CN106784722B - A kind of lithium titanate/titanium dioxide combination electrode material and preparation method thereof - Google Patents
A kind of lithium titanate/titanium dioxide combination electrode material and preparation method thereof Download PDFInfo
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- CN106784722B CN106784722B CN201710021108.2A CN201710021108A CN106784722B CN 106784722 B CN106784722 B CN 106784722B CN 201710021108 A CN201710021108 A CN 201710021108A CN 106784722 B CN106784722 B CN 106784722B
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- 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
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- 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
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Abstract
The invention belongs to electrode material fields, more particularly to a kind of lithium titanate/titanium dioxide combination electrode material, provided combination electrode material has special space structure, and the electrode material includes nanometer sheet and nanometer rods, which is hollow oval or/and close ellipsoidal structure.Lithium titanate provided by the invention/titanium dioxide combination electrode material has excellent cyclical stability, has excellent chemical property and specific capacity in high current density situation；The present invention also provides the method for preparing the combination electrode material, preparation process very simple and production energy consumption is low, resulting product morphology and size is stable and easily controllable, it is easy to accomplish extensive industrialization.
Description
Technical field
The invention belongs to electrode material field more particularly to a kind of lithium titanate/titanium dioxide combination electrode material and its systems
Preparation Method.
Background technique
Lithium ion battery does not have memory effect because of its characteristic with high-energy-density and high-specific-power, instead of nickel
Hydrogen battery has obtained wide in the small-sized movables field of electronic device such as mobile phone, hand-held computer, video camera, bluetooth headset
General application, while being also current electric vehicle and the most suitable energy storage device of hybrid electric vehicle.
Result of study shows spinel lithium titanate (Li4Ti5O12) material voltage platform with higher (1.55V vs Li/
Li+), will not as graphite type material formed SEI film and generate Li dendrite, in charge and discharge process will not thermal runaway, compare graphite
Class material significantly enhances the safety of lithium ion battery；Simultaneously during its insertion and deintercalate lithium ions, lattice is normal
Several variations is less than 1%, referred to as " zero strain " material, therefore it is with excellent cyclical stability, the theoretical specific volume of lithium titanate
Amount is 175mAh/g, lower than graphite type material, but lithium titanate cyclical stability is splendid, and reversible capacity is still than graphite-like material
Material wants one of ideal material that is high, therefore becoming energy storage device.
However, due to lithium titanate material electronic conductivity (< 10-13And the ionic diffusion coefficient (10 of lithium ion s)-9X10- 13cm2/ s) it is lower, in high current density charge and discharge, polarization phenomena cause capacity attenuation fast than more serious, high rate performance compared with
Difference.
In conclusion since charge-discharge magnification performance is poor under high current density for lithium titanate material, capacity attenuation it is fast and compared with
Low conductivity, to limit its application on electrode material.Therefore, a kind of high conductivity, the good titanium of high rate performance are found
Sour lithium material is those skilled in the art's technical problem urgently to be resolved.
Summary of the invention
In view of this, providing a kind of lithium titanate/titanium dioxide combination electrode the present invention overcomes the deficiencies in the prior art
Material, the combination electrode material have excellent cyclical stability, also have good electrochemistry under high current density
Energy and specific capacity.
Lithium titanate provided by the invention/titanium dioxide combination electrode material includes nanometer sheet and nanometer rods, the nanometer sheet
Hollow ellipse shape or/and close ellipse is assembled into nanometer rods.
Preferably, the nanometer leaf length is in 200nm-350nm, width in 50nm-150nm, thickness in 10-25nm,
The nanometer stick diameter in 7-10nm, grow in 200-500nm by stick, and the hollow cavity diameter is in 400-600nm.
Preferably, the hollow ellipse shape or/and nearly oval diameter are at 1.4 μm -3 μm.
The present invention also provides the lithium titanate/titanium dioxide combination electrode material preparation methods, comprising the following steps:
Lithium solution, titanium solution and hydrogen peroxide mixing, carry out hydro-thermal reaction and obtain product one；By product one in inert gas
Under atmosphere, calcine up to lithium titanate/titanium dioxide combination electrode material.
