CN108933252A - Lithium ion battery lithium titanate and composite titania material and preparation method thereof - Google Patents
Lithium ion battery lithium titanate and composite titania material and preparation method thereof Download PDFInfo
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- CN108933252A CN108933252A CN201811024042.3A CN201811024042A CN108933252A CN 108933252 A CN108933252 A CN 108933252A CN 201811024042 A CN201811024042 A CN 201811024042A CN 108933252 A CN108933252 A CN 108933252A
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- lithium
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- ion battery
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to technical field of lithium ion, a kind of lithium ion battery lithium titanate and composite titania material and preparation method thereof are disclosed.This method is that titanium source is added in solvent, adds the deionized water solution containing a certain amount of lithium source, after mixing to uniformly, carries out hydro-thermal reaction；After gained precipitation and separation, washing, drying, grinding, calcining obtains final product under high temperature.It takes method of the invention, it is possible to simple, the inexpensive lithium titanate and composite titania material for preparing nano-scale.When being used as negative electrode material, excellent circulation and high rate performance are shown.
Description
Technical field
The present invention relates to a kind of lithium ion battery lithium titanate and composite titania materials and preparation method thereof, belong to lithium
Ion battery technology field.
Background technique
Why lithium ion battery is popularized, and is because having many advantages, such as excellent cycle performance and high-energy density.
For now, graphite is still the primary raw material of commercial li-ion cell negative electrode material.However, while having the advantage that,
It also has certain defect.For example, with Li in charge and discharge process+Insertion and abjection, can graphite surface formed Li dendrite,
Accumulation can pierce through diaphragm, cause internal short-circuit of battery for a long time, and there are security risks.
Lithium titanate (Li4Ti5O12) possess the high working voltage platform of ~ 1.55 V, will not its surface generate Li dendrite and
Solid electrolyte interface (SEI) film, can be used as the candidate material of graphite.In addition, Li4Ti5O12Possess the characteristic of " zero strain ",
That is Li+Its volume will not substantially be impacted in the insertion and abjection of material internal, cycle performance is excellent；And its high lithium
Ionic diffusion coefficient is conducive to fast charging and discharging, i.e. high rate performance is excellent.However, Li4Ti5O12Theoretical capacity it is lower than graphite,
Only ~ 175 mAh/g, and have lower electric conductivity (~ 10-13S/cm).
Studies have shown that Li4Ti5O12And TiO2Composite material (LTO-TO), due to Li4Ti5O12And TiO2Interface effect
It answers, Li can be made4Ti5O12Chemical property be improved.The characteristics of size is small and large specific surface area is nano material, as
Electrode material can shorten Li+Diffusion path, come into full contact with electrolyte, finally play more preferably chemical property.Therefore,
It is a kind of feasible method that preparing, which has the LTO-TO composite material of Nano grade particle size,.
Summary of the invention
The purpose of the present invention is with simple, inexpensive approach, provide a kind of lithium ion battery lithium titanate and titanium dioxide
Titanium composite material and preparation method thereof, resulting materials have excellent circulation and high rate performance.
Technical solution according to the invention, the preparation side of the lithium ion battery lithium titanate and composite titania material
Method, comprising the following steps:
(1) solvent is placed in a beaker, under the conditions of magnetic agitation, titanium source is added, is stirred until homogeneous to obtain solution 1；
(2) lithium source is dissolved in deionized water, obtains solution 2；
(3) solution 2 is poured into solution 1, obtain mixed solution and continues to stir 25-35 min；
(4) mixed solution obtained in (3) is transferred in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining, is placed in baking oven
Middle carry out hydro-thermal reaction；
(5) after being cooled to room temperature, products therefrom is centrifuged, is washed, alcohol is washed and 70-90 °C of dry 10-14 h；
(6) it after grinding product, is placed in Muffle furnace, carries out high temperature in air atmosphere with the heating rate of 4-6 °C/min and forge
It burns, final product, i.e. lithium titanate and composite titania material is obtained after being cooled to room temperature.
Further, the solvent in the step (1) is dehydrated alcohol, and titanium source is tetra-n-butyl titanate, titanium source and solvent
Volume ratio be 1:4-6.
