CN105206815A - Carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite and preparation and application thereof - Google Patents

Carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite and preparation and application thereof Download PDF

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CN105206815A
CN105206815A CN201510629316.1A CN201510629316A CN105206815A CN 105206815 A CN105206815 A CN 105206815A CN 201510629316 A CN201510629316 A CN 201510629316A CN 105206815 A CN105206815 A CN 105206815A
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aqueous solution
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tio
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CN105206815B (en
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唐子龙
王诗童
张中太
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Tsinghua University
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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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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Abstract

The invention belongs to the technical field of preparation and application of nano materials and particularly relates to a carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite and preparation and application thereof. The carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite is composed of 19wt%-65wt% of Li4Ti5O12, 11wt%-57wt% of TiO2, 23wt%-49wt% of Sn and 1wt%-24wt% of a carbon coating layer. The carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite gives play to synergistic effects of the carbon coating layer with functions of electronic conductivity improvement and ion permeability improvement, the metal Sn with high specific capacity and a one-dimensional nano Li4Ti5O12-TiO2 substrate with small size change in an electrochemical lithium intercalation process, shows excellent electrochemical performances and has a promising application prospect in fields of lithium ion batteries in fast-charge electronic products, electric vehicles and the like.

Description

The coated Li of a kind of carbon 4ti 5o 12-TiO 2/ Sn nano composite material and Synthesis and applications thereof
Technical field
The invention belongs to nano material preparations and applicatio technical field, be specifically related to the coated Li of a kind of carbon 4ti 5o 12-TiO 2/ Sn nano composite material and Synthesis and applications thereof.
Background technology
Along with the aggravation of oil crisis and problem of environmental pollution, clean energy resource becomes one of most important subject under discussion in the whole world.Lithium ion battery is widely used in daily life with its advantage such as high-energy-density, long circulation life.At present, researcher just constantly makes great efforts to improve the power density of lithium ion battery, cycle life and fail safe, meets the needs that it is applied at extensive energy storage device (particularly in pure electric automobile field).
Compare with graphite cathode, during the negative material of titanium base material (comprising lithium titanate and titanium dioxide) as lithium ion battery, the change of removal lithium embedded process crystal volume is little, cyclical stability is good, fail safe is superior, becomes study hotspot.Wherein, lithium titanate Li 4ti 5o 12have almost no change at lithiumation process unit cell volume, and intercalation potential is high, not easily forms Li dendrite; Anatase TiO 2there is lithium ion embed fast/deviate from, the advantages such as embedding lithium process change in volume little (3-4%).Therefore, one of titanium base material power battery electrode material becoming most potentiality, has huge researching value and commercial application prospect.But the maximum shortcoming of titanium base material is that its electronic conductivity is low, and cause large rate capability little, cycle performance is unsatisfactory.Research finds, can improve its chemical property to a certain extent by nanometer, doping and the method such as coated.
Can be provided from surface to inner continuous print conductive path by the material (such as carbon) high in the coated electrical conductance of material surface, thus improve the electronic conductivity of material, be considered to the most simple and effective electrode material method of modifying.Research shows, mixes nitrogen element and not only can improve electronic conductance, can also strengthen Li in conductive carbon layer +diffusion and the transfer of surface charge, thus significantly improve reversible capacity and the high rate performance of electrode material.Dopamine, a kind of biomolecule containing catechol and amido functional group, auto polymerization can be there is at basic ph, obtain the carbon coating layer of continuous and uniform N doping, the thickness of coating layer can be regulated and controled by the concentration of dopamine and polymerization time, to the design of material and optimization, there is important effect.
