CN105206815B - A kind of carbon coating Li4Ti5O12‑TiO2/ Sn nano composite materials and its preparation and application - Google Patents

A kind of carbon coating Li4Ti5O12‑TiO2/ Sn nano composite materials and its preparation and application Download PDF

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CN105206815B
CN105206815B CN201510629316.1A CN201510629316A CN105206815B CN 105206815 B CN105206815 B CN 105206815B CN 201510629316 A CN201510629316 A CN 201510629316A CN 105206815 B CN105206815 B CN 105206815B
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lithium
carbon coating
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aqueous solution
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CN105206815A (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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • 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
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • H—ELECTRICITY
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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Abstract

The invention belongs to nano material preparation and applied technical field, and in particular to a kind of carbon coating Li4Ti5O12‑TiO2/ Sn nano composite materials and its preparation and application.Wherein, Li4Ti5O12Content be 19wt%~65wt%, TiO2Content be 11wt%~57wt%, Sn content is 23wt%~49wt%；The content of carbon coating layer is 1wt%~24wt%.The composite that the present invention is prepared has played monodimension nanometer material Li4Ti5O12‑TiO2Matrix Electrochemical lithiation process Volume Changes are small, metal Sn height ratio capacities and carbon coating layer improve the synergy such as electronic conductance and ion permeability, excellent chemical property is shown, the field such as lithium ion battery in electric automobile and fast charge electronic product has broad application prospects.

Description

A kind of carbon coating Li4Ti5O12-TiO2/ Sn nano composite materials and its preparation and application
Technical field
The invention belongs to nano material preparation and applied technical field, and in particular to a kind of carbon coating Li4Ti5O12-TiO2/ Sn nano composite materials and its preparation and application.
Background technology
With the aggravation of oil crisis and problem of environmental pollution, clean energy resource become the most important subject under discussion in the whole world it One.Lithium ion battery is widely used in daily life with the advantages that its high-energy-density, long circulation life.Mesh Before, researcher is just continually striving to improve power density, cycle life and the security of lithium ion battery, meets it extensive The needs of energy storage device (particularly in pure electric automobile field) application.
Compared with graphite cathode, negative material of the titanium base material (including lithium titanate and titanium dioxide) as lithium ion battery When, the change of removal lithium embedded process crystal volume is small, cyclical stability is good, security is superior, becomes study hotspot.Wherein, titanium Sour lithium Li4Ti5O12Had almost no change in lithiumation process unit cell volume, and intercalation potential is high, is not easy to form Li dendrite；Rutile titania Ore deposit TiO2With the quick intercalation/deintercalation of lithium ion, the advantage such as process of intercalation Volume Changes small (3-4%).Therefore, titanium base material into For one of most potential power battery electrode material, there is huge researching value and commercial application prospect.However, titanium-based The shortcomings that material maximum is that its electronic conductivity is low, causes that big rate capability is small, and cycle performance is unsatisfactory.Research is found, is led to The methods of crossing nanosizing, doping and cladding can improve its chemical property to a certain extent.
Continuously led from surface to inside by that can be provided in the high material (such as carbon) of material surface cladding electrical conductance Electric pathway, so as to improve the electronic conductivity of material, it is considered to be most simple and effective electrode material method of modifying.Study table Bright, incorporation nitrogen can not only improve electronic conductance in conductive carbon layer, can also strengthen Li+Diffusion and surface charge Transfer, so as to significantly improve the reversible capacity of electrode material and high rate performance.Dopamine, one kind contain catechol and amino official The biomolecule that can be rolled into a ball, auto polymerization can occur at basic ph, obtain the carbon coating layer of continuous and uniform N doping, pass through The concentration and polymerization time of dopamine can regulate and control the thickness of clad, and the design and optimization to material have the function that important.
