CN103618076A - Boron doped submicron-sphere TiO2 electrode material as well as preparation method and application thereof in lithium ion battery thereof - Google Patents

Boron doped submicron-sphere TiO2 electrode material as well as preparation method and application thereof in lithium ion battery thereof Download PDF

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CN103618076A
CN103618076A CN201310685139.XA CN201310685139A CN103618076A CN 103618076 A CN103618076 A CN 103618076A CN 201310685139 A CN201310685139 A CN 201310685139A CN 103618076 A CN103618076 A CN 103618076A
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electrode material
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boron
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tio
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CN103618076B (en
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田华军
韩伟强
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Ningbo Institute of Material Technology and Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • 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

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Abstract

The invention relates to a boron doped submicron-sphere TiO2 electrode material as well as a preparation method and application thereof in a lithium ion battery thereof, and particularly discloses a boron doped TiO2 electrode material, wherein the electrode material is the TiO2 submicron-sphere electrode material; the submicron-sphere consists of rutile-type TiO2 nanoparticles, and has the size of 300-1000nm; the particle diameters of the nano particles are 10-60nm. According to the total mole ratio of the electrode material, the mole percentage composition of the boron element is 0.1-10%. The electrode material disclosed by the invention has excellent electrical conductivity and rate performance. Besides, the invention also discloses the preparation method and application of the electrode material.

Description

Boron doping sub-micron ball TiO 2electrode material and method for making thereof and the application in lithium ion battery
Technical field
The present invention relates to battery material field, relate to particularly a kind of boron doped sub-micron ball TiO 2electrode material and preparation method thereof and the application in lithium ion battery.
Background technology
In recent years, spinel lithium titanate and TiO 2deng titanium base negative material, become the focus of lithium ion battery electrode material research.Spinel lithium titanate is during as the negative material of lithium ion, because it has excellent security performance, simple preparation technology, cheap raw material and the characteristic such as pollution-free, more and more causes people's concern.Li 4ti 5o 12with Li/Li +potential between reference electrode is 1.55V, and its relatively high potential is fundamentally avoided the insecurity of carbon electrode.Meanwhile, Li 4ti 5o 12as lithium ion battery negative material, when discharging and recharging, when lithium ion embeds and takes off embedding, on almost not impact of material structure, cell parameter a changes very little, only from 0.836nm, is increased to 0.837nm.Therefore, Li 4ti 5o 12be called as " zero strain " electrode material, and Li 4ti 5o 12skeleton has three-dimensional channel and is conducive to Li +diffusion, even when embedding lithium, almost there is no change in volume, thereby be conducive to obtain long service life cycle.Although Li 4ti 5o 12theoretical capacity only have 175mAh/g, but because the de-embedding ratio of its reversible lithium ion approaches 100%, its actual capacity generally remains on 150～160mAh/g.
TiO 2with Li 4ti 5o 12there is similar feature, nano-TiO 2when high current charge-discharge, its change in volume is also very little, and approximately 3%.Meanwhile, in the de-process of lithium ion embedding, TiO 2steady chemical structure, security performance are better.Common well behaved spinelle Li 4ti 5o 12can pass through TiO 2with LiCO 3, the lithium source such as LiOH obtains by preparing craft.And, TiO 2preparation technology is simple, cheap, thereby can become, energy density is required relatively low, and cost and cycle life is required to the desirable negative material of high energy-storage battery.Simultaneously due to Li +in traditional lithium ion battery negative utmost point material, diffusion coefficient is smaller, causes the slower charge-discharge velocity of battery, has affected lithium ion battery in application widely such as power vehicles.And the particle size of regulation and control electrode material, particularly because granule electrode material can effectively shorten Li +the evolving path, nano particle can quick adsorption and is stored a large amount of lithium ions and can not cause the degeneration rapidly of electrode material performance.In addition, nano particle can improve the conduction of the specific area of electrode, the evolving path that shortens lithium ion and quickening electronics.Just because of the impact of above nanometer size effect, make to study nanoscale TiO 2material is an important directions of negative material research now.
But nano particle has higher surface free energy and surface reaction activity, may cause electrolyte in the decomposition reaction of electrode surface.And the aperture of the lithium ion battery separator used of general business is in micron dimension, some ultra-fine nano-grain is easily deposited on electrode through barrier film in charge and discharge process from surface comes off, and can cause battery capacity to decline.In sum, the titanium dioxide cathode material of micro-nano hierarchy becomes one of effective ways that overcome the above problems.