Preferably, the molar ratio of lithium ion and titanium ion in titanium solution is (3:1)~(10:1) in the lithium solution；Institute
Stating lithium ion and hydrogen peroxide molar ratio in lithium solution is (1.2:1)~(1:1.25).
Preferably, lithium ion and hydrogen peroxide molar ratio are 1:1.2 in the lithium solution.
Preferably, the lithium-containing compound of the lithium solution is lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, lithium oxalate
One of or it is a variety of.
Preferably, the titanium-containing compound of the titanium solution is butyl titanate.
Preferably, the hydrothermal temperature is 120 DEG C -180 DEG C, time 3-24 hour.
Preferably, the inert gas is argon gas or nitrogen.
Preferably, the calcination temperature is 300 DEG C -800 DEG C, the time is 3-24 hours.
Preferably, the calcining heating rate is 10 DEG C/min.
The invention also discloses the lithium titanate/titanium dioxide combination electrode material or/and using made from the method
Application of the combination electrode material in battery electrode.
Further, the present invention is reacted to each other using hydrogen peroxide, lithium ion and titanium ion, is calcined under specific molar ratio
Lithium titanate/titanium dioxide combination electrode material is prepared, the combination electrode material is for special hollow ellipse shape or/and closely
Ellipse.
Lithium titanate provided by the invention/titanium dioxide combination electrode material, including two-dimensional nano piece and monodimension nano stick are certainly
Assembling forms hollow oval or/and close ellipse, which imparts lithium titanate/titanium dioxide (Li4Ti5O12-
TiO2) the excellent chemical property of combination electrode material and specific capacity, advantage it is as follows:
1) Li provided by the invention4Ti5O12-TiO2Combination electrode material is hollow shape, therefore specific surface with higher
Product, increases the contact area of active material and electrolyte, improves the utilization rate of active material, and then is conducive to improve material
Chemical property under high current density charge and discharge.
2) Li provided by the invention4Ti5O12-TiO2Combination electrode material is stacked by two-dimensional nano piece and monodimension nano stick
It forms, two-dimensional nanometer sheet and one-dimensional nanometer rods reduce the diffusion length of lithium ion, are formed simultaneously one-dimensional two-dimensional interaction
Structure helps to further increase ion diffusion rates；Combination electrode material is micron scale construction simultaneously, has micro materials steady
Qualitative good advantage, transmission range can also be lowered by being not susceptible to reunite.
3) Li provided by the invention4Ti5O12-TiO2Combination electrode material, with the rutile TiO with height ratio capacity2Knot
It closes, compound obtained electrode material not only has excellent cyclical stability, also has superior electrification under high current density
Learn performance and specific capacity.
4) prepare the technique very simple of combination electrode material of the invention and production energy consumption be low, resulting product pattern and
Dimensionally stable and easily controllable, it is easy to accomplish scale of mass production.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 shows X-ray diffraction (XRD) map of embodiment 1；
Fig. 2 shows 11000 times of field emission microscope (FR-SEM) photos of embodiment 1；
Fig. 3 shows 35000 times of field emission microscope (FR-SEM) photos of embodiment 1；
Fig. 4 shows high-resolution-ration transmission electric-lens (HRTEM) photo of embodiment 1；
Fig. 5 shows high-resolution-ration transmission electric-lens (HRTEM) photo of embodiment 1；
Fig. 6 shows the first charge-discharge curve of embodiment 1；
Fig. 7 shows the first charge-discharge curve of commercial material；
Fig. 8 shows the cycle performance figure under 10C multiplying power of embodiment 1 Yu commercial material；
35000 times of field emission microscope (FR-SEM) photos of the comparative example 1 that Fig. 9 shows；
15000 times of field emission microscope (FR-SEM) photos of the comparative example 2 that Figure 10 shows；
35000 times of field emission microscope (FR-SEM) photos of the comparative example 3 that Figure 11 shows.