In addition, relatively low (the Li of the theoretical specific capacity of titanium-based negative material4Ti5O12：175mAh g-1；TiO2：335mAh g-1), Can not meet the needs of lithium ion battery with high energy density, researcher's generally use and the electrode material with height ratio capacity are answered Close to be modified.The electrode material of height ratio capacity includes alloy series material (Sn bases, Si bases, Sb bases etc.) and metal oxide (Co3O4、Fe3O4、NiO、Cu2O、MoO2、VO2、SnO2、WO2Deng).Alloy series negative material because having high theoretical specific capacity, Fast charging and discharging ability, with solvent compatibility the advantages that good as most application prospect lithium ion battery negative material it One.Wherein, Sn theoretical specific capacities (992mAh g-1) it is almost graphite electrode specific capacity (372mAh g-1) 3 times, receive wide General attention.But due to LixThe specific volume of Sn phases is bigger than metal Sn 3 times, and metal Sn particles alloying produces during charging 300% volumetric expansion, removal alloying causes the rupture or efflorescence of active particle again with violent volume contraction during electric discharge, Electrical conductance is caused to reduce, material reversible capacity sharp-decay, and then electrode failure.Research shows, after Sn particle nanosizings, not only The migration distance of lithium ion can be shortened, the volumetric expansion during Lithium-ion embeding/abjection can also be alleviated.But due to Sn Nano particle is easily reunited, and its cyclical stability is still unsatisfactory.At present, on Li4Ti5O12It is composite modified with Sn metals Report, be only simple physical mixing, Sn nano-powders still have serious agglomeration, and reversible capacity and circulation are steady It is qualitative unsatisfactory.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of carbon coating Li4Ti5O12-TiO2/ Sn nano composite materials And its prepare and apply, concrete scheme is as follows：
A kind of carbon coating Li4Ti5O12-TiO2/ Sn nano composite materials, the carbon coating Li4Ti5O12-TiO2In/Sn, Li4Ti5O12Content be 19wt%~65wt%, TiO2Content be 11wt%~57wt%, Sn content for 23wt%~ 49wt%；The content of carbon coating layer is 1wt%~24wt%.
Preferably, the cladding source of the carbon coating is dopamine.
The carbon coating Li4Ti5O12-TiO2The preparation method of/Sn nano composite materials comprises the following steps：
(1) preparation of metatitanic acid nano-powder：
The compound of titanium is mixed with alkaline aqueous solution, after stirring 3h~5h, carries out hydro-thermal reaction 24h~96h, hydro-thermal is anti- It is 120 DEG C~200 DEG C to answer temperature；After reaction terminates, product is added to stirring 0.5h~12h in enough acidic aqueous solutions, Through centrifuging or filtering, product is collected, through being dried to obtain metatitanic acid nano-powder after products therefrom washing.
The compound of the titanium is anatase titanium dioxide, rutile titanium dioxide, metatitanic acid, amorphous titanium dioxide One or more in titanium and titanate.
The alkaline aqueous solution is sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
The alkaline aqueous solution concentration is 8mol/L~20mol/L, the compound of the titanium and the dosage of alkaline aqueous solution Ratio is that the compound of 3.0g~14.0g titaniums is used per 100mL alkaline aqueous solutions.
The acidic aqueous solution is that aqueous solution of nitric acid, aqueous hydrochloric acid solution, aqueous sulfuric acid, aqueous acetic acid, phosphoric acid are water-soluble One or more in liquid and oxalic acid aqueous solution, concentration are 0.1mol/L~0.8mol/L.
(2)Li1.81H0.19Ti2O5·xH2O/SnO2The preparation of presoma：
Metatitanic acid nano-powder is mixed with the soluble lithium salt aqueous solution, it is 8~14 to make pH, and adds a certain amount of solubility Tin source, after stirring 0.5h~4h, hydro-thermal reaction 0.5h~12h is carried out, hydrothermal temperature is 120 DEG C~200 DEG C；Reaction terminates Product centrifugation or filtering and washing are obtained into Li afterwards1.81H0.19Ti2O5·xH2O/SnO2Persursor material.