In addition, the lower (Li of the theoretical specific capacity of titanium base negative material 4ti 5o 12: 175mAhg -1; TiO 2: 335mAhg -1), the demand of lithium ion battery with high energy density cannot be met, researcher usually adopt and there is height ratio capacity electrode material compound to carry out modification.The electrode material of height ratio capacity comprises alloy series material (Sn base, Si base, Sb base etc.) and metal oxide (Co 3o 4, Fe 3o 4, NiO, Cu 2o, MoO 2, VO 2, SnO 2, WO 2deng).Alloy series negative material is because having high theoretical specific capacity, and fast charging and discharging ability, advantage becomes one of lithium ion battery negative material with application prospect most with solvent compatibility is good etc.Wherein, Sn theoretical specific capacity (992mAhg -1) be almost graphite electrode specific capacity (372mAhg -1) 3 times, receive and pay attention to widely.But, due to Li xlarger than metal Sn 3 times of the specific volume of Sn phase, during charging, metal Sn particle alloying produces the volumetric expansion of 300%, and during electric discharge, removal alloying is again with violent volume contraction, cause breaking or efflorescence of active particle, electrical conductance is caused to reduce, material reversible capacity sharp-decay, and then electrode failure.Research shows, after Sn particle nanometer, not only can shorten the migration distance of lithium ion, can also alleviate Lithium-ion embeding/the deviate from volumetric expansion in process.But because Sn nano particle is very easily reunited, its cyclical stability is still unsatisfactory.At present, about Li 4ti 5o 12with the composite modified report of Sn metal, be only simple physical property mixing, still there is serious agglomeration in Sn nano-powder, reversible capacity and cyclical stability unsatisfactory.
Summary of the invention
For the deficiencies in the prior art, the invention provides the coated Li of a kind of carbon 4ti 5o 12-TiO 2/ Sn nano composite material and Synthesis and applications thereof, concrete scheme is as follows:
The coated Li of a kind of carbon 4ti 5o 12-TiO 2/ Sn nano composite material, the coated Li of described carbon 4ti 5o 12-TiO 2in/Sn, Li 4ti 5o 12content be 19wt% ~ 65wt%, TiO 2content be the content of 11wt% ~ 57wt%, Sn be 23wt% ~ 49wt%; The content of carbon coating layer is 1wt% ~ 24wt%.
Preferably, the coated source that described carbon is coated is dopamine.
The coated Li of described carbon 4ti 5o 12-TiO 2the preparation method of/Sn nano composite material comprises the following steps:
(1) preparation of metatitanic acid nano-powder:
Mixed with alkaline aqueous solution by the compound of titanium, after stirring 3h ~ 5h, carry out hydro-thermal reaction 24h ~ 96h, hydrothermal temperature is 120 DEG C ~ 200 DEG C; After reaction terminates, product is joined in enough acidic aqueous solutions and stirs 0.5h ~ 12h, through centrifugal or suction filtration, collect product, after products therefrom washing, obtain metatitanic acid nano-powder through drying.
The compound of described titanium is one or more in anatase titanium dioxide, rutile titanium dioxide, metatitanic acid, amorphous titania and titanate.
Described alkaline aqueous solution is sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
Described alkaline aqueous solution concentration is 8mol/L ~ 20mol/L, and the compound of described titanium and the usage ratio of alkaline aqueous solution are the compound that every 100mL alkaline aqueous solution uses 3.0g ~ 14.0g titanium.
Described acidic aqueous solution is one or more in aqueous solution of nitric acid, aqueous hydrochloric acid solution, aqueous sulfuric acid, aqueous acetic acid, phosphate aqueous solution and oxalic acid aqueous solution, and concentration is 0.1mol/L ~ 0.8mol/L.
(2) Li 1.81h 0.19ti 2o 5xH 2o/SnO 2the preparation of presoma:
By metatitanic acid nano-powder and soluble lithium salt aqueous solution, make pH be 8 ~ 14, and add a certain amount of solubility Xi Yuan, after stirring 0.5h ~ 4h, carry out hydro-thermal reaction 0.5h ~ 12h, hydrothermal temperature is 120 DEG C ~ 200 DEG C; After reaction terminates, by product, centrifugal or filtering and washing obtains Li 1.81h 0.19ti 2o 5xH 2o/SnO 2persursor material.
The concentration of the described soluble lithium salt aqueous solution is 0.05mol/L ~ 2.0mol/L, the usage ratio of described metatitanic acid nano-powder and the soluble lithium salt aqueous solution is that every 100mL soluble lithium salt aqueous solution uses 0.1g ~ 2.0g metatitanic acid nano-powder, and the usage ratio of described Xi Yuan and metatitanic acid nano-powder is the Xi Yuan that every 1.0g metatitanic acid nano-powder uses 0.1g ~ 10.0g.
