CN106532003A - Ti4O7-coated modified lithium titanate composite material and preparation method thereof - Google Patents
Ti4O7-coated modified lithium titanate composite material and preparation method thereof Download PDFInfo
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- CN106532003A CN106532003A CN201611117064.5A CN201611117064A CN106532003A CN 106532003 A CN106532003 A CN 106532003A CN 201611117064 A CN201611117064 A CN 201611117064A CN 106532003 A CN106532003 A CN 106532003A
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- Prior art keywords
- lithium titanate
- titanium
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- oxide
- coated modified
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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
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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 discloses a Ti4O7-coated modified lithium titanate composite material and a preparation method thereof. A chemical formula of the Ti4O7-coated modified lithium titanate composite material is Li4Ti5O12/Ti4O7. According to the technical scheme, lithium titanate is modified by adopting Ti4O7 with good conductivity and corrosion resistance as a coating layer, and a layer of Ti4O7 film coats the surface of the lithium titanate, so that the conductivity of the lithium titanate is effectively improved, corrosion of an electrolyte to a lithium titanate material is inhibited, the rate capability and the cycle performance are significantly improved, the Ti4O7-coated modified lithium titanate composite material adapts to the requirements of a power lithium-ion battery, and furthermore, the technique is simple in operation process and suitable for industrial production.
Description
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of sub- titanium-oxide-coated modified lithium titanate composite wood
Material and preparation method thereof.
Background technology
Spinel type lithium titanate becomes carbon with its excellent properties as a kind of new cathode material of lithium-ion power battery
The substitution material of negative material.In charge and discharge process, the embedded and abjection of lithium ion will not cause crystal to tie to the material substantially
Structure changes, and is referred to as " zero strain material ".Also, lithium titanate has higher intercalation potential, is difficult to form Li dendrite, with very
Good security performance.But, as lithium titanate electric conductivity is poor, its specific capacity decays in high power charging-discharging rapidly, and this is
The key of lithium titanate Commercialization application is restricted at present.Therefore, extensive application of the lithium titanate in power lithium-ion battery is realized,
Need to improve the electric conductivity of the material.Using increase specific surface area, modification by ion-doping and conductive phase doping more than conventional method
And coating modification.Wherein, the covering material used in coating modification method mainly adopts material with carbon element.But material with carbon element corrosion resistance
Difference, and during Lithium-ion embeding abjection, structure is susceptible to change, causes cycle performance of lithium ion battery poor.
The content of the invention
For prior art problem, the invention discloses a kind of sub- titanium-oxide-coated modified lithium titanate composite and its system
Preparation Method, its innovation are the design of composite and preparation method.The sub- titanium-oxide-coated Modified Titanium that the present invention is provided
Sour lithium composite material chemical formula is Li4Ti5O12/Ti4O7.Sub- titanium oxide (Ti4O7) electric conductivity and decay resistance be superior to carbon
Material, can effectively reduce internal resistance, improve the high rate performance of lithium titanate material.The preparation method that the present invention is provided, step are as follows:
Step 1 lithium titanate powder is dried 2 ~ 10h at 30 ~ 200 DEG C;
Step 2 is added in dehydrated alcohol butyl titanate after stirring, sequentially adds acetic acid and deionized water, after 3 ~ 24h of stirring
Sol solution is obtained, wherein, the butyl titanate and the volume ratio of acetic acid stated is (2 ~ 5.5):1, the consumption of the deionized water
For the 1/10 of butyl titanate volume;
Step 3 is added to the lithium titanate described in step 1 in the sol solution described in step 2, vacuum filtration after 6 ~ 48h of stirring,
2 ~ 10h is dried at 30 ~ 150 DEG C and obtains precursor powder, the amount ratio of the lithium titanate and the material of butyl titanate for (4.5~
11):1;
Precursor powder described in step 3 is reduced 3 ~ 6h in 830~870 DEG C by step 4 in a hydrogen atmosphere, is cooled to 100 DEG C
Under come out of the stove, that is, obtain sub- titanium-oxide-coated modified lithium titanate composite.
In said method, the volume ratio of butyl titanate and dehydrated alcohol is 1:(2~4).
The invention has the advantages that:
The present invention carries out coating modification to lithium titanate material using the sub- titanium oxide with high conductivity, is formed on lithium titanate surface
One layer of sub- thin film of titanium oxide, significantly improves the electric conductivity of lithium titanate.Sub- titanium oxide is used as a kind of high conductivity material, chemically stable
Property it is excellent, it is corrosion-resistant under the conditions of high current density or peracid and be not susceptible to passivation.Therefore, the modified metatitanic acid of sub- titanium-oxide-coated
Lithium composite material can further improve the high rate performance and stable circulation performance of lithium titanate material.And, technical solution of the present invention
Simple process it is easy to operate, be adapted to industrialized production.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture of sub- titanium-oxide-coated modified lithium titanate composite prepared by embodiment 1.
Fig. 2 is sub- titanium-oxide-coated modified lithium titanate composite constant current charge-discharge curve chart prepared by embodiment 1.
Specific embodiment
With reference to embodiment, describe the present invention.
Embodiment 1
(1)Nanoscale lithium titanate powder is dried into 2h at 200 DEG C;(2)By butyl titanate and dehydrated alcohol by volume 1:4 adopt
Stirred with agitator, gradually Deca acetic acid and deionized water successively in whipping process, the volume ratio of acetic acid and butyl titanate
For 1:5.5, deionized water is 1 with the volume ratio of butyl titanate:10, stirring 3h obtains uniform sol solution;(3)According to lithium titanate
Compare 4.5 with the amount of the material of butyl titanate:1, lithium titanate powdery is added in titania sol solution, is carried out after stirring 6h true
Empty sucking filtration, and precursor powder is obtained in 30 DEG C of vacuum drying 10h;(4)830 DEG C of reduction in hydrogen atmosphere stove by precursor powder
6h, is cooled at 100 DEG C and comes out of the stove, and obtains final product sub- titanium-oxide-coated modified lithium titanate composite.