The concentration of the soluble lithium salt aqueous solution is 0.05mol/L~2.0mol/L, the metatitanic acid nano-powder with can The usage ratio of dissolubility Aqueous Lithium Salts is to use 0.1g~2.0g metatitanic acid nano-powders per the 100mL soluble lithium salts aqueous solution, The tin source and the usage ratio of metatitanic acid nano-powder are that 0.1g~10.0g tin source is used per 1.0g metatitanic acids nano-powder.
The soluble tin source includes stannic chloride, stannous chloride, STANNOUS SULPHATE CRYSTALLINE, nitric acid tin and one kind or one kind in tin oxalate More than.
The soluble lithium salt is lithium hydroxide, lithium nitrate, lithium sulfate, lithium carbonate, lithium phosphate, lithium chlorate, lithium fluoride, chlorine Change the one or more in lithium, lithium bromide and lithium iodide.
When including lithium hydroxide in the soluble lithium salt used, it is not necessary to adjust pH scopes using alkaline solution；When can Dissolubility lithium salts is in lithium nitrate, lithium sulfate, lithium carbonate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide and lithium iodide When one or more kinds of, it is 8~14 to adjust pH scopes using alkaline solutions such as sodium hydroxide, potassium hydroxide.
(3) carbon coating Li4Ti5O12-TiO2The preparation of/Sn nano composite materials：
By a certain amount of Li1.81H0.19Ti2O5·xH2O/SnO2Presoma is added to the Tris-buffer containing dopamine In aqueous buffer solution (pH=8.5), 1~48h of reaction is carried out, reaction temperature is 25 DEG C~120 DEG C；Reaction terminate after by product from The heart or filtering and washing；Then products therefrom is heat-treated, to 350 DEG C~700 DEG C and 0.5h~8h is incubated from room temperature, Obtain carbon coating Li4Ti5O12-TiO2/ Sn nano composite materials.
The Li1.81H0.19Ti2O5·xH2The usage ratio of O/SnO presomas and Tris-buffer aqueous buffer solutions is every 100mL Tris-buffer aqueous buffer solutions 0.1g~2.0g Li1.81H0.19Ti2O5·xH2O/SnO presomas；It is described Li1.81H0.19Ti2O5·xH2O/SnO2The usage ratio of presoma and dopamine is per 1.0g Li1.81H0.19Ti2O5·xH2O/ SnO2Presoma uses 0.1g~10.0g dopamine.
The heating rate is 2 DEG C/min~10 DEG C/min.
The atmosphere of the heat treatment is vacuum, inert gas or reducibility gas.
Carbon coating Li as described above4Ti5O12-TiO2/ Sn nano composite materials answering in terms of battery electrode diaphragm is prepared With.
The preparation of battery electrode diaphragm：
By carbon coating Li4Ti5O12-TiO2/ Sn nano composite materials and conductive black (Super P), binding agent polyvinylidene fluoride Alkene (PVDF), by 8:1:1 mass ratio is added in 1-METHYLPYRROLIDONE (NMP) solvent, and aluminium foil is coated on after well mixed Or on copper foil, electrode diaphragm is made after 100 DEG C of vacuum drying.
The assembling test of battery：Using metal lithium sheet as negative pole, prepared composite electrode diaphragm is positive pole, The microporous polypropylene membranes of Celgard 2400 are barrier film, and concentration is 1mol/L LiPF6Ethylene carbonate (EC) solution and diformazan (wherein EC is 1 with DMC volume ratios to base carbonic ester (DMC) mixed liquor:1) it is electrolyte, 1ppm height is below in water oxygen content 2032 type button cells are assembled in the glove box of pure argon atmosphere.Using LAND battery test systems in 0.01V~3.0V voltages In the range of test button cell electrochemistry cycle characteristics.
The present invention principle be：
The present invention devises a kind of Li4Ti5O12-TiO2The combination electrode material of monodimension nanometer material and Sn nano particles, hair Li is waved4Ti5O12-TiO2Matrix Electrochemical lithiation process Volume Changes are small and the synergy of metal Sn height ratio capacities, Li4Ti5O12-TiO2Specific capacity is added significantly on the basis of excellent cyclical stability.