Further, lithium source is a hydronium(ion) lithia in the step (2), and lithium source dosage is according to lithium titanium molar ratio 3.5-
4.5:5。
Further, the volume ratio of the titanium source and deionized water is 2:2.5-3.5.
Further, the temperature of hydro-thermal reaction is 160-200 °C in the step (4), and the time is 10-14 h.
Further, calcination temperature is 450-600 °C in the step (6), the time is 2-4 h.
Another aspect provides a kind of lithium ion battery lithium titanates and dioxy that above-mentioned preparation method obtains
Change titanium composite material.
The beneficial effects of the present invention are:
(1) composite material prepared contains Li4Ti5O12, anatase and rutile TiO2Three kinds of components, have Nano grade
Sheet and graininess pattern, and be evenly distributed；
(2) the LTO-TO composite material prepared shows excellent circulation and high rate performance in testing；
(3) preparation method is easy to operate, nontoxic, environmental-friendly, at low cost.
Detailed description of the invention
Fig. 1 is the XRD diagram of LTO-TO composite material.
Fig. 2 is that the SEM of LTO-TO composite material schemes.
Fig. 3 is the preceding charging and discharging curve three times of LTO-TO composite material at room temperature.
Fig. 4 is the cycle performance figure of LTO-TO composite material.
Fig. 5 is the high rate performance figure of LTO-TO composite material.
Specific embodiment
Below with reference to embodiment and attached drawing, technical scheme is described further.
Embodiment 1
(1) dehydrated alcohol of 50mL is measured first in beaker, under the conditions of magnetic agitation, is measured 10mL tetra-n-butyl titanate and is added
Wherein, it is stirred until homogeneous to obtain solution 1；
(2) according to the lithium titanium molar ratio of 4:5, the hydronium(ion) lithia for weighing 1.0174g is dissolved in 15mL deionized water, obtains
To solution 2；
(3) solution 2 is poured into solution 1, obtain mixed solution and continues to stir 30min；
(4) mixed solution obtained in (3) is then transferred to the stainless steel hydrothermal reaction kettle of 100mL polytetrafluoroethyllining lining
In, it is placed in baking oven and carries out hydro-thermal reaction, condition is 180 °C, 12h；
(5) after being cooled to room temperature, products therefrom is centrifuged, is washed, alcohol is washed and 80 °C of dry 12h；
(6) it after grinding product, is placed in Muffle furnace, high-temperature calcination is carried out in air atmosphere with the heating rate of 5 °C/min,
Condition is 600 °C, 3h.Final product, i.e. lithium titanate and composite titania material are obtained after being cooled to room temperature.
Embodiment 2
(1) dehydrated alcohol of 40mL is measured first in beaker, under the conditions of magnetic agitation, is measured 10mL tetra-n-butyl titanate and is added
Wherein, it is stirred until homogeneous to obtain solution 1；
(2) according to the lithium titanium molar ratio of 3.5:5, the hydronium(ion) lithia for weighing 0.8903g is dissolved in 12.5mL deionized water
In, obtain solution 2；
(3) solution 2 is poured into solution 1, obtain mixed solution and continues to stir 25min；
(4) mixed solution obtained in (3) is then transferred to the stainless steel hydrothermal reaction kettle of 100mL polytetrafluoroethyllining lining
In, it is placed in baking oven and carries out hydro-thermal reaction, condition is 160 °C, 10h；
(5) after being cooled to room temperature, products therefrom is centrifuged, is washed, alcohol is washed and 70 °C of dry 14h；
(6) it after grinding product, is placed in Muffle furnace, high-temperature calcination is carried out in air atmosphere with the heating rate of 4 °C/min,
Condition is 450 °C, 3h.Final product, i.e. lithium titanate and composite titania material are obtained after being cooled to room temperature.