11000 times of field emission microscope (FR-SEM) photos of the comparative example 4 that Figure 12 shows.
Specific embodiment
The present invention provides a kind of combination electrode materials and preparation method thereof, for solving lithium titanate material in the prior art
The technological deficiency that conductivity is poor, high rate performance is bad.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Wherein, raw material used in the embodiment of the present invention is commercially available, and commercial material is bought from Shenzhen Bei Terui nanometers of section
Skill Co., Ltd, production number LTO-2.
Embodiment 1
1, the monohydrate lithium hydroxide under magnetic stirring, weighing 2.68g is dissolved in deionized water, is allowed to equal under stirring
Even dissolution；
2,30% hydrogenperoxide steam generator for measuring 8ml, is added drop-wise in the resulting solution of step 1 with the rate of 5ml/min；
3, the butyl titanate for measuring 5.44ml, is added drop-wise in the solution of step 2 with the rate of 1ml/min；
4, after mixing liquid obtained in step 3 being stirred half an hour, the stainless steel for being transferred to polytetrafluoroethyllining lining is anti-
It answers in kettle, postposition is sealed in a vacuum drying oven, keep the temperature 6 hours at 150 DEG C；
5, after step 4 reaction be cooled to room temperature after, take out reaction kettle in liquid and precipitating, filtered, and spend from
Sub- water and ethanol wash for several times, then, will be dried to obtain Huang in the vacuum oven for being deposited in 70 DEG C resulting after filtering and washing
Green powder；
6, yellow green powder obtained in step 5 is ground；
7, by step 6 grinding after powder be placed in tube furnace, at 500 DEG C under nitrogen atmosphere calcine 4 hours to get
To Li4Ti5O12-TiO2Combination electrode material.
Embodiment 2
1, it under magnetic stirring, weighs two water lithium acetate of 4.9g and is dissolved in deionized water, be allowed to uniformly molten under stirring
Solution；
2,30% hydrogenperoxide steam generator of 4ml is measured, is added drop-wise in the resulting solution of step 1 with the rate of 5ml/min；
3,5.44ml butyl titanate is measured, the solution of step 2 is added drop-wise to the rate of 1ml/min；
4, after mixing liquid obtained in step 3 being stirred half an hour, the stainless steel for being transferred to polytetrafluoroethyllining lining is anti-
It answers in kettle, postposition is sealed in a vacuum drying oven, keep the temperature 24 hours at 120 DEG C；
5, after step 4 reaction be cooled to room temperature after, take out reaction kettle in liquid and precipitating, filtered, and spend from
Sub- water and ethanol wash are for several times, then, yellowish green by being dried to obtain in the resulting vacuum oven for being deposited in 70 DEG C of filtering and washing
Toner body；
6, yellow green powder obtained in step 5 is ground；
7, the powder after step 6 grinding is placed in tube furnace, at 300 DEG C, 24 hours is calcined under argon atmosphere, i.e.,
Obtain Li4Ti5O12-TiO2Combination electrode material.
Embodiment 3
1, the lithium carbonate under magnetic stirring, weighing 4.73g is dissolved in deionized water, is allowed to uniformly molten under stirring
Solution；
2,30% hydrogenperoxide steam generator for measuring 8ml, is added drop-wise in the resulting solution of step 1 with the rate of 5ml/min；
3, the butyl titanate for measuring 2.17ml, is added drop-wise in the solution of step 2 with the rate of 1ml/min；
4, after mixing liquid obtained in step 3 being stirred half an hour, the stainless steel for being transferred to polytetrafluoroethyllining lining is anti-
It answers in kettle, postposition is sealed in a vacuum drying oven, keep the temperature 3 hours at 180 DEG C；
5, after step 4 reaction be cooled to room temperature after, take out reaction kettle in liquid and precipitating, filtered, and spend from
Sub- water and ethanol wash for several times, then, will be dried to obtain Huang in the vacuum oven for being deposited in 70 DEG C resulting after filtering and washing
Green powder；
6, yellow green powder obtained in step 5 is ground；
7, the powder after step 6 grinding is placed in tube furnace, at 800 DEG C, 3 hours is calcined under argon atmosphere, i.e.,
Obtain Li4Ti5O12-TiO2Combination electrode material.
