CN108155372B - Lithium titanate material and preparation and application thereof - Google Patents
Lithium titanate material and preparation and application thereof Download PDFInfo
- Publication number
- CN108155372B CN108155372B CN201611098897.1A CN201611098897A CN108155372B CN 108155372 B CN108155372 B CN 108155372B CN 201611098897 A CN201611098897 A CN 201611098897A CN 108155372 B CN108155372 B CN 108155372B
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- lithium titanate
- fluorinated
- fluorinated graphene
- graphite
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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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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- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a modified lithium titanate material which is prepared by mixing lithium titanate powder and fluorinated graphene and/or fluorinated graphite according to a mass ratio of 100: 1-1: 4. The lithium titanate electrode material is used in lithium titanate batteries or lithium titanate capacitors as an electrode material. Effectively inhibiting the problem of flatulence of the lithium titanate battery.
Description
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a lithium titanate battery and a lithium titanate capacitor.
Background
Spinel type Lithium Titanate (LTO), since it is not substantially deformed during charge and discharge, is called a zero strain electrode material. Has good application prospect. The advantages of LTO are mainly reflected in the following aspects: 1. LTO has a large solid diffusion coefficient of lithium ions and excellent fast charge and fast discharge performance (5 min > 80% DOD); 2. compared with negative electrodes such as graphite, LTO has good low-temperature performance; 3. the safety is good. Potential safety hazards such as lithium separation dendrites of negative electrodes such as graphite cannot occur. 4. Excellent cycle performance. In conclusion, the lithium titanate material has excellent structural stability and safety performance, so the lithium titanate material is considered to be an excellent cathode material of a power lithium battery and a hybrid capacitor, and has wide application prospects in electric vehicles and large-scale energy storage.
However, no mature industrialization development has been achieved so far, and the main reason is that lithium titanate batteries have a "gas expansion problem" in the charge-discharge cycle and storage process, that is, the battery performance is rapidly reduced due to the continuous generation of gas inside the battery, which is the biggest obstacle restricting the practical application, and has become the consensus in the industry. Only by solving the problem of flatulence, the lithium titanate battery can be really practical.
Disclosure of Invention
In order to solve the main technical problems mentioned above, a lithium titanate with a good flatulence-inhibiting function and a preparation method thereof are provided.
In order to achieve the purpose, the invention adopts the specific technical scheme that a lithium titanate material containing fluorinated graphene (or graphite fluoride) is prepared, so that the fluorinated graphene (or graphite fluoride) can protect lithium titanate and inhibit flatulence.
The lithium titanate powder is mixed with fluorinated graphene and/or fluorinated graphite according to a mass ratio of 100: 1-1: 4.
The mass ratio of the lithium titanate powder to the fluorinated graphene and/or the fluorinated graphite is 20: 1-1: 2.
The lithium titanate powder is one or a mixture of lithium titanate and doped lithium titanate; the particle size of the lithium titanate powder is 0.02-100 microns;
the doped lithium titanate contains one or more than two of aluminum, boron, potassium, manganese, nickel and iron oxide red, and the doping amount is 0.01-10 wt%.
The fluorine-carbon ratio of the fluorinated graphene or the fluorinated graphite is 0.3-1.3, wherein the fluorine-carbon ratio is preferably 0.6-1.2, and the most preferably 0.8-1.1.
The preparation method of the lithium titanate material comprises the steps of putting lithium titanate powder and fluorinated graphene and/or fluorinated graphite into a solvent, carrying out ultrasonic dispersion for 0.1-12 hours, centrifuging, removing a supernatant, and carrying out vacuum drying on a precipitate at 70-120 ℃ to obtain the lithium titanate material.
The ultrasonic frequency is set to be 20-50 KHZ.
The solvent is one or a mixture of more than two of acetone, ethanol, isopropanol, formic acid, acetic acid and butanol; one or both of acetone and ethanol are preferable.
The mass ratio of the lithium titanate powder in the solvent is 1-50%.
The lithium titanate material is used as an electrode material for a lithium titanate battery or a lithium titanate capacitor. The invention has the advantages of
In the ultrasonic process, the graphene fluoride (or graphite fluoride) and lithium titanate are effectively compounded, and fluorine on the surface of the graphite fluoride and hydroxyl of the lithium titanate form a hydrogen bond, so that the surface of the lithium titanate is passivated, and further lithium titanate flatulence is inhibited.
Detailed Description
Examples 1,
Putting 10g of lithium titanate powder with the particle size of 10 microns and 5g of fluorinated graphene into 100ml of absolute ethyl alcohol, performing ultrasonic dispersion for 10 hours, centrifuging, removing supernate, and drying the precipitate in vacuum at 100 ℃ to obtain the lithium titanate material containing the fluorinated graphene.
Examples 2,
Putting 10g of lithium titanate powder with the particle size of 20 microns and 4g of graphite fluoride into 100ml of acetone, performing ultrasonic dispersion for 12 hours, centrifuging, removing supernatant, and performing vacuum drying on the precipitate at 80 ℃ to obtain the lithium titanate material containing the graphene fluoride.
Examples 3,
Putting 10g of lithium titanate powder with the particle size of 50 microns and 5g of fluorinated graphene into 100ml of absolute ethyl alcohol, performing ultrasonic dispersion for 10 hours, centrifuging, removing supernate, and performing vacuum drying on the precipitate at 100 ℃ to obtain the lithium titanate material containing the fluorinated graphene.