Described solubility Xi Yuan comprise in stannic chloride, stannous chloride, STANNOUS SULPHATE CRYSTALLINE, nitric acid tin and tin oxalate one or more.
Described soluble lithium salt is one or more in lithium hydroxide, lithium nitrate, lithium sulfate, lithium carbonate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide and lithium iodide.
When comprising lithium hydroxide in the soluble lithium salt used, do not need to use alkaline solution to regulate pH scope; When soluble lithium salt is one or more in lithium nitrate, lithium sulfate, lithium carbonate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide and lithium iodide, the alkaline solution such as NaOH, potassium hydroxide is used to regulate pH scope to be 8 ~ 14.
(3) the coated Li of carbon 4ti 5o 12-TiO 2the preparation of/Sn nano composite material:
By a certain amount of Li 1.81h 0.19ti 2o 5xH 2o/SnO 2presoma joins in the Tris-buffer aqueous buffer solution (pH=8.5) containing dopamine, carries out reaction 1 ~ 48h, and reaction temperature is 25 DEG C ~ 120 DEG C; Reaction terminate after by product centrifugal or filtering and washing; Subsequently products therefrom is heat-treated, be incubated 0.5h ~ 8h from room temperature to 350 DEG C ~ 700 DEG C, obtain the coated Li of carbon 4ti 5o 12-TiO 2/ Sn nano composite material.
Described Li 1.81h 0.19ti 2o 5xH 2the usage ratio of O/SnO presoma and Tris-buffer aqueous buffer solution is every 100mLTris-buffer aqueous buffer solution 0.1g ~ 2.0gLi 1.81h 0.19ti 2o 5xH 2o/SnO presoma; Described Li 1.81h 0.19ti 2o 5xH 2o/SnO 2the usage ratio of presoma and dopamine is every 1.0gLi 1.81h 0.19ti 2o 5xH 2o/SnO 2presoma uses the dopamine of 0.1g ~ 10.0g.
Described heating rate is 2 DEG C/min ~ 10 DEG C/min.
Described heat treated atmosphere is vacuum, inert gas or reducibility gas.
The coated Li of carbon described above 4ti 5o 12-TiO 2/ Sn nano composite material is preparing the application in battery electrode diaphragm.
The preparation of battery electrode diaphragm:
By coated for carbon Li 4ti 5o 12-TiO 2/ Sn nano composite material and conductive black (SuperP), binding agent Kynoar (PVDF), join in 1-METHYLPYRROLIDONE (NMP) solvent by the mass ratio of 8:1:1, be coated on aluminium foil or Copper Foil after mixing, obtained electrode diaphragm after 100 DEG C of vacuumize.
The assembling test of battery: take metal lithium sheet as negative pole, prepared composite electrode diaphragm is positive pole, and Celgard2400 microporous polypropylene membrane is barrier film, and concentration is the LiPF of 1mol/L 6ethylene carbonate (EC) solution and dimethyl carbonate (DMC) mixed liquor (wherein EC and DMC volume ratio is 1:1) be electrolyte, in the glove box of water oxygen content all lower than the high-purity argon gas atmosphere of 1ppm, assemble 2032 type button cells.Adopt LAND battery test system at the electrochemistry cycle characteristics of 0.01V ~ 3.0V voltage range build-in test button cell.
Principle of the present invention is:
The present invention devises a kind of Li 4ti 5o 12-TiO 2the combination electrode material of monodimension nanometer material and Sn nano particle, has played Li 4ti 5o 12-TiO 2the synergy of matrix little in Electrochemical lithiation process change in volume of metal Sn height ratio capacity, at Li 4ti 5o 12-TiO 2excellent cyclical stability basis significantly adds specific capacity.