Embodiment 4
1, the lithium oxalate under magnetic stirring, weighing 6.53g is dissolved in deionized water, is allowed to uniformly molten under stirring
Solution；
2,30% hydrogenperoxide steam generator for measuring 6.4ml, is added drop-wise in the resulting solution of step 1 with the rate of 5ml/min；
3, the butyl titanate for measuring 2.72ml, is added drop-wise in the solution of step 2 with the rate of 1ml/min；
4, after mixing liquid obtained in step 3 being stirred half an hour, the stainless steel for being transferred to polytetrafluoroethyllining lining is anti-
It answers in kettle, postposition is sealed in a vacuum drying oven, keep the temperature 4 hours at 150 DEG C；
5, after step 4 reaction be cooled to room temperature after, take out reaction kettle in liquid and precipitating, filtered, and spend from
Sub- water and ethanol wash for several times, then will be dried to obtain yellowish green in the vacuum oven for being deposited in 70 DEG C resulting after filtering and washing
Toner body；
6, yellow green powder obtained in step 5 is ground；
7, the powder after step 6 grinding is placed in tube furnace, at 550 DEG C, 6 hours is calcined under air atmosphere, i.e.,
Obtain Li4Ti5O12-TiO2Combination electrode material.
Embodiment 5
Utilize the getable Li of the method for Examples 1 to 44Ti5O12-TiO2Combination electrode material, therefore measure wherein one
Kind can illustrate the characteristic of combination electrode material of the present invention, choose embodiment 1 below and measure its chemical property.
The XRD spectrum of embodiment 1 is measured, Fig. 1 is as it can be seen that 1 composite material diffraction maximum of embodiment and lithium titanate (Li4Ti5O12)
Standard diffraction peak card match, while there are also seven diffraction maximums and rutile titanium dioxide (TiO2) coincide, illustrate to prepare
Sample be Li4Ti5O12-TiO2Combination electrode material.
Embodiment 6
Utilize Li in field emission microscope (FR-SEM) observation embodiment 14Ti5O12-TiO2Combination electrode material is shown
Micro-structure,
Fig. 2 as it can be seen that under 11000 times of field emission microscopes, 1 combination electrode material of embodiment be hollow ellipse shape or/
Nearly elliptical shape.
For Fig. 3 as it can be seen that under 35000 times of field emission microscopes, 1 combination electrode material of embodiment is on chip by a large amount of nanometer
At hollow oval or/and close elliptical shape.
Embodiment 7
Utilize Li in high-resolution-ration transmission electric-lens (HRTEM) observation embodiment 14Ti5O12-TiO2Combination electrode material it is micro-
Structure.
Shown in Fig. 4, under high-resolution-ration transmission electric-lens, 1 combination electrode material of embodiment is each oval or/and close oval
There is fine strip shape protrusion.
Shown in Fig. 5, under high-resolution-ration transmission electric-lens, 1 combination electrode material of embodiment is each oval or/and close oval
It is formed by the nanometer sheet build stack of dark nanorod structure and light color.
Embodiment 8
First charge-discharge experimental procedure is as follows: 1, preparing Li using the method for embodiment 14Ti5O12-TiO2Combination electrode material
Material；2, negative electrode slurry is prepared, by Li4Ti5O12-TiO2Combination electrode material and conductive agent acetylene black are mixed according to the mass ratio of 8:1
It closes, is ground, be allowed to be sufficiently mixed, obtain mixed-powder.By sanlose (CMC) and polymerized sbr
(SBR) mixed emulsion is mixed to get according to the ratio of 1:1.Above-mentioned mixed-powder and mixed emulsion are mixed in the ratio of 97:3,
And be dissolved in deionized water, uniform stirring 12h, the slurry with certain viscosity and mobility is made；3, slurry is uniformly applied
The surface of aluminium foil is overlayed on, is rolled after 120 DEG C of vacuum drying 12h by roll squeezer, Li is made4Ti5O12-TiO2Combination electrode material
Cathode pole piece；4 by obtained Li4Ti5O12-TiO2The cathode pole piece of combination electrode material is punched into the circle that diameter is 14mm
Piece, diaphragm Cellgard2400, positive plate is the lithium piece of 16mm, in water content < 2ppm, oxygen content < 1ppm glove box
It is assembled into 2032 button cells；5, the first charge-discharge curve of 1 combination electrode material of embodiment is measured；Meanwhile it is above-mentioned same
Mode measures the first charge-discharge curve of commercial material.