Embodiment 3
(1) dehydrated alcohol of 50mL is measured first in beaker, under the conditions of magnetic agitation, is measured 10mL tetra-n-butyl titanate and is added
Wherein, it is stirred until homogeneous to obtain solution 1；
(2) according to the lithium titanium molar ratio of 3.5:5, the hydronium(ion) lithia for weighing 0.8903g is dissolved in 17.5mL deionized water
In, obtain solution 2；
(3) solution 2 is poured into solution 1, obtain mixed solution and continues to stir 35min；
(4) mixed solution obtained in (3) is then transferred to the stainless steel hydrothermal reaction kettle of 100mL polytetrafluoroethyllining lining
In, it is placed in baking oven and carries out hydro-thermal reaction, condition is 200 °C, 14h；
(5) after being cooled to room temperature, products therefrom is centrifuged, is washed, alcohol is washed and 80 °C of dry 12h；
(6) it after grinding product, is placed in Muffle furnace, high-temperature calcination is carried out in air atmosphere with the heating rate of 6 °C/min,
Condition is 500 °C, 4h.Final product, i.e. lithium titanate and composite titania material are obtained after being cooled to room temperature.
Embodiment 4
(1) dehydrated alcohol of 60mL is measured first in beaker, under the conditions of magnetic agitation, is measured 10mL tetra-n-butyl titanate and is added
Wherein, it is stirred until homogeneous to obtain solution 1；
(2) according to the lithium titanium molar ratio of 4.2:5, the hydronium(ion) lithia for weighing 1.0683g is dissolved in 15mL deionized water,
Obtain solution 2；
(3) solution 2 is poured into solution 1, obtain mixed solution and continues to stir 32min；
(4) mixed solution obtained in (3) is then transferred to the stainless steel hydrothermal reaction kettle of 100mL polytetrafluoroethyllining lining
In, it is placed in baking oven and carries out hydro-thermal reaction, condition is 170 °C, 10h；
(5) after being cooled to room temperature, products therefrom is centrifuged, is washed, alcohol is washed and 90 °C of dry 10h；
(6) it after grinding product, is placed in Muffle furnace, high-temperature calcination is carried out in air atmosphere with the heating rate of 5 °C/min,
Condition is 600 °C, 2h.Final product is obtained after being cooled to room temperature, and is lithium titanate and composite titania material.
Embodiment 5
(1) dehydrated alcohol of 55mL is measured first in beaker, under the conditions of magnetic agitation, is measured 10mL tetra-n-butyl titanate and is added
Wherein, it is stirred until homogeneous to obtain solution 1；
(2) according to the lithium titanium molar ratio of 4.5:5, the hydronium(ion) lithia for weighing 1.1446g is dissolved in 16mL deionized water,
Obtain solution 2；
(3) solution 2 is poured into solution 1, obtain mixed solution and continues to stir 35min；
(4) mixed solution obtained in (3) is then transferred to the stainless steel hydrothermal reaction kettle of 100mL polytetrafluoroethyllining lining
In, it is placed in baking oven and carries out hydro-thermal reaction, condition is 190 °C, 13h；
(5) after being cooled to room temperature, products therefrom is centrifuged, is washed, alcohol is washed and 85 °C of dry 13h；
(6) it after grinding product, is placed in Muffle furnace, carries out high temperature in air atmosphere with the heating rate of 5.5 °C/min and forge
It burns, condition is 550 °C, 2.5h.Final product is obtained after being cooled to room temperature, and is lithium titanate and composite titania material.
As seen from Figure 1, the material that embodiment 1 is prepared contains Li4Ti5O12, anatase and rutile TiO2Three kinds of groups
Point (TO-A and TO-R respectively correspond anatase and rutile TiO2).Sharp peak shape illustrates that the crystallinity of the material is high.
From Figure 2 it can be seen that the pattern that the material that the present invention is prepared shows sheet and graininess coexists, having a size of nanometer
Rank and distribution it is relatively uniform.
Electrode slice is made in lithium titanate prepared by the present invention and composite titania material, is assembled into button cell.In room
Under conditions of mild high temperature (55 °C), voltage 1-3 V and certain current density (mA/g of 1 C=170), carries out constant current and fill
Discharge test.Fig. 3 is the preceding charging and discharging curve figure three times of loop test, and first charge-discharge curve shows higher specific capacity,
Close to the theoretical specific capacity of lithium titanate；And third time and secondary electric discharge are not distinguished significantly with charging curve, it was demonstrated that
The good reversibility of the material.Fig. 4 is cycle performance figure, it can be seen that the material has good cycle performance, and passes through 50 times
After circulation, capacity retention ratio is higher.Fig. 5 be high rate performance figure, even if under high current density, the specific capacity of the material still compared with
Height, and possess preferable recovery capability, show excellent high rate performance.