The present invention prepares Li at metatitanic acid nano-powder and soluble lithium salt aqueous solution hydro-thermal 1.81h 0.19ti 2o 5xH 2on the Process ba-sis of O, add solubility Xi Yuan wherein, synthesize Li 1.81h 0.19ti 2o 5xH 2o/SnO 2, wherein alkaline aqueous solution is Li 1.81h 0.19ti 2o 5xH 2the reactant of O, further provides the alkaline environment of Xi Yuan hydrolysis.Subsequently, Li 1.81h 0.19ti 2o 5xH 2o Dehydration under inertia or reducing atmosphere generates Li 4ti 5o 12-TiO 2, SnO simultaneously 2in-situ reducing generates Sn.
Beneficial effect of the present invention is:
1) composite material that the present invention prepares has played monodimension nanometer material Li 4ti 5o 12-TiO 2matrix Electrochemical lithiation process change in volume is little, metal Sn height ratio capacity and carbon coating layer improve the synergy such as electronic conductance and ion permeability.In addition, one-dimensional nano structure and nano composite structure also serve shorten lithium ion migration distance, increase and electrolyte contact area, alleviate the effect of stress that Lithium-ion embeding/deviate from process produces and volumetric expansion.Therefore, this composite material shows excellent chemical property, at 1000mAg -1large multiplying power under circulation 600 times, capacity keep be stabilized in 300mAhg -1.
2) the invention solves the on the low side and alloy series metal Sn nano-powder of titanium base system row material specific capacity and acutely cause the problem of capacity sharp-decay due to change in volume in embedding lithium/de-lithium process, the design and optimization of titanium base series material and other alloy series and metal oxide series material compound is provided to larger inspiration and instructs foundation.
3) the present invention is by in-situ reducing SnO 2method metal Sn nano particle is dispersed in Li 4ti 5o 12-TiO 2the surface of nano wire, effectively alleviates the problem of easily reuniting in nano particle preparation and electrochemistry cyclic process.And the relevant Li of existing bibliographical information 4ti 5o 12with the composite material of nanometer Sn, be simple physical property compound, nanometer Sn particle is very easily reunited, and causes capacity rapid decay.
4) the present invention has prepared the coated Li of carbon 4ti 5o 12-TiO 2/ Sn nano composite material, material preparation process gentleness is controlled, has not only simplified synthesis technique, also effectively reduces energy consumption and pollution, meets the requirement of country " 12 " energy-saving and emission-reduction planning.The energy storage fields such as in addition, cheaper starting materials is easy to get, and productive rate is high, easily realizes large-scale industrial production, the lithium ion battery in the sub-product of hybrid vehicle, pure electric automobile and charging quickly have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the TEM figure of resulting materials in the embodiment of the present invention 3;
Fig. 2 is the TEM figure of resulting materials in the embodiment of the present invention 6;
Fig. 3 is the XRD spectra of resulting materials in the embodiment of the present invention 8;
Fig. 4 is the TEM figure of resulting materials in the embodiment of the present invention 8;
Fig. 5 is the HRTEM figure of resulting materials in the embodiment of the present invention 8;
Fig. 6 is the SEM figure of resulting materials in the embodiment of the present invention 8;
Fig. 7 is the specific discharge capacity figure of test battery under different current density of resulting materials in the embodiment of the present invention 8;
Fig. 8 is that the test battery of resulting materials in the embodiment of the present invention 8 is at 1000mAg -1current density under cycle performance and coulombic efficiency figure.
Embodiment
The preparation of metatitanic acid nano-powder
Embodiment 1
By 2.5gP25TiO 2the NaOH solution being 10mol/L with 80mL concentration mixes, and carry out hydro-thermal reaction 96h after stirring 4h, hydrothermal temperature is 120 DEG C.After reaction terminates, product being joined concentration is stir 0.5h in the excessive dust technology of 0.1mol/L, after centrifugal, product is dry at 60 DEG C, obtains the metatitanic acid nano-powder of white puff.
Embodiment 2
By 6.5g rutile TiO 2the KOH solution being 15mol/L with 80mL concentration mixes, and carry out hydro-thermal reaction 30h after stirring 5h, hydrothermal temperature is 150 DEG C.After reaction terminates, product being joined concentration is stir 12h in the excessive watery hydrochloric acid of 0.8mol/L, after suction filtration, product is dry at 60 DEG C, obtains the metatitanic acid nano-powder of white puff.