Shown in Fig. 6, the first charge-discharge curve of 1 combination electrode material of embodiment, under the multiplying power of 0.1C, material is for the first time
Discharge capacity has reached 269mAh/g, and initial charge capacity has reached 268mAh/g；Fig. 7 is that the first charge-discharge of commercial material is bent
Line, under the multiplying power of 0.1C, in discharge capacity 163mAh/g for the first time, initial charge capacity 161mAh/g, it can be seen that, the present invention
Combination electrode material capacitance performance is very excellent for the first time.
Embodiment 9
Steps are as follows for cycle performance test experiments: 1, preparing Li using the method for embodiment 14Ti5O12-TiO2Combination electrode
Material；2, negative electrode slurry is prepared, by Li4Ti5O12-TiO2Combination electrode material and conductive agent acetylene black are mixed according to the mass ratio of 8:1
It closes, is ground, be allowed to be sufficiently mixed, obtain mixed-powder.By sanlose (CMC) and polymerized sbr
(SBR) mixed emulsion is mixed to get according to the ratio of 1:1.Above-mentioned mixed-powder and mixed emulsion are mixed in the ratio of 97:3,
And be dissolved in deionized water, uniform stirring 12h, the slurry with certain viscosity and mobility is made；3, slurry is uniformly applied
The surface of aluminium foil is overlayed on, is rolled after 120 DEG C of vacuum drying 12h by roll squeezer, Li is made4Ti5O12-TiO2Combination electrode material
Cathode pole piece；4 by obtained Li4Ti5O12-TiO2The cathode pole piece of combination electrode material is punched into the circle that diameter is 14mm
Piece, diaphragm Cellgard2400, positive plate is the lithium piece of 16mm, in water content < 2ppm, oxygen content < 1ppm glove box
It is assembled into 2032 button cells；5, the cycle performance of embodiment 1 combination electrode material and commercial material is measured.
Shown in Fig. 8, the cycle performance figure of 1 combination electrode material of embodiment, under the multiplying power of 10C, the initial specific volume of material
Amount is 220mAh/g, and after 500 charge and discharge cycles, specific capacity still has 200mAh/g, illustrates material before height ratio capacity
It puts, there is excellent multiplying power stability；And commercial material is under the multiplying power of 10C, the initial specific capacities of material are 136mAh/g,
After 500 charge and discharge cycles, specific capacity 93mAh/g, with this as it can be seen that electrode material of the invention is on chemical property
It is superior to commercial material significantly.
Comparative example 1
1, the monohydrate lithium hydroxide under magnetic stirring, weighing 2.68g is dissolved in deionized water, is allowed to equal under stirring
Even dissolution；
2,30% hydrogenperoxide steam generator for measuring 8ml, is added drop-wise in the resulting solution of step 1 with the rate of 5ml/min；
3, the butyl titanate for measuring 1.81ml, is added drop-wise in the solution of step 2 with the rate of 1ml/min；
4, after mixing liquid obtained in step 3 being stirred half an hour, the stainless steel for being transferred to polytetrafluoroethyllining lining is anti-
It answers in kettle, postposition is sealed in a vacuum drying oven, keep the temperature 6 hours at 150 DEG C；
5, after step 4 reaction be cooled to room temperature after, take out reaction kettle in liquid and precipitating, filtered, and spend from
Sub- water and ethanol wash for several times, then will be dried to obtain yellowish green in the vacuum oven for being deposited in 70 DEG C resulting after filtering and washing
Toner body；
6, yellow green powder obtained in step 5 is ground；
7, the powder after step 6 grinding is placed in tube furnace, calcines 4 hours under nitrogen atmosphere at 500 DEG C, obtains
The electrode material of comparative example 1.