On the other hand, titanium dioxide is owing to being wide bandgap semiconductor, and conductivity is bad, and this has had a strong impact on its application in lithium ion battery field.
Therefore be necessary on the basis of micro-nano hierarchy that does not change titanium dioxide uniqueness, by titanium dioxide is carried out to doping vario-property, improve the electric conductivity of titanium dioxide, particularly improve circulation and the high rate performance of the titanium dioxide cathode material lithium ion battery based on micro-nano hierarchy.
Summary of the invention
The object of the present invention is to provide a kind of novel TiO 2electrode material and its preparation method and application.By to TiO 2carry out boron doping, thereby obtain having with respect to doped Ti O not 2better conductivity and excellent doubly forthright electrode material.
In first aspect present invention, provide a kind of boron doped TiO 2electrode material, described electrode material is TiO 2sub-micron ball electrode material, described sub-micron ball is by rutile TiO 2nano particle forms, wherein,
Described sub-micron ball is of a size of 300～1000nm, is preferably 350～750nm;
The particle diameter of described nano particle is 10～60nm, is preferably 15～40nm;
By electrode material total mole number, the molar content of boron element is 0.1%～10%, is preferably 0.5%～6.0%.
In second aspect present invention, the preparation method of electrode material described in a kind of first aspect present invention is provided, said method comprising the steps of:
(a) provide respectively solution A and solution B, wherein, the alcoholic solution that solution A is titanium compound, the aqueous solution that solution B is boron compound;
(b) after the solution A in step (a) and solution B are reacted, separation is precipitated thing;
(c) gained sediment washed successively, dries, calcined and grinds, obtaining described electrode material.
In another preference, in step (b), the solution A in step (a) and solution B are mixed and stirred and react.
In another preference, in step (a), the mass ratio of titanium compound and boron compound is 15～100:1～5, is preferably 15～30:1～5.
In another preference, described alcoholic solution is selected from: ethanol, ethylene glycol, propyl alcohol, propylene glycol, glycerol, butanols, butanediol or its combination.
In another preference, described titanium compound is selected from: titanium tetrachloride, titanium trichloride, titanium sulfate, tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate or its combination.
In another preference, described boron compound is selected from: boric acid, anhydrous boric acid, triethyl borate or its combination.
In another preference, in step (b), described reaction is carried out at 50～80 ℃, and 8～24h is carried out in described reaction.
In another preference, in step (c), described calcining is carried out at 500～850 ℃, and described calcining is carried out 1～24 hour.
In another preference, in step (c), described calcining heat slowly raises; Typically, per minute with 2-20 ℃, 3-15 ℃ preferably, the speed of 4～10 ℃ heats up best.
In another preference, in step (c), described calcining is carried out in being selected from the atmosphere of lower group: argon gas, hydrogen and argon gas, nitrogen, hydrogen and nitrogen, air.
In third aspect present invention, the purposes of electrode material described in a kind of first aspect present invention is provided, described material is for the preparation of energy storage electrode material.
In another preference, described energy storage electrode material comprises lithium rechargeable battery, nickel-cadmium cell.
In fourth aspect present invention, a kind of lithium rechargeable battery is provided, described lithium rechargeable battery comprises boron doped TiO claimed in claim 1 2electrode material.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, at this, tire out and state no longer one by one.
Accompanying drawing explanation
Fig. 1 is the prepared boron doped Ti of embodiment 1 O 2the XRD figure of sub-micron ball electrode material.
Fig. 2 is the prepared boron doped Ti of embodiment 1 O 2the SEM figure of sub-micron ball electrode material.
Fig. 3 is the prepared boron doped Ti of embodiment 1 O 2the TEM figure of sub-micron ball electrode material.
Fig. 4 is the prepared boron doped Ti of embodiment 1 O 2sub-micron ball electrode material is the battery performance curve chart of the circulation under 0.5C, 1C, 2C multiplying power 500 times respectively.
Fig. 5 is the prepared boron doped Ti of embodiment 1 O 2sub-micron ball electrode material is the cycle performance curve chart under 0.5C, 1C, 2C, 5C, 10C multiplying power respectively.
Fig. 6 is the TiO of the prepared not doped with boron of comparative example 1 2the cycle performance curve chart of sub-micron ball electrode material under 1C multiplying power.