Embodiment 3
By 9.5g Detitanium-ore-type TiO 2the NaOH solution being 20mol/L with 80mL concentration mixes, and carry out hydro-thermal reaction 72h after stirring 3h, hydrothermal temperature is 180 DEG C.After reaction terminates, product being joined concentration is stir 10h in the excessive watery hydrochloric acid of 0.5mol/L, after suction filtration, product is dry at 60 DEG C, obtains the metatitanic acid nano-powder of white puff.The TEM image of material is shown in Fig. 1.
Li 1.81h 0.19ti 2o 5xH 2o/SnO 2the preparation of presoma
Embodiment 4
By the LiCl aqueous solution that 0.1g metatitanic acid nano-powder and 100mL concentration are 0.1mol/L, using the NaOH solution of 1mol/L to adjust its pH value is 8, adds the SnCl of 0.5g subsequently 45H 2o also stirs 2h, then carries out hydro-thermal reaction 4h, and hydrothermal temperature is 120 DEG C.Reaction terminate after by product centrifugal or filtering and washing, obtain Li 1.81h 0.19ti 2o 5xH 2o/SnO 2presoma.
Embodiment 5
By the LiOH aqueous solution that 0.8g metatitanic acid nano-powder and 100mL concentration are 1mol/L, add the SnCl of 0.3g subsequently 22H 2o also stirs 0.5h, then carries out hydro-thermal reaction 12h, and hydrothermal temperature is 150 DEG C.Reaction terminate after by product centrifugal or filtering and washing, obtain Li 1.81h 0.19ti 2o 5xH 2o/SnO 2presoma.
Embodiment 6
Be the Li of 2mol/L by 2.0g metatitanic acid nano-powder and 100mL concentration 2sO 4aqueous solution, using the KOH solution of 1mol/L to adjust its pH value is 14, adds the SnSO of 5.0g subsequently 4and stir 4h, then carry out hydro-thermal reaction 0.5h, hydrothermal temperature is 180 DEG C.Reaction terminate after by product centrifugal or filtering and washing, obtain Li 1.81h 0.19ti 2o 5xH 2o/SnO 2presoma.The TEM image of material is shown in Fig. 2.
The coated Li of carbon 4ti 5o 12-TiO 2the preparation of/Sn composite material
Embodiment 7
By 1.0gLi 1.81h 0.19ti 2o 5xH 2o/SnO 2presoma joins in the 100mLTris-buffer cushioning liquid containing 0.5g dopamine, carries out reaction 5h, and reaction temperature is 70 DEG C; Reaction terminate after by product centrifugal or filtering and washing; Heat-treated by products therefrom subsequently, heating rate is 10 DEG C/min, and product is incubated 2h under the Ar atmosphere of 650 DEG C, obtains the coated Li of carbon that covering amount is 3wt% 4ti 5o 12-TiO 2/ Sn composite material.
Embodiment 8
By 0.1gLi 1.81h 0.19ti 2o 5xH 2o/SnO 2presoma joins in the 100mLTris-buffer cushioning liquid containing 0.8g dopamine, carries out reaction 48h, and reaction temperature is 30 DEG C; Reaction terminate after by product centrifugal or filtering and washing; Heat-treated by products therefrom subsequently, heating rate is 2 DEG C/min, and product is at the Ar/H of 500 DEG C 2(Ar/H 2: 95%/5%) be incubated 6h under atmosphere, obtain the coated Li of carbon that covering amount is 21wt% 4ti 5o 12-TiO 2/ Sn composite material.The XRD spectra of material, TEM image, HRTEM image and SEM image are shown in Fig. 3, Fig. 4, Fig. 5 and Fig. 6.
Embodiment 9
By 2.0gLi 1.81h 0.19ti 2o 5xH 2o/SnO 2presoma joins in the 100mLTris-buffer cushioning liquid containing 1.5g dopamine, carries out reaction 48h, and reaction temperature is 50 DEG C; Reaction terminate after by product centrifugal or filtering and washing; Heat-treated by products therefrom subsequently, heating rate is 5 DEG C/min, and product is incubated 8h under the argon gas atmosphere of 500 DEG C, obtains the coated Li of carbon that covering amount is 14wt% 4ti 5o 12-TiO 2/ Sn composite material.