The present invention prepares Li in metatitanic acid nano-powder and soluble lithium salt aqueous solution hydro-thermal1.81H0.19Ti2O5·xH2O work On the basis of skill, soluble tin source is added thereto, has synthesized Li1.81H0.19Ti2O5·xH2O/SnO2, wherein alkaline aqueous solution It is both Li1.81H0.19Ti2O5·xH2O reactant, the alkaline environment of tin source hydrolysis is provided again.Then, Li1.81H0.19Ti2O5·xH2O Dehydrations under inertia or reducing atmosphere generate Li4Ti5O12-TiO2, while SnO2In-situ reducing Generate Sn.
Beneficial effects of the present invention are：
1) composite that the present invention is prepared has played monodimension nanometer material Li4Ti5O12-TiO2Matrix electrochemistry is embedding Lithium process Volume Changes are small, metal Sn height ratio capacities and carbon coating layer improve the collaboration such as electronic conductance and ion permeability and made With.In addition, one-dimensional nano structure and nano composite structure also act the migration distance for shortening lithium ion, increase and electrolyte Contact area, alleviate Lithium-ion embeding/effect of stress and volumetric expansion caused by abjection process.Therefore, the composite exhibition Reveal excellent chemical property, in 1000mAg-1Big multiplying power under circulate 600 times, capacity is kept stable at 300mAh g-1。
2) present invention solves that titanium-based series material specific capacity is relatively low and alloy series metal Sn nano-powders are due to embedding The problem of Volume Changes acutely cause capacity sharp-decay during lithium/de- lithium, to titanium-based series material and other alloy series And the compound design of metal oxide series material and optimization provide larger inspiration and instruct foundation.
3) present invention passes through in-situ reducing SnO2Method metal Sn nano particles are dispersed in Li4Ti5O12-TiO2 The surface of nano wire, effectively alleviate the problem of nano particle is prepared with easily reuniting in electrochemistry cyclic process.And existing document The relevant Li of report4Ti5O12With nanometer Sn composite, to be simple physical compound, nanometer Sn particles are easily reunited, and are made Into capacity rapid decay.
4) present invention is prepared for carbon coating Li4Ti5O12-TiO2/ Sn nano composite materials, material preparation process is gently controllable, Synthesis technique has not only been simplified, has also effectively reduced energy consumption and pollution, has met the requirement of national " 12 " energy-saving and emission-reduction planning.This Outside, raw material is cheap and easy to get, and yield is high, easily realizes large-scale industrial production, in hybrid vehicle, pure electric automobile and fast The energy storage such as lithium ion battery filled in electronic product field has broad application prospects.
Brief description of the drawings
Fig. 1 is the TEM figures of resulting materials in the embodiment of the present invention 3；
Fig. 2 is the TEM figures 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 figures of resulting materials in the embodiment of the present invention 8；
Fig. 5 is the HRTEM figures of resulting materials in the embodiment of the present invention 8；
Fig. 6 is the SEM figures of resulting materials in the embodiment of the present invention 8；
Fig. 7 is specific discharge capacity figure of the test battery of resulting materials in the embodiment of the present invention 8 under different current densities；
Fig. 8 is the test battery of resulting materials in the embodiment of the present invention 8 in 1000mAg-1Current density under circulation Performance and coulombic efficiency figure.
Embodiment
The preparation of metatitanic acid nano-powder
Embodiment 1
By the TiO of 2.5g P 252Mixed with the NaOH solution that 80mL concentration is 10mol/L, the laggard water-filling heat of stirring 4h is anti- 96h is answered, hydrothermal temperature is 120 DEG C.After reaction terminates, product is added in the excessive dust technology that concentration is 0.1mol/L and stirred 0.5h, product is dried at 60 DEG C after centrifugation, obtains the metatitanic acid nano-powder of white puff.
Embodiment 2
By 6.5g rutile TiOs2Mixed with the KOH solution that 80mL concentration is 15mol/L, the laggard water-filling heat of stirring 5h is anti- 30h is answered, hydrothermal temperature is 150 DEG C.After reaction terminates, product is added in the excessive watery hydrochloric acid that concentration is 0.8mol/L and stirred 12h, product is dried at 60 DEG C after suction filtration, obtain the metatitanic acid nano-powder of white puff.
