CN109473654A - Li4Ti5O12- TiN-TiC material and preparation method thereof - Google Patents
Li4Ti5O12- TiN-TiC material and preparation method thereof Download PDFInfo
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- CN109473654A CN109473654A CN201811399130.1A CN201811399130A CN109473654A CN 109473654 A CN109473654 A CN 109473654A CN 201811399130 A CN201811399130 A CN 201811399130A CN 109473654 A CN109473654 A CN 109473654A
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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
- H01M4/364—Composites as mixtures
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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
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Abstract
The invention belongs to lithium ion battery negative material fields in electrochmical power source, and in particular to Li4Ti5O12- TiN-TiC material and preparation method thereof.Technical problem to be solved by the invention is to provide a kind of Li4Ti5O12The preparation method of-TiN-TiC material, comprising the following steps: TiO2、Li2CO3, C and metal Ti mix 850~900 DEG C of sintering in a nitrogen atmosphere of gained mixture, obtain Li4Ti5O12- TiN-TiC material.One step of the method for the present invention modifies Li4Ti5O12The Li being prepared4Ti5O12- TiN-TiC material, the material have than Li4Ti5O12Better high rate performance.
Description
Technical field
The invention belongs to lithium ion battery negative material fields in electrochmical power source, and in particular to Li4Ti5O12- TiN-TiC material
Material and preparation method thereof.
Background technique
Lithium titanate (Li4Ti5O12) it is used as lithium ion battery negative material, there is superelevation safety, overlength cyclicity, wide in range
The advantages of operating temperature, however there is also compared with high working voltage 1.55V (vs.Li+/ Li), lower theoretical capacity 175mAhg-1, make
With being easy to produce the poor disadvantage of gas, high rate capability in the process.In conjunction with field of lithium battery application comprehensive analysis, can obtain as
Draw a conclusion: on the one hand, higher li voltage, lower reversible capacity are not suitable as 3C number lithium ion battery negative material；Separately
On the one hand, it is empty to be relatively suitable as electric car, peak load regulation network, photovoltaic for superelevation safety, overlength cyclicity, wide in range operating temperature
Adjust the extensive energy storage lithium ion battery negative electrode material such as power supply.
Since lithium titanate material belongs to stable Ti-O compound structure, one side cycle performance is good, on the other hand electricity
Son and outer ion migration rate in lattice are slow.The electronic conductivity of lithium titanate material is (ca.10-8~10-13S cm-1), ionic diffusion coefficient is (ca.10-9~10-16cm2s-1), decay in high power charging-discharging reversible capacity too fast, causes high power
Rate performance is performed poor, therefore is improved its high rate performance and had a very important significance.
The method that existing method improves lithium titanate material high rate performance is very more, respectively there is itself advantage and disadvantage.Such as pass through water
Thermal synthesis, high-temperature gas reduction process can form conductive materials TiN on lithium titanate surface, to improve lithium titanate material
Electron conduction, to improve the high rate performance of material.But this method preparation process is complicated, expensive used.
Summary of the invention
In view of the above-mentioned drawbacks of the prior art, present approach provides a kind of Li4Ti5O12- TiN-TiC material and
Preparation method, the Li that this method is prepared4Ti5O12- TiN-TiC material has than Li4Ti5O12Better electric conductivity.
First technical problem to be solved by this invention is to provide a kind of Li4Ti5O12The preparation side of-TiN-TiC material
Method.Method includes the following steps: TiO2、Li2CO3, C and metal Ti mix gained mixture in a nitrogen atmosphere 850~900
DEG C sintering, obtain Li4Ti5O12- TiN-TiC material.
Specifically, above-mentioned Li4Ti5O12In the preparation method of-TiN-TiC material, the TiO2Middle Ti and Li2CO3Middle lithium
Molar ratio is 5~5.5 ﹕ 4.
Specifically, above-mentioned Li4Ti5O12In the preparation method of-TiN-TiC material, the C is graphite powder or carbon dust.
Specifically, above-mentioned Li4Ti5O12In the preparation method of-TiN-TiC material, the additive amount of the C is TiO2With
Li2CO3The 1~2% of gross mass.
Specifically, above-mentioned Li4Ti5O12In the preparation method of-TiN-TiC material, the metal Ti granularity is less than 50 microns.
Specifically, above-mentioned Li4Ti5O12In the preparation method of-TiN-TiC material, the additive amount of the metal Ti is TiO2With
Li2CO3The 3~5% of gross mass.
