mol/L, adds 15gH then
2O
2, stirring reaction is after 2 hours, gets deposition after centrifugal, and washing obtains polyaniline, and to coat chemical composition be Li
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, forming concentration is the graphite oxide aqueous solution of 1g/mL, obtains the solution system of brown;
IV) get above-mentioned steps III) to coat chemical composition be Li for the polyaniline that obtains
4Ti
4.8Ni
0.2O
12Nanoparticle 0.1mol, graphite oxide aqueous solution (wherein containing graphene oxide 5g) evenly mix, and obtain mixed liquor;
V) with step IV) resulting mixed liquor stirs and is warming up to 70 ℃, after system becomes muddy, puts into 80 ℃ of air dry ovens and continues dryly more than 5 hours, obtains the lithium titanate composite material precursor;
VI) with 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, and natural cooling grinds and promptly obtains lithium titanate composite material after sieving.
Embodiment three
Embodiment of the invention lithium titanate composite material preparation method comprises the steps:
I) be that 4: 4.8: 0.2 ratio joins in the ball grinder with lithium nitrate, titanium dioxide and chromium oxide according to elemental lithium, titanium elements, chromium element mol ratio; Add ethanolic solution, after 3 hours, again the mixture behind the ball milling is being put into crucible with the rotating speed ball milling of 250r/min on the ball mill; Place Muffle furnace; 600 ℃ of calcining 12h, behind the natural cooling, obtaining chemical composition is Li
4Ti
4.8Cr
0.2O
12Nanoparticle;
II) under stirring condition with step I) nanoparticle that obtains joins in the aniline solution that concentration is 1.72mol/L, adds 20gH then
2O
2, stirring reaction is after 2 hours, gets deposition after centrifugal, and washing obtains polyaniline, and to coat chemical composition be Li
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, forming concentration is the graphite oxide aqueous solution of 1g/mL, obtains the solution system of brown;
IV) get above-mentioned steps III) to coat chemical composition be Li for the polyaniline that obtains
4Ti
4.8Cr
0.2O
12Nanoparticle 0.1mol, graphite oxide aqueous solution (wherein containing graphene oxide 5g) evenly mix, and obtain mixed liquor;
V) with step IV) resulting mixed liquor stirs and is warming up to 70 ℃, after system becomes muddy, puts into 80 ℃ of air dry ovens and continues dryly more than 1 hour, obtains the lithium titanate composite material precursor;
VI) with 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; Natural cooling promptly obtains lithium titanate composite material after grinding is sieved.
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. lithium titanate composite material; Said lithium titanate composite material comprises Graphene and nanoscale metatitanic acid lithium particulate; Said nanoscale metatitanic acid lithium particulate outer surface has carbon coating layer, and it is outside that said Graphene is distributed in said carbon coating layer, and said nanoscale metatitanic acid lithium particulate chemistry consists of Li
4Ti
5-xM
xO
12, wherein, 0.001≤x＜5, M is a transition metal.
2. lithium titanate composite material as claimed in claim 1 is characterized in that said carbon coating layer is incorporated into the Graphene surface.
3. lithium titanate composite material as claimed in claim 1 is characterized in that, said nanoscale metatitanic acid lithium diameter of particle is 50 nanometers～100 micron.
4. lithium titanate composite material as claimed in claim 1 is characterized in that, said Graphene is the aggregation that the single-layer graphene film of single-layer graphene film or 2-100 layer constitutes.
5. lithium titanate composite material as claimed in claim 1 is characterized in that, said x scope is 0.003≤x＜0.3.
6. lithium titanate composite material as claimed in claim 1 is characterized in that, in said transition metal M chosen from Fe, cobalt, chromium, aluminium and the nickel one or more.
7. a lithium titanate composite material preparation method comprises the steps:
Press lithium, titanium and metal M mol ratio 4: 5-x: the x oxide mixing with source compound, titanium dioxide and the metal M of lithium, ground 1-10 hour, under 400-900 ℃ of temperature, calcining is 1-16 hour in air, and obtaining chemical composition is Li
4Ti
5-xM
xO
12Nanoparticle, 0.001≤x＜5, M is a transition metal;
Said nanoparticle and organic carbon source monomer were mixed stirring reaction 20 minutes-2 hours in solvent, obtain the organic carbon source monomer and coat the lithium titanate nanoparticle;
Said organic carbon source monomer clad nano particulate and graphene oxide are mixed in solvent, and stirring reaction obtains mixed solution;
Said mixed solution is dry, grinding obtains the lithium titanate composite material precursor;
Said lithium titanate composite material precursor in reducing atmosphere and 400-1000 ℃ temperature lower calcination 1-24 hour, is obtained lithium titanate composite material.
8. lithium titanate composite material preparation method as claimed in claim 7 is characterized in that, the scope of x is 0.003≤x＜0.3, in said metal M chosen from Fe, cobalt, chromium, aluminium, nickel, the copper one or more.
9. lithium titanate composite material preparation method as claimed in claim 7 is characterized in that, said organic carbon source monomer be in pyrrole monomer or derivatives thereof, aniline monomer or derivatives thereof and the thiophene monomer or derivatives thereof one or more.
10. like each said lithium titanate composite material application in battery or capacitor of claim 1-6.
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