As shown in figure 9, material as described in Figure 9 can be obtained if lithium ion and titanium ion molar ratio exceed the scope of the invention
Material, which is not that nanometer sheet and nanometer rods assemble, and does not form hollow shape yet.
Comparative example 2
1, the monohydrate lithium hydroxide under magnetic stirring, weighing 2.68g is dissolved in deionized water, is allowed to equal under stirring
Even dissolution；
2,30% hydrogenperoxide steam generator for measuring 8ml, is added drop-wise in the resulting solution of step 1 with the rate of 5ml/min；
3, the butyl titanate for measuring 10.88ml, is added drop-wise in the solution of step 2 with the rate of 1ml/min；
4, after mixing liquid obtained in step 3 being stirred half an hour, the stainless steel for being transferred to polytetrafluoroethyllining lining is anti-
It answers in kettle, postposition is sealed in a vacuum drying oven, keep the temperature 6 hours at 150 DEG C；
5, after step 4 reaction be cooled to room temperature after, take out reaction kettle in liquid and precipitating, filtered, and spend from
Sub- water and ethanol wash for several times, then will be dried to obtain yellowish green in the vacuum oven for being deposited in 70 DEG C resulting after filtering and washing
Toner body；
6, yellow green powder obtained in step 5 is ground；
7, the powder after step 6 grinding is placed in tube furnace, calcines 4 hours under nitrogen atmosphere at 500 DEG C, obtains
The electrode material of comparative example.
As shown in Figure 10, it if lithium ion and titanium ion molar ratio exceed the scope of the invention, can obtain as described in Figure 10
Material, the material sub-fraction are assembled by nanometer sheet and nanometer rods, however most of is undefined structure.
Comparative example 3
1, the monohydrate lithium hydroxide under magnetic stirring, weighing 2.68g is dissolved in deionized water, is allowed to equal under stirring
Even dissolution；
2,30% hydrogenperoxide steam generator for measuring 8ml ml, is added drop-wise to the resulting solution of step 1 with the rate of 5ml/min
In；
3, the butyl titanate for measuring 21.76ml, is added drop-wise in the solution of step 2 with the rate of 1ml/min；
4, after mixing liquid obtained in step 3 being stirred half an hour, the stainless steel for being transferred to polytetrafluoroethyllining lining is anti-
It answers in kettle, postposition is sealed in a vacuum drying oven, keep the temperature 6 hours at 150 DEG C；
5, after step 4 reaction be cooled to room temperature after, take out reaction kettle in liquid and precipitating, filtered, and spend from
Sub- water and ethanol wash for several times, then will be dried to obtain yellowish green in the vacuum oven for being deposited in 70 DEG C resulting after filtering and washing
Toner body；
6, yellow green powder obtained in step 5 is ground；
7, the powder after step 6 grinding is placed in tube furnace, calcines 4 hours under nitrogen atmosphere at 500 DEG C, obtains
The electrode material of comparative example.
As shown in figure 11, it if lithium ion and titanium ion molar ratio exceed the scope of the invention, can obtain as described in Figure 11
Material, the material are undefined structure.