Embodiment 3
By 9.5g Detitanium-ore-types TiO2Mixed with the NaOH solution that 80mL concentration is 20mol/L, the laggard water-filling heat of stirring 3h 72h is reacted, hydrothermal temperature is 180 DEG C.After reaction terminates, product is added in the excessive watery hydrochloric acid that concentration is 0.5mol/L and stirred 10h is mixed, product is dried at 60 DEG C after suction filtration, obtains the metatitanic acid nano-powder of white puff.The TEM image of material is shown in Fig. 1.
Li1.81H0.19Ti2O5·xH2O/SnO2The preparation of presoma
Embodiment 4
0.1g metatitanic acids nano-powder is mixed with the LiCl aqueous solution that 100mL concentration is 0.1mol/L, uses 1mol/L's It is 8 that NaOH solution, which adjusts its pH value, then adds 0.5g SnCl4·5H2O simultaneously stirs 2h, then carries out hydro-thermal reaction 4h, water Hot temperature is 120 DEG C.React product centrifugation or filtering and washing after terminating, obtain Li1.81H0.19Ti2O5·xH2O/SnO2Forerunner Body.
Embodiment 5
0.8g metatitanic acids nano-powder is mixed with the LiOH aqueous solution that 100mL concentration is 1mol/L, then adds 0.3g's SnCl2·2H2O simultaneously stirs 0.5h, then carries out hydro-thermal reaction 12h, and hydrothermal temperature is 150 DEG C.Reaction centrifuges product after terminating Or filtering and washing, obtain Li1.81H0.19Ti2O5·xH2O/SnO2Presoma.
Embodiment 6
Li by 2.0g metatitanic acids nano-powder with 100mL concentration for 2mol/L2SO4The aqueous solution mixes, and uses 1mol/L's It is 14 that KOH solution, which adjusts its pH value, then adds 5.0g SnSO4And 4h is stirred, then carry out hydro-thermal reaction 0.5h, hydro-thermal temperature Spend for 180 DEG C.React product centrifugation or filtering and washing after terminating, obtain Li1.81H0.19Ti2O5·xH2O/SnO2Presoma.Material The TEM image of material is shown in Fig. 2.
Carbon coating Li4Ti5O12-TiO2The preparation of/Sn composites
Embodiment 7
By 1.0g Li1.81H0.19Ti2O5·xH2O/SnO2Presoma is added to the 100mL Tris- containing 0.5g dopamines In buffer cushioning liquid, reaction 5h is carried out, reaction temperature is 70 DEG C；React product centrifugation or filtering and washing after terminating；With Products therefrom is heat-treated afterwards, heating rate is 10 DEG C/min, and product is incubated 2h under 650 DEG C of Ar atmosphere, wrapped The amount of covering is 3wt% carbon coating Li4Ti5O12-TiO2/ Sn composites.
Embodiment 8
By 0.1g Li1.81H0.19Ti2O5·xH2O/SnO2Presoma is added to the 100mL Tris- containing 0.8g dopamines In buffer cushioning liquid, reaction 48h is carried out, reaction temperature is 30 DEG C；React product centrifugation or filtering and washing after terminating；With Products therefrom is heat-treated afterwards, heating rate is 2 DEG C/min, Ar/H of the product at 500 DEG C2(Ar/H2:95%/5%) gas 6h is incubated under atmosphere, obtains the carbon coating Li that covering amount is 21wt%4Ti5O12-TiO2/ Sn composites.The XRD spectra of material, TEM image, HRTEM images and SEM image are shown in Fig. 3, Fig. 4, Fig. 5 and Fig. 6.
Embodiment 9
By 2.0g Li1.81H0.19Ti2O5·xH2O/SnO2Presoma is added to the 100mL Tris- containing 1.5g dopamines In buffer cushioning liquid, reaction 48h is carried out, reaction temperature is 50 DEG C；React product centrifugation or filtering and washing after terminating；With Products therefrom is heat-treated afterwards, heating rate is 5 DEG C/min, and product is incubated 8h under 500 DEG C of argon gas atmosphere, wrapped The amount of covering is 14wt% carbon coating Li4Ti5O12-TiO2/ Sn composites.