Embodiment
Inventor finds through research extensively and profoundly, by TiO 2in electrode material, doped with boron element can significantly improve TiO 2the electric conductivity of electrode material and high rate performance, and prepared by boron doped rutile TiO by hydro thermal method 2the sub-micron ball electrode material that nano particle forms, this electrode material is suitable for lithium ion battery and other energy storage electrode materials, and can on the basis of micro-nano hierarchy that does not change titanium dioxide uniqueness, effectively improve circulation and the high rate performance of lithium ion battery.
Boron doped TiO 2electrode material and preparation method thereof
Boron doped Ti O of the present invention 2electrode material is the TiO with sub-micron ball pattern 2electrode material, this sub-micron ball is by rutile TiO 2nano particle forms, and wherein, sub-micron ball is of a size of 300～1000nm, is preferably 350～750nm, and the particle diameter of nano particle is 10～60nm, is preferably 15～40nm.
By electrode material total mole number, the molar content of boron element is 0.1%～10%, is preferably 0.5%～6.0%
Inventor finds through repeatedly a large amount of test, and when boron doping amount is lower than 0.1% time, less on the physical property of electrode material (as conductivity) impact, performance improves not obvious, and boron doping amount is higher than 10% time, is unfavorable for the formation of sub-micron ball.
Boron doped Ti O of the present invention 2electrode material is prepared by hydro thermal method, mainly comprises the following steps:
(a) provide respectively solution A and solution B, wherein, the alcoholic solution that solution A is titanium compound, the aqueous solution that solution B is boron compound;
(b) after solution A and solution B are mixed, at 50～80 ℃, react 8h～24h, separation is precipitated thing;
(c) gained sediment washed successively, dries, calcined and grinds, obtaining electrode material of the present invention.
Wherein, titanium compound comprises inorganic titanium compound and organic titanic compound, and inorganic titanium compound comprises titanium tetrachloride, titanium trichloride, titanium sulfate etc.; Organic titanic compound comprises tetraisopropyl titanate, tetraethyl titanate and tetra-n-butyl titanate etc.The purity of the titanium compound that the present invention is used can or be analyzed pure etc. for technical grade purity, chemical pure.
Boron compound of the present invention can be selected one or more in boric acid, anhydrous boric acid and triethyl borate.
Inventor finds through a large amount of tests and data screening repeatedly, by controlling the content of boron compound, can effectively improve conductivity and the high rate performance of prepared positive electrode.In one embodiment of the present invention, the mass ratio of titanium compound and boron compound is 15～100:1～5, is preferably 15～30:1～5.
Solution A of the present invention can, by titanium compound is slowly added drop-wise in alcohol, prepare after magnetic force stirs.Described alcoholic solvent preferred alcohol, ethylene glycol, propyl alcohol, propylene glycol, glycerol, butanols, butanediol or its combination.The amount of solvent is not particularly limited, as long as fully dissolve titanium compound.
In step (b), when solution A and solution B are carried out to hybrid reaction, preferably for solution A is slowly added dropwise in solution B, or solution B is slowly added dropwise in solution A and is reacted; Preferably, described reaction temperature is controlled at 50～80 ℃ and/or described reaction time and is controlled at 8～24h; Or described reaction is carried out under constantly stirring.
Reaction finishes rear cooling static, until there is sediment to separate out.To after sediment separation, wash.Separated step can select the separation method of this area routine to carry out separation, as normal pressure or filtration under diminished pressure, centrifugation etc.
In the present invention's one class preferred embodiment, by the sediment to separated, with deionized water and absolute ethyl alcohol, clean repeatedly respectively, to remove, in course of reaction, be adsorbed in sediment surface or inner impurity.
Sediment after washing is dried to rear calcining, dry and preferably under 50～80 ℃ of conditions, carry out.The preferred calcining heat of the present invention is 500～850 ℃, and calcination time is 1～24 hour.Preferably, calcining heat is slowly to raise, and as the speed with 4～6 ℃/min is warming up to 500～850 ℃, is preferably 500～700 ℃.
Calcination process of the present invention preferably carries out in following atmosphere: argon gas, hydrogen and argon gas, nitrogen, hydrogen and nitrogen, air.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can combination in any.All features that this case specification discloses can with any composition forms use, each feature disclosing in specification, can be replaced by any alternative characteristics of identical, impartial or similar object that provide.Therefore except there being special instruction, the feature disclosing is only the general example of equalization or similar features.