The coated Li of embodiment 10 carbon 4ti 5o 12-TiO 2the electrochemical property test of/Sn nano composite material
The coated Li of carbon 4ti 5o 12-TiO 2the preparation of/Sn electrode: by coated for a certain amount of carbon Li 4ti 5o 12-TiO 2/ Sn material powder and conductive black (SuperP), binding agent Kynoar (PVDF), join in 1-METHYLPYRROLIDONE (NMP) solvent of 10mL by the mass ratio of 8:1:1 successively, be coated on aluminium foil after stirring 4h, vacuumize 10h at 100 DEG C, obtained electrode diaphragm.
The assembling of test battery: take metal lithium sheet as negative pole, the coated Li of carbon 4ti 5o 12-TiO 2/ Sn electrode is positive pole, and Celgard2400 microporous polypropylene membrane is barrier film, and concentration is the LiPF of 1mol/L 6ethylene carbonate (EC) solution and dimethyl carbonate (DMC) mixed solution (EC and DMC volume ratio is 1:1) be electrolyte, in the glove box of water oxygen content all lower than the high-purity argon gas atmosphere of 1ppm, assemble 2032 type button cells.
The test of chemical property: adopt LAND battery test system at the electrochemistry cycle characteristics of 0.01V ~ 3.0V voltage range build-in test button cell.Fig. 7 is the coated Li of carbon 4ti 5o 12-TiO 2the test battery of/Sn is respectively at 50mAg -1, 100mAg -1, 200mAg -1, 500mAg -1and 1000mAg -1specific discharge capacity figure under uniform current density, Fig. 8 are the coated Li of carbon 4ti 5o 12-TiO 2the test battery of/Sn is at 1000mAg -1current density under cycle performance and coulombic efficiency figure.Can find out, this composite material has played monodimension nanometer material Li 4ti 5o 12-TiO 2matrix Electrochemical lithiation process change in volume is little, metal Sn height ratio capacity and carbon coating layer improve the synergy such as electronic conductance and ion permeability, has shown excellent chemical property.At 1000mAg -1large multiplying power under circulation 600 times (namely completing discharge cycles at about 20min), capacity keep be stabilized in 300mAhg -1.
Above example should not be construed as restriction of the present invention, every make based on technological thought of the present invention other pro forma amendments, replacement or change and the invention realized all belongs to the scope of the invention.Can be under the premise of not departing from the present invention for those skilled in the art; some improvement can be done to the present invention; therefore all equivalences done according to method, feature and the principle described in patent claim of the present invention change or modify; such as; reaction raw materials, reaction time; heat treatment temperature, time, atmosphere and material amounts ratio etc., these features belong to the scope of patent application protection equally.

Claims (10)

1. the coated Li of carbon 4ti 5o 12-TiO 2/ Sn nano composite material, is characterized in that, the coated Li of described carbon 4ti 5o 12-TiO 2in/Sn nano composite material, Li 4ti 5o 12content be 19wt% ~ 65wt%, TiO 2content be the content of 11wt% ~ 57wt%, Sn be 23wt% ~ 49wt%; The content of carbon coating layer is 1wt% ~ 24wt%.
2. the coated Li of a kind of carbon according to claim 1 4ti 5o 12-TiO 2/ Sn nano composite material, is characterized in that, the coated carbon source of described carbon is dopamine.