The carbon coating Li of embodiment 104Ti5O12-TiO2The electrochemical property test of/Sn nano composite materials
Carbon coating Li4Ti5O12-TiO2The preparation of/Sn electrodes：By a certain amount of carbon coating Li4Ti5O12-TiO2/ Sn materials Powder and conductive black (Super P), binding agent Kynoar (PVDF), successively by 8:1:1 mass ratio is added to 10mL 1-METHYLPYRROLIDONE (NMP) solvent in, stir after 4h coated on aluminium foil, be dried in vacuo 10h at 100 DEG C, electricity is made Pole diaphragm.
Test the assembling of battery：Using metal lithium sheet as negative pole, carbon coating Li4Ti5O12-TiO2/ Sn electrodes are positive pole, The microporous polypropylene membranes of Celgard 2400 are barrier film, and concentration is 1mol/L LiPF6Ethylene carbonate (EC) solution and diformazan (EC is 1 with DMC volume ratios to base carbonic ester (DMC) mixed solution:1) it is electrolyte, the high-purity of 1ppm is below in water oxygen content 2032 type button cells are assembled in the glove box of argon gas atmosphere.
The test of chemical property：Button is tested in 0.01V~3.0V voltage ranges using LAND battery test systems The electrochemistry cycle characteristics of battery.Fig. 7 is carbon coating Li4Ti5O12-TiO2/ Sn test battery is respectively in 50mAg-1、 100mA·g-1、200mA·g-1、500mA·g-1And 1000mAg-1Specific discharge capacity figure under uniform current density, Fig. 8 are carbon Coat Li4Ti5O12-TiO2/ Sn test battery is in 1000mAg-1Current density under cycle performance and coulombic efficiency figure. As can be seen that the composite has played monodimension nanometer material Li4Ti5O12-TiO2Matrix Electrochemical lithiation process Volume Changes Small, metal Sn height ratio capacities and carbon coating layer improve the synergy such as electronic conductance and ion permeability, have shown excellent Chemical property.In 1000mAg-1Big multiplying power under circulate 600 times (i.e. 20min or so complete discharge cycles), capacity is protected Keep steady and be scheduled on 300mAh g-1。
Above example should not be construed as the limitation of the present invention, the other forms that every technological thought based on the present invention is done On modification, replacement or change and the invention realized belongs to the scope of the invention.Can be not for those skilled in the art On the premise of departing from the present invention, some improvement can be made to the present invention, therefore all methods according to described in present patent application scope, The equivalent change or modification that feature and principle are done, for example, reaction raw materials, reaction time, heat treatment temperature, the time, atmosphere with And material amounts ratio etc., these features also belong to the scope of patent application protection.

Claims (9)

  1. A kind of 1. Li of carbon coating4Ti5O12-TiO2The preparation method of/Sn nano composite materials, it is characterised in that including following step Suddenly：
    (1) preparation of metatitanic acid nano-powder：
    The compound of titanium is mixed with alkaline aqueous solution, after stirring 3h~5h, carries out hydro-thermal reaction 24h~96h, hydro-thermal reaction temperature Spend for 120 DEG C~200 DEG C；After reaction terminates, product is added to stirring 0.5h~12h in acidic aqueous solution, through centrifuging or taking out Filter, product is collected, through being dried to obtain metatitanic acid nano-powder after products therefrom washing；
    (2)Li1.81H0.19Ti2O5·xH2O/SnO2The preparation of presoma：
    Metatitanic acid nano-powder is mixed with the soluble lithium salt aqueous solution, it is 8~14 to make pH, and adds soluble tin source, is stirred After 0.5h~4h, hydro-thermal reaction 0.5h~12h is carried out, temperature is 120 DEG C~200 DEG C；Product is centrifuged or taken out after terminating by reaction Filter washing, obtain Li1.81H0.19Ti2O5·xH2O/SnO2Presoma；
    (3) Li of carbon coating4Ti5O12-TiO2The preparation of/Sn nano composite materials：
    By Li1.81H0.19Ti2O5·xH2O/SnO2Presoma is added in the Tris-buffer aqueous buffer solutions containing dopamine, PH=8.5, reacts 1~48h, and temperature is 25 DEG C~120 DEG C；React product centrifugation or filtering and washing after terminating；Then by institute Obtain product to be heat-treated, to 350 DEG C~700 DEG C and be incubated 0.5h~8h from room temperature, obtain the Li of carbon coating4Ti5O12- TiO2/ Sn nano composite materials.