Compared with prior art, the present invention has following beneficial effect:
(1) boron doped TiO of the present invention 2electrode material has unique sub-micron ball pattern, and after the boron element by the certain content of doping, electric conductivity and the high rate performance of electrode material are all improved significantly.
(2) preparation method's Raw wide material sources of electrode material of the present invention, technological process is simple, and without complicated equipment, cost is low, is applicable to large-scale production.
(3) electrode material of the present invention can be applicable to the preparation of electrode material and other energy storage electrode materials of lithium ion battery.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise percentage and umber calculate by weight.
Unless otherwise defined, the familiar meaning of all specialties of using in literary composition and scientific words and one skilled in the art is identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
In following examples, the test condition of charge-discharge property test and cycle performance test is:
Specific capacity is pressed 335mAh/g and is calculated, and rate of charge is 1C (by theoretical calculation of capacity, discharging and recharging each needs 1 hour), and charging/discharging voltage scope is 1.0V～3.0V.
The instrument using in embodiment is respectively:
XRD: adopt German Brooker company/Bruker AXS; Model: D8Advance;
SEM: adopt HIT; Model: S～4800;
TEM: adopt U.S. FEI Co.; Model: Tecnai F20.
Embodiment 1
By chemical pure titanium tetrachloride 4ml, slowly be added drop-wise in 12ml absolute ethyl alcohol, magnetic agitation is even, pours in the spherical reaction utensil being equipped with containing the 100ml deionized water solution of 0.5g boric acid, in stirred reactor at 60 ℃, react 12 hours, filter and be precipitated thing.This sediment is obtained to boron doping sub-micron ball structure Ti O for 2～3 times with distilled water washing 2presoma, the lower calcining of this presoma 500 ℃ (speed with 5 ℃/min is warming up to 500 ℃) under air atmosphere is obtained to lithium ion battery negative material boron doping sub-micron ball TiO for 5 hours 2.
Embodiment 2
By chemical pure titanium trichloride 5ml, be slowly added drop-wise in 20ml absolute ethyl alcohol, magnetic agitation is even, pours in the spherical reaction utensil being equipped with containing the 100ml deionized water solution of 1g boric acid, reacts 8 hours in the stirred reactor at 70 ℃, filters and is precipitated thing.This sediment is obtained to boron doping sub-micron ball structure Ti O for 2～3 times with distilled water washing 2presoma; This presoma is obtained to lithium ion battery negative material boron doping sub-micron ball TiO for 8 hours in 600 ℃ (speed with 10 ℃/min is warming up to 600 ℃) lower calcining 2.
Embodiment 3
By chemical pure tetraethyl titanate 10ml, slowly be added drop-wise in 45ml absolute ethyl alcohol, magnetic agitation is even, pours in the spherical reaction utensil being equipped with containing the 120ml deionized water solution of 2g boric acid, in stirred reactor at 80 ℃, react 4 hours, filter and be precipitated thing.This sediment is obtained to boron doping sub-micron ball structure Ti O for 2～3 times with distilled water washing 2presoma; This presoma is obtained to lithium ion battery negative material boron doping sub-micron ball TiO for 10 hours in 500 ℃ (speed with 5 ℃/min is warming up to 500 ℃) lower calcining 2.
Embodiment 4
By chemical pure tetraisopropyl titanate 10ml, slowly be added drop-wise in 40ml absolute ethyl alcohol, magnetic agitation is even, pours in the spherical reaction utensil being equipped with containing the 100ml deionized water solution of 1.5g boric acid, in stirred reactor at 60 ℃, react 8 hours, filter and be precipitated thing.This sediment is obtained to boron doping sub-micron ball structure Ti O for 2～3 times with distilled water washing 2presoma; This presoma is obtained to lithium ion battery negative material boron doping sub-micron ball TiO for 24 hours in 700 ℃ (speed with 6 ℃/min is warming up to 700 ℃) lower calcining 2.
Embodiment 5
By chemical pure titanium tetra-n-butyl titanate 5ml, slowly be added drop-wise in 30ml absolute ethyl alcohol, magnetic agitation is even, pours in the spherical reaction utensil being equipped with containing the 100ml deionized water solution of 0.5g boric acid, in stirred reactor at 80 ℃, react 12 hours, filter and be precipitated thing.This sediment is obtained to boron doping sub-micron ball structure Ti O for 2～3 times with distilled water washing 2presoma; This presoma is obtained to lithium ion battery negative material boron doping sub-micron ball TiO for 12 hours in 510 ℃ (speed with 5 ℃/min is warming up to 510 ℃) lower calcining 2.