Comparative example 4
1, the monohydrate lithium hydroxide under magnetic stirring, weighing 2.68g is dissolved in deionized water, is allowed to equal under stirring
Even dissolution；
2,30% hydrogenperoxide steam generator for measuring 5.1ml, is added drop-wise in the resulting solution of step 1 with the rate of 5ml/min；
3, the butyl titanate for measuring 5.44ml, is added drop-wise in the solution of step 2 with the rate of 1ml/min；
4, after mixing liquid obtained in step 3 being stirred half an hour, the stainless steel for being transferred to polytetrafluoroethyllining lining is anti-
It answers in kettle, postposition is sealed in a vacuum drying oven, keep the temperature 6 hours at 150 DEG C；
5, after step 4 reaction be cooled to room temperature after, take out reaction kettle in liquid and precipitating, filtered, and spend from
Sub- water and ethanol wash for several times, then will be dried to obtain yellowish green in the vacuum oven for being deposited in 70 DEG C resulting after filtering and washing
Toner body；
6, yellow green powder obtained in step 5 is ground；
7, the powder after step 6 grinding is placed in tube furnace, calcines 4 hours under nitrogen atmosphere at 500 DEG C, obtains
The electrode material of comparative example.
As shown in figure 12, it if lithium ion and surfactant molar ratio exceed the scope of the invention, can obtain such as Figure 12 institute
The material stated, the material be nanoparticle agglomerates at undefined structure.
In conclusion it is an object of the invention to solve lithium titanate material charge-discharge magnification performance under high current density
Difference, the fast technological deficiency of capacity attenuation, the present invention provides a kind of combination electrode material with special space feature, the electricity
Pole material has excellent cyclical stability, in the excellent chemical property of high current density situation, also has specific capacity excellent
Characteristic, the present invention also provides the method for preparing the combination electrode material, the preparation process very simple and production energy
Consume low, resulting product morphology and size is stable and easily controllable, it is easy to accomplish scale of mass production.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (3)
1. a kind of lithium titanate/titanium dioxide combination electrode material, which is characterized in that including nanometer sheet and nanometer rods, the nanometer
Piece and nanometer rods are assembled into hollow ellipse shape or/and nearly ellipse；
Wherein, lithium titanate/titanium dioxide combination electrode material preparation method, comprising the following steps: lithium solution, titanium solution and mistake
Hydrogen oxide mixing obtains product one after carrying out hydro-thermal reaction；Under inert gas atmosphere by product one, it calcines up to lithium titanate/bis-
Titanium oxide combination electrode material；The nanometer leaf length is in 200nm-350nm, and width is in 50nm-150nm, and thickness is in 10-
25nm, the nanometer stick diameter in 7-10nm, grow in 200-500nm by stick；The hollow cavity diameter of the hollow structure is in 400-
600nm, the diameter of oval or/and close ellipse is at 1.4 μm -3 μm.
2. a kind of lithium titanate/titanium dioxide combination electrode material preparation method, which comprises the following steps:
Lithium solution, titanium solution and hydrogen peroxide mixing obtain product one after carrying out hydro-thermal reaction；By product one in inert gas gas
Under atmosphere, calcine up to lithium titanate/titanium dioxide combination electrode material；The lithium ion of the lithium solution and the titanium ion of titanium solution rub
You are than being (3:1) ~ (10:1)；The lithium ion and hydrogen peroxide molar ratio of the lithium solution are (1.2:1) ~ (1:1.25)；It is described
Lithium-containing compound in lithium solution is lithium hydroxide, lithium acetate, lithium carbonate, lithium nitrate, one of lithium oxalate or a variety of；It is described
The titanium-containing compound of titanium solution is butyl titanate；The hydrothermal temperature is 120 DEG C -180 DEG C, and the time is 3-24 hours；
The calcination temperature is 300 DEG C -800 DEG C, and the time is 3-24 hours, and calcining heating rate is 10 DEG C/min.
3. lithium titanate described in claim 1/titanium dioxide combination electrode material or preparation method as claimed in claim 2 are made
Lithium titanate/application of the titanium dioxide combination electrode material in battery electrode.
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| CN104617273A (en) * | 2015-02-04 | 2015-05-13 | 安徽师范大学 | Spherical porous lithium titanate/titanium dioxide composite material as well as preparation method and application of composite material |
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| CN104617273A (en) * | 2015-02-04 | 2015-05-13 | 安徽师范大学 | Spherical porous lithium titanate/titanium dioxide composite material as well as preparation method and application of composite material |
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