  2. 2. preparation method according to claim 1, it is characterised in that in step (1), the compound of the titanium is anatase One or more in type titanium dioxide, rutile titanium dioxide, metatitanic acid, amorphous titania and titanate.
  3. 3. preparation method according to claim 1, it is characterised in that in step (1), the alkaline aqueous solution is hydroxide Sodium water solution or potassium hydroxide aqueous solution；The alkaline aqueous solution concentration is 8mol/L~20mol/L, the compound of the titanium with The amount ratio of alkaline aqueous solution is (3.0g~14.0g)：100mL；
    The acidic aqueous solution be aqueous solution of nitric acid, aqueous hydrochloric acid solution, aqueous sulfuric acid, aqueous acetic acid, phosphate aqueous solution and The one or more of oxalic acid aqueous solution, concentration are 0.1mol/L~0.8mol/L.
  4. 4. preparation method according to claim 1, it is characterised in that in step (2), the soluble lithium salt aqueous solution PH scopes are 8~14, and concentration is 0.05mol/L~2.0mol/L；
    The amount ratio of the metatitanic acid nano-powder and the soluble lithium salt aqueous solution is (0.1g~2.0g)：100mL, the tin source with The amount ratio of metatitanic acid nano-powder is (0.1g~10.0)：1.0g.
  5. 5. preparation method according to claim 1, it is characterised in that in step (2), the soluble lithium salt is hydroxide One kind in lithium, lithium nitrate, lithium sulfate, lithium carbonate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide and lithium iodide or More than one；
    The soluble tin source include stannic chloride, stannous chloride, STANNOUS SULPHATE CRYSTALLINE, nitric acid tin and one kind in tin oxalate or it is a kind of with On.
  6. 6. preparation method according to claim 1, it is characterised in that in step (3), the Li1.81H0.19Ti2O5· xH2O/SnO2The amount ratio of presoma and Tris-buffer aqueous buffer solutions is (0.1g~2.0g)：100mL；It is described Li1.81H0.19Ti2O5·xH2O/SnO2The amount ratio of presoma and dopamine is 1.0g：(0.1g~10.0g)；
    The heating rate is 2 DEG C/min~10 DEG C/min；The atmosphere of the heat treatment is vacuum, inert gas or reproducibility gas Body.
  7. 7. the Li of carbon coating prepared by any one of the claim 1-6 preparation methods4Ti5O12-TiO2/ Sn nano composite materials, Characterized in that, the Li of the carbon coating4Ti5O12-TiO2In/Sn nano composite materials, Li4Ti5O12Content for 19wt%~ 65wt%, TiO2Content be 11wt%~57wt%, Sn content is 23wt%~49wt%；The content of carbon coating layer is 1wt%~24wt%；The carbon source of the carbon coating is dopamine.
  8. A kind of 8. Li of carbon coating described in claim 74Ti5O12-TiO2/ Sn nano composite materials are preparing battery electrode film Application in terms of piece.
  9. 9. application according to claim 8, it is characterised in that by the Li of carbon coating4Ti5O12-TiO2The nano combined materials of/Sn Material and conductive black, Kynoar, in mass ratio 8:1:1 is added in 1-METHYLPYRROLIDONE, and aluminium foil is coated on after mixing Or on copper foil, electrode diaphragm is made after 100 DEG C of vacuum drying.
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