Claims (7)
1. the preparation method of lithium ion battery lithium titanate and composite titania material, which comprises the following steps:
(1) solvent is placed in a beaker, under the conditions of magnetic agitation, titanium source is added, is stirred until homogeneous to obtain solution 1；
(2) lithium source is dissolved in deionized water, obtains solution 2；
(3) solution 2 is poured into solution 1, obtain mixed solution and continues to stir 25-35 min；
(4) mixed solution obtained in (3) is transferred in the stainless steel hydrothermal reaction kettle of polytetrafluoroethyllining lining, is placed in baking oven
Middle carry out hydro-thermal reaction；
(5) after being cooled to room temperature, products therefrom is centrifuged, is washed, alcohol is washed and 70-90 °C of dry 10-14 h；
(6) it after grinding product, is placed in Muffle furnace, carries out high temperature in air atmosphere with the heating rate of 4-6 °C/min and forge
It burns, final product, i.e. lithium titanate and composite titania material is obtained after being cooled to room temperature.
2. the preparation method of lithium ion battery lithium titanate and composite titania material as described in claim 1, feature
It is, the solvent in the step (1) is dehydrated alcohol, and titanium source is tetra-n-butyl titanate, and the volume ratio of titanium source and solvent is 1:
4-6。
3. the preparation method of lithium ion battery lithium titanate and composite titania material as described in claim 1, feature
It is, lithium source is a hydronium(ion) lithia in the step (2), and lithium source dosage is according to lithium titanium molar ratio 3.5-4.5:5.
4. the preparation method of lithium ion battery lithium titanate and composite titania material as described in claim 1, feature
It is, the volume ratio of the titanium source and deionized water is 2:2.5-3.5.
5. the preparation method of lithium ion battery lithium titanate and composite titania material as described in claim 1, feature
It is, the temperature of hydro-thermal reaction is 160-200 °C in the step (4), and the time is 10-14 h.
6. the preparation method of lithium ion battery lithium titanate and composite titania material as described in claim 1, feature
It is, calcination temperature is 450-600 °C in the step (6), the time is 2-4 h.
7. lithium ion battery lithium titanate and titanium dioxide composite wood that the preparation method as described in claim 1-6 is any obtains
Material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115036489A (en) * | 2022-06-27 | 2022-09-09 | 电子科技大学 | Preparation method of high-safety lithium storage material based on lithium titanate heterostructure |
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| CN102386385A (en) * | 2011-10-09 | 2012-03-21 | 北京科技大学 | Preparation method of Li4Ti5O12-TiO2 composite electrode material |
| CN102956880A (en) * | 2012-11-15 | 2013-03-06 | 华中科技大学 | Method for preparing Li4Ti5O12-TiO2 (lithium titanate - titanium oxide) nano composite material and Li4Ti5O12-TiO2 nano composite material thereof |
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2018
- 2018-09-04 CN CN201811024042.3A patent/CN108933252A/en active Pending
Patent Citations (2)
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| CN102386385A (en) * | 2011-10-09 | 2012-03-21 | 北京科技大学 | Preparation method of Li4Ti5O12-TiO2 composite electrode material |
| CN102956880A (en) * | 2012-11-15 | 2013-03-06 | 华中科技大学 | Method for preparing Li4Ti5O12-TiO2 (lithium titanate - titanium oxide) nano composite material and Li4Ti5O12-TiO2 nano composite material thereof |
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| 吕文俊等: "锂离子电池负极材料Li4Ti5O12的固相法制备及性能研究", 《化工新型材料》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115036489A (en) * | 2022-06-27 | 2022-09-09 | 电子科技大学 | Preparation method of high-safety lithium storage material based on lithium titanate heterostructure |
| CN115036489B (en) * | 2022-06-27 | 2023-11-17 | 电子科技大学 | Preparation method of lithium storage material based on lithium titanate heterostructure |
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