Embodiment 6
Take respectively the titanium tetrachloride of 5ml and the tetraisopropyl titanate of 5ml, be slowly added drop-wise in 30～60ml absolute ethyl alcohol, magnetic agitation is even, pour in the spherical reaction utensil being equipped with containing the 100ml deionized water solution of 1.7g boric acid, in stirred reactor at 70 ℃, react, react 12 hours, cooling.Filtration is precipitated thing.This sediment is obtained to boron doping sub-micron ball structure Ti O for 2～3 times with distilled water washing 2presoma; And this Primary product being placed in to the Muffle furnace heating and calcining of atmosphere, temperature, 750 ℃ (speed with 6 ℃/min is warming up to 750 ℃), obtains end product boron doped Ti O 2sub-micron ball.
Embodiment 7: boron doped Ti O 2the sign of sub-micron ball
Boron doped Ti O to embodiment 1 preparation 2sub-micron ball has carried out XRD structural analysis, and test result as shown in Figure 1.As can be seen from Figure 1, prepared boron doped Ti O 2sub-micron ball is Rutile Type.The TiO of preparation 2sub-micron ball contains obvious Rutile Type characteristic peak: main peak value is at 27.45 ° (110 faces), 36.09 ° (101 face), 39.19 ° (200 face), 41.23 ° (111 face), 44.05 ° (210 face), 54.32 ° (211 face), 56.64 ° (220 face), 62.74 ° (002 face), 64.04 ° (310 face), 65.48 ° (221 face), 69.01 ° (301 face), 69.79 ° (112 face), 72.41 ° (311 face), 74.41 ° (320 face), 76.51 ° (202 face), 79.82 ° (212 face).And there is no obvious Detitanium-ore-type TiO in material phase analysis spectrum 2characteristic peak, show preparation boron doped Ti O 2sub-micron ball is purer Rutile Type structure.
As can be seen from Figure 2, the boron doped Ti O of preparation 2the size of sub-micron ball is between 350nm～750nm.Fig. 3 has shown boron doped Ti O 2the microscopic appearance of sub-micron ball forms.As can be seen from Figure 3, boron doped Ti O 2sub-micron ball is comprised of the nano particle of 20nm～40nm, and the reunion between particle and particle is formed with the sub-micron ball structure of regular morphology.
Embodiment 8: the cycle performance test of boron doped Ti O2 sub-micron ball
With the prepared boron doping sub-micron ball TiO of example 1 2material, as electrode active material, is tested its cycle performance in 2032 button cells.Electrode material consists of (mass percent): 80% boron doping sub-micron ball TiO 2material, 10% conductive carbon black, 10%PVdF: to electrode, be lithium metal.Electrolyte is 1mol/LiPF 6eC/DEC (volume ratio is 1:1) solution, barrier film is Cellgard2300 barrier film.Charging/discharging voltage scope is 1.0～3.0V, and charge-discharge velocity is 1C.
Fig. 4 is boron doping sub-micron ball TiO 2the cycle performance curve of electrode.As can be seen from Figure 4 this electrode first discharge capacity be 160mAh/g, 150 1C charge and discharge cycles are still 156mAh/g later, after 500 1C charge and discharge cycles, battery is more stable rises to 185mAh/g, and this result shows that electrode material of the present invention has excellent cyclical stability.
Embodiment 9: boron doped Ti O 2the high rate performance test of sub-micron ball
With the prepared boron doping sub-micron ball TiO of example 1 2material, as electrode active material, is tested its cycle performance in 2032 button cells.Electrode material forms (mass percent): 80% boron doping sub-micron ball TiO 2material, 10% conductive carbon black, 10%PVdF: to electrode, be lithium metal.Electrolyte is 1mol/LiPF 6eC/DMC (volume ratio is 1:1) solution, barrier film is Cellgard2300 barrier film.Charging/discharging voltage scope is 1.0～3.0V, and charge-discharge velocity is 0.5C, 1C, 2C, 5C, 10C.
Fig. 5 is boron doping sub-micron ball TiO 2electrode obtains cycle performance curve.As can be seen from Figure 5 this electrode first discharge capacity be 166mAh/g, it is still 166mAh/g that 120 later 1C of different multiplying charge and discharge cycles discharge and recharge under condition, and stable performance under different multiplying condition, shows that electrode material of the present invention has good cyclical stability.