With lithium piece as negative pole, in the glove box full of argon, button cell is made, constant current is done in 1 ~ 3V voltage ranges
Charge-discharge test, under 0.2C, 0.5C, 1C, 2C, 5C, 10C multiplying power, capacity be respectively 166.2mAh/g, 162.1mAh/g,
160.2 mAh/g、156.6 mAh/g、147.5 mAh/g、137.1 mAh/g。
Embodiment 2
(1)Micron order lithium titanate powder is dried into 10h at 30 DEG C;(2)By butyl titanate and dehydrated alcohol by volume 1:2 adopt
It is uniform with magnetic agitation, gradually Deca acetic acid and deionized water successively in whipping process, acetic acid with the volume ratio of butyl titanate is
1:2, deionized water is 1 with the volume ratio of butyl titanate:10, stirring 24h obtains uniform sol solution;(3)According to lithium titanate with
The amount of the material of butyl titanate compares 11:1, lithium titanate powdery is added in titania sol solution, after stirring 48h, vacuum is carried out
Sucking filtration, and precursor powder is obtained in 150 DEG C of vacuum drying 2h;(4)870 DEG C of reduction in hydrogen atmosphere stove by precursor powder
3h, is cooled at 100 DEG C and comes out of the stove, obtain final product the lithium titanate composite material of sub- titanium-oxide-coated.
With lithium piece as negative pole, in the glove box full of argon, button cell is made, constant current is done in 1 ~ 3V voltage ranges
Charge-discharge test, under 0.2C, 0.5C, 1C, 2C, 5C, 10C multiplying power, capacity be respectively 168.3mAh/g, 165.2mAh/g,
162.2 mAh/g、159.5 mAh/g、149.5 mAh/g、138.1 mAh/g。
Claims (4)
1. a kind of sub- titanium-oxide-coated modified lithium titanate composite, it is characterised in that:The lithium titanate surface of the composite
Sub- titanium oxide is coated with, its chemical formula is Li4Ti5O12/Ti4O7。
2. sub- titanium-oxide-coated modified lithium titanate composite according to claim 1, it is characterised in that:Using following step
Suddenly prepare:
Step 1 lithium titanate powder is dried 2 ~ 10h at 30 ~ 200 DEG C;
Step 2 is added to butyl titanate in dehydrated alcohol and stirs, and is gradually added into acetic acid and deionized water successively, stirs 3 ~ 24h
After obtain sol solution, wherein, the volume ratio of the butyl titanate and acetic acid is (2 ~ 5.5):1, the consumption of the deionized water
For the 1/10 of butyl titanate volume;
Step 3 is added to the lithium titanate described in step 1 in the sol solution described in step 2, vacuum filtration after 6 ~ 48h of stirring,
2 ~ 10h is dried at 30 ~ 150 DEG C and obtains precursor powder;
Precursor powder in step 3 is sintered 3 ~ 6h in 830~870 DEG C by step 4 in a hydrogen atmosphere, is cooled at 100 DEG C
Come out of the stove, that is, obtain sub- titanium-oxide-coated modified lithium titanate composite.
3. sub- titanium-oxide-coated modified lithium titanate composite material preparation according to claim 2, it is characterised in that titanium
Sour lithium is (4.5~11) with the amount ratio of the material of butyl titanate:1.
4. sub- titanium-oxide-coated modified lithium titanate composite material preparation according to claim 2, it is characterised in that titanium
The volume ratio of acid butyl ester and dehydrated alcohol is 1:(2~4).
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109449408A (en) * | 2018-10-30 | 2019-03-08 | 中科廊坊过程工程研究院 | A kind of ferric flouride-Asia titanium oxide composite positive pole and its preparation method and application |
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CN102496704A (en) * | 2011-12-08 | 2012-06-13 | 中信国安盟固利电源技术有限公司 | Lithium titanate/titanium black anode material and preparation method thereof |
US20150108399A1 (en) * | 2007-08-10 | 2015-04-23 | Kabushiki Kaisha Toshiba | Active material for battery, manufacturing method of the same, non-aqueous electrolytic battery and battery pack |
CN105489864A (en) * | 2016-01-13 | 2016-04-13 | 李震祺 | Titanium sub-oxide coated and modified lithium iron phosphate composite material and preparation method thereof |
-
2016
- 2016-12-07 CN CN201611117064.5A patent/CN106532003A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US20150108399A1 (en) * | 2007-08-10 | 2015-04-23 | Kabushiki Kaisha Toshiba | Active material for battery, manufacturing method of the same, non-aqueous electrolytic battery and battery pack |
CN102496704A (en) * | 2011-12-08 | 2012-06-13 | 中信国安盟固利电源技术有限公司 | Lithium titanate/titanium black anode material and preparation method thereof |
CN105489864A (en) * | 2016-01-13 | 2016-04-13 | 李震祺 | Titanium sub-oxide coated and modified lithium iron phosphate composite material and preparation method thereof |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109449408A (en) * | 2018-10-30 | 2019-03-08 | 中科廊坊过程工程研究院 | A kind of ferric flouride-Asia titanium oxide composite positive pole and its preparation method and application |
CN109449408B (en) * | 2018-10-30 | 2021-08-17 | 中科廊坊过程工程研究院 | Ferric fluoride-titanium suboxide composite positive electrode material and preparation method and application thereof |
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