3. the coated Li of a kind of carbon described in any one of claim 1-2 4ti 5o 12-TiO 2the preparation method of/Sn nano composite material, is characterized in that, comprises the following steps:
(1) preparation of metatitanic acid nano-powder:
Mixed with alkaline aqueous solution by the compound of titanium, after stirring 3h ~ 5h, carry out hydro-thermal reaction 24h ~ 96h, hydrothermal temperature is 120 DEG C ~ 200 DEG C; After reaction terminates, product is joined in acidic aqueous solution and stirs 0.5h ~ 12h, through centrifugal or suction filtration, collect product, after products therefrom washing, obtain metatitanic acid nano-powder through drying;
(2) Li 1.81h 0.19ti 2o 5xH 2o/SnO 2the preparation of presoma:
By metatitanic acid nano-powder and soluble lithium salt aqueous solution, make pH be 8 ~ 14, and add solubility Xi Yuan, after stirring 0.5h ~ 4h, carry out hydro-thermal reaction 0.5h ~ 12h, temperature is 120 DEG C ~ 200 DEG C; Reaction terminate after by product centrifugal or filtering and washing, obtain Li 1.81h 0.19ti 2o 5xH 2o/SnO 2presoma;
(3) the coated Li of carbon 4ti 5o 12-TiO 2the preparation of/Sn nano composite material:
By Li 1.81h 0.19ti 2o 5xH 2oSnO 2presoma joins in the Tris-buffer aqueous buffer solution containing dopamine, pH=8.5, reaction 1 ~ 48h, and temperature is 25 DEG C ~ 120 DEG C; Reaction terminate after by product centrifugal or filtering and washing; Subsequently products therefrom is heat-treated, be incubated 0.5h ~ 8h from room temperature to 350 DEG C ~ 700 DEG C, obtain the coated Li of carbon 4ti 5o 12-TiO 2/ Sn nano composite material.
4. preparation method according to claim 3, it is characterized in that, in step (1), the compound of described titanium is one or more in anatase titanium dioxide, rutile titanium dioxide, metatitanic acid, amorphous titania and titanate.
5. preparation method according to claim 3, is characterized in that, in step (1), described alkaline aqueous solution is sodium hydrate aqueous solution or potassium hydroxide aqueous solution; Described alkaline aqueous solution concentration is 8mol/L ~ 20mol/L, and the compound of described titanium and the amount ratio of alkaline aqueous solution are (3.0g ~ 14.0g): 100mL;
Described acidic aqueous solution is one or more of aqueous solution of nitric acid, aqueous hydrochloric acid solution, aqueous sulfuric acid, aqueous acetic acid, phosphate aqueous solution and oxalic acid aqueous solution, and concentration is 0.1mol/L ~ 0.8mol/L.
6. preparation method according to claim 3, is characterized in that, in step (2), the pH scope of the described soluble lithium salt aqueous solution is 8 ~ 14, and concentration is 0.05mol/L ~ 2.0mol/L;
The amount ratio of described metatitanic acid nano-powder and the soluble lithium salt aqueous solution is (0.1g ~ 2.0g): 100mL, and the amount ratio of described Xi Yuan and metatitanic acid nano-powder is (0.1g ~ 10.0): 1.0g.
7. preparation method according to claim 3, it is characterized in that, in step (2), described soluble lithium salt is one or more in lithium hydroxide, lithium nitrate, lithium sulfate, lithium carbonate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide and lithium iodide;
Described solubility Xi Yuan comprise in stannic chloride, stannous chloride, STANNOUS SULPHATE CRYSTALLINE, nitric acid tin and tin oxalate one or more.
8. preparation method according to claim 3, is characterized in that, in step (3), and described Li 1.81h 0.19ti 2o 5xH 2o/SnO 2the amount ratio of presoma and Tris-buffer aqueous buffer solution is (0.1g ~ 2.0g): 100mL; Described Li 1.81h 0.19ti 2o 5xH 2o/SnO 2the amount ratio of presoma and dopamine is 1.0g:(0.1g ~ 10.0g);
Described heating rate is 2 DEG C/min ~ 10 DEG C/min; Described heat treated atmosphere is vacuum, inert gas or reducibility gas.
9. the coated Li of a kind of carbon described in any one of claim 1-2 4ti 5o 12-TiO 2/ Sn nano composite material is preparing the application in battery electrode diaphragm.
10. application according to claim 9, is characterized in that, by coated for carbon Li 4ti 5o 12-TiO 2/ Sn nano composite material and conductive black, Kynoar, 8:1:1 joins in 1-METHYLPYRROLIDONE in mass ratio, is coated on aluminium foil or Copper Foil after mixing, obtained electrode diaphragm after 100 DEG C of vacuumize.
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