Examples 4,
Putting 10g of lithium titanate powder with the particle size of 1 micron and 5g of fluorinated graphene into 100ml of absolute ethyl alcohol, performing ultrasonic dispersion for 10 hours, centrifuging, removing supernatant, and performing vacuum drying on the precipitate at 100 ℃ to obtain the lithium titanate material containing the fluorinated graphene.
Comparative examples 1,
10g of lithium titanate powder with the particle size of 10 microns is put into 100ml of absolute ethyl alcohol, ultrasonic dispersion is carried out for 10 hours, centrifugation is carried out, supernatant is removed, and the precipitate is dried in vacuum at 100 ℃, so as to obtain the comparative lithium titanate material.
Table 1 shows cycle thickness variation data and energy density (based on active material) of a 053048 type square battery assembled from lithium titanate batteries, under the test conditions of 60 ℃, 2C charge-discharge cycle, and cutoff voltage of 1.6-2.8V.
TABLE 1
It can be seen that the lithium titanate material containing fluorinated graphene (or fluorinated graphite) has significantly less thickness variation than the lithium titanate assembled cell of the comparative example; the fluorinated graphene (or the fluorinated graphite) can well inhibit lithium titanate flatulence, and the energy density of the battery cannot be influenced.
Claims (7)
1. A preparation method of a modified lithium titanate material is characterized by comprising the following steps: the modified lithium titanate material is prepared by mixing lithium titanate powder and fluorinated graphene and/or fluorinated graphite according to a mass ratio of 100: 1-1: 4,
the preparation method comprises the following steps:
the preparation method of the modified lithium titanate material comprises the steps of putting lithium titanate powder and fluorinated graphene and/or fluorinated graphite into a solvent, carrying out ultrasonic dispersion for 0.1-12 hours, centrifuging, removing a supernatant, and drying a precipitate at 70-120 ℃ in vacuum to obtain the modified lithium titanate material; the ultrasonic frequency is set to be 20-50kHz, and the mass ratio of the lithium titanate powder in the solvent is 1% -50%.
2. The method of claim 1, wherein:
the mass ratio of the modified lithium titanate powder to the fluorinated graphene and/or the fluorinated graphite is 20: 1-1: 2.
3. The method of claim 1, wherein:
the modified lithium titanate powder is one or a mixture of lithium titanate and doped lithium titanate; the particle size of the modified lithium titanate powder is 0.02-100 microns;
the doped lithium titanate contains one or more than two of aluminum, boron, potassium, manganese, nickel and iron oxide red, and the doping amount is 0.01-10 wt%.
4. The method of claim 1, wherein:
the fluorine-carbon ratio of the fluorinated graphene or the fluorinated graphite is 0.3-1.3.
5. The method of claim 4, wherein:
the fluorine-carbon ratio of the fluorinated graphene or the fluorinated graphite is 0.6-1.2.
6. The method of claim 5, wherein:
the fluorine-carbon ratio of the fluorinated graphene or the fluorinated graphite is 0.8-1.1.
7. The method of claim 1, wherein:
the solvent is one or a mixture of more than two of acetone, ethanol, isopropanol, formic acid, acetic acid and butanol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611098897.1A CN108155372B (en) | 2016-12-04 | 2016-12-04 | Lithium titanate material and preparation and application thereof |
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| CN201611098897.1A CN108155372B (en) | 2016-12-04 | 2016-12-04 | Lithium titanate material and preparation and application thereof |
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| CN108155372A CN108155372A (en) | 2018-06-12 |
| CN108155372B true CN108155372B (en) | 2020-05-26 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111244402B (en) * | 2018-11-29 | 2021-05-04 | 中国科学院大连化学物理研究所 | Fluorinated graphene modified lithium titanate material, preparation and application |
| CN114551844A (en) * | 2022-03-01 | 2022-05-27 | 深圳博磊达新能源科技有限公司 | Lithium titanate composite negative electrode material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2083463B1 (en) * | 2006-10-18 | 2011-07-27 | Panasonic Corporation | Lithium primary battery |
| CN102569769A (en) * | 2012-02-24 | 2012-07-11 | 清华大学深圳研究生院 | Preparation method for lithium titanate and graphene composite electrode materials |
| CN103563156A (en) * | 2012-03-30 | 2014-02-05 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary cell and method for manufacturing same |
| CN105098166A (en) * | 2014-05-07 | 2015-11-25 | 江南大学 | Preparation method for high-performance graphene lithium titanate composite battery material |
| WO2016047031A1 (en) * | 2014-09-26 | 2016-03-31 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
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- 2016-12-04 CN CN201611098897.1A patent/CN108155372B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2083463B1 (en) * | 2006-10-18 | 2011-07-27 | Panasonic Corporation | Lithium primary battery |
| CN102569769A (en) * | 2012-02-24 | 2012-07-11 | 清华大学深圳研究生院 | Preparation method for lithium titanate and graphene composite electrode materials |
| CN103563156A (en) * | 2012-03-30 | 2014-02-05 | 松下电器产业株式会社 | Non-aqueous electrolyte secondary cell and method for manufacturing same |
| CN105098166A (en) * | 2014-05-07 | 2015-11-25 | 江南大学 | Preparation method for high-performance graphene lithium titanate composite battery material |
| WO2016047031A1 (en) * | 2014-09-26 | 2016-03-31 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| 《石墨烯用于锂离子电池负极材料的应用基础研究》;王赟;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20140930;18-20 * |
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