To boron doped Ti O prepared in embodiment 1～6 2material carries out materialization sign, can both better keep the pattern of good sub-micron ball structure and comparatively similar phase structure, therefore only provides the result of example 1.The battery performance result of embodiment 1～6 is similar simultaneously, all shows good circulation ratio performance, therefore only provides cycle performance and the high rate performance of example 1 prepared electrode material.
Comparative example 1
By chemical pure titanium tetrachloride 4ml, be slowly added drop-wise in 12ml absolute ethyl alcohol, magnetic agitation is even, regulates pH value consistent with this solution pH value in example 1, reacts 12 hours in the stirred reactor at 60 ℃, filters and is precipitated thing.This sediment is washed to the sub-micron ball structure Ti O that obtains not adulterating for 2～3 times with distilled water 2presoma, this presoma is calcined at 500 ℃ and within 5 hours, is obtained lithium ion battery negative material sub-micron ball TiO under air atmosphere 2.
Fig. 6 is the boron doping sub-micron ball TiO of comparative example 1 2the charge-discharge performance curve of electrode.This electrode is under 1C first charge-discharge condition as can be seen from Figure 6, and specific discharge capacity is 143mAh/g, and 150 the later battery special capacity fades that also circulate under 1C discharges and recharges condition to 105mAh/g simultaneously.This result shows with respect to doped Ti O not 2electrode, based on boron doped sub-micron ball structure Ti O 2can effectively improve the stability of lithium ion battery.
In contrast to this, the electrode material of embodiments of the invention 1, even after 500 1C charge and discharge cycles, battery is still highly stable, and battery specific capacity is about 185mAh/g (seeing Fig. 4).This result shows that electrode material of the present invention has very excellent cyclical stability.
All documents of mentioning in the present invention are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.

Claims (11)

1. a boron doped TiO 2electrode material, is characterized in that, described electrode material is TiO 2sub-micron ball electrode material, described sub-micron ball is by rutile TiO 2nano particle forms, wherein,
Described sub-micron ball is of a size of 300～1000nm, is preferably 350～750nm;
The particle diameter of described nano particle is 10～60nm, is preferably 15～40nm;
By electrode material total mole number, the molar content of boron element is 0.1%～10%, is preferably 0.5%～6.0%.
2. a preparation method for electrode material as claimed in claim 1, is characterized in that, said method comprising the steps of:
(a) provide respectively solution A and solution B, wherein, the alcoholic solution that solution A is titanium compound, the aqueous solution that solution B is boron compound;
(b) after the solution A in step (a) and solution B are reacted, separation is precipitated thing;
(c) gained sediment washed successively, dries, calcined and grinds, obtaining described electrode material.
3. method as claimed in claim 2, is characterized in that, in step (a), the mass ratio of titanium compound and boron compound is 15～100:1～5, is preferably 15～30:1～5.
4. method as claimed in claim 2, is characterized in that, described alcoholic solution is selected from: ethanol, ethylene glycol, propyl alcohol, propylene glycol, glycerol, butanols, butanediol or its combination.
5. method as claimed in claim 2, is characterized in that, described titanium compound is selected from: titanium tetrachloride, titanium trichloride, titanium sulfate, tetraethyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate or its combination.
6. method as claimed in claim 2, is characterized in that, described boron compound is selected from: boric acid, anhydrous boric acid, triethyl borate or its combination.
7. method as claimed in claim 2, is characterized in that, in step (b), described reaction is carried out at 50～80 ℃, and 8～24h is carried out in described reaction.
8. method as claimed in claim 2, is characterized in that, in step (c), described calcining is carried out at 500～850 ℃, and described calcining is carried out 1～24 hour.
9. method as claimed in claim 2, is characterized in that, in step (c), described calcining is carried out in being selected from the atmosphere of lower group: argon gas, hydrogen and argon gas, nitrogen, hydrogen and nitrogen, air.
10. a purposes for electrode material as claimed in claim 1, is characterized in that, described material is for the preparation of energy storage electrode material.
11. 1 kinds of lithium rechargeable batteries, is characterized in that, described lithium rechargeable battery comprises boron doped TiO claimed in claim 1 2electrode material.
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CN104128172A (en) * 2014-07-29 2014-11-05 南昌航空大学 Method for regulating and controlling morphology of nano TiO2-CeO2 into ball shape, dumbbell shape or sheet shape
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