Specifically, above-mentioned Li4Ti5O12In the preparation method of-TiN-TiC material, when roasting material mass when within 5g,
Nitrogen flow is 2m3/h。
Specifically, above-mentioned Li4Ti5O12In the preparation method of-TiN-TiC material, it is warming up to the heating rate of sintering temperature
For 10 DEG C of min-1。
Specifically, above-mentioned Li4Ti5O12In the preparation method of-TiN-TiC material, the sintering time is 6~8h.
Second technical problem to be solved by this invention is to provide above-mentioned Li4Ti5O12The preparation side of-TiN-TiC material
The Li that method is prepared4Ti5O12- TiN-TiC material.
The method of the present invention is by a step solid-phase sintering successfully in Li4Ti5O12On be added to TiN and TiC, to improve
The electron conduction of material.The Li that the method for the present invention obtains4Ti5O12- TiN-TiC material has than Li4Ti5O12Better multiplying power
Performance.
Detailed description of the invention
Fig. 1, Li of the present invention4Ti5O12- TiN-TiC and pure phase Li4Ti5O12XRD diagram；
Fig. 2, Li of the present invention4Ti5O12- TiN-TiC and pure phase Li4Ti5O12Raman spectrum；
Fig. 3, pure phase Li4Ti5O12With Li of the present invention4Ti5O12- TiN-TiC charging and discharging curve；Wherein, a) pure phase Li4Ti5O12
Charging and discharging curve, b) Li4Ti5O12- TiN-TiC charging and discharging curve.
Specific embodiment
The present invention is by solid phase synthesis process, with TiO2For titanium source, Li2CO3For lithium source, metallic titanium powder and graphite powder are added
Or carbon dust is sintered 6~8h in the nitrogen that mixture flows at 850~900 DEG C as mixing reducing agent, it will by reduction reaction
Ti in the lithium titanate of generation4+It is reduced to Ti3+, respectively with N2TiN and TiC is generated with C, so that it is bis- modified to form TiN and TiC
LTO-TiN-TiC composite material, solid powder become black and blue color powder, to generate stable Li4Ti5O12-TiN-TiC.This
Metallic titanium powder reacts with graphite powder, nitrogen during inventive method, and codope improves the electron conduction of lithium titanate, thus
Improve lithium titanate high rate performance.
Embodiment 1
With 13.1g TiO2As the initial titanium source of reaction, 4.88gLi2CO3As the initial lithium source of reaction, 4% is added
Metallic titanium powder and 2% graphite powder, in the agate mortar, first by TiO2And Li2CO3It is uniformly mixed using agate grinding rod, then
Graphite powder and metallic titanium powder are proportionally added into mixture, reuses stainless steel spoon and is uniformly mixed, above-mentioned substance is put
Enter in tube furnace, in N2Under gas shield, 6h is roasted under conditions of 850 DEG C of highest maturing temperature, obtains Li4Ti5O12-TiN-
TiC composite material.
Embodiment 2
With 13.1g TiO2As the initial titanium source of reaction, 4.88gLi2CO3As the initial lithium source of reaction, 3% is added
Metallic titanium powder and 1% graphite powder, in the agate mortar, first by TiO2And Li2CO3It is uniformly mixed using agate grinding rod, then
Graphite powder and metallic titanium powder are proportionally added into mixture, reuses stainless steel spoon and is uniformly mixed, above-mentioned substance is put
Enter in tube furnace, in N2Under gas shield, under conditions of 900 DEG C of highest maturing temperature, 8h is roasted, Li is obtained4Ti5O12-TiN-
TiC composite material.
Claims (10)
1.Li4Ti5O12The preparation method of-TiN-TiC material, it is characterised in that: the following steps are included: TiO2、Li2CO3, C and gold
Belong to Ti and mix 850~900 DEG C of sintering in a nitrogen atmosphere of gained mixture, obtains Li4Ti5O12- TiN-TiC material.
2. Li according to claim 14Ti5O12The preparation method of-TiN-TiC material, it is characterised in that: the TiO2In
Ti and Li2CO3The molar ratio of middle lithium is 5~5.5 ﹕ 4.
3. Li according to claim 14Ti5O12The preparation method of-TiN-TiC material, it is characterised in that: the C is graphite
Powder or carbon dust.
4. Li according to claim 2 or 34Ti5O12The preparation method of-TiN-TiC material, it is characterised in that: the C's
Additive amount is TiO2And Li2CO3The 1~2% of gross mass.
5. Li according to claim 14Ti5O12The preparation method of-TiN-TiC material, it is characterised in that: the metal Ti
Granularity is less than 50 microns.
6. Li according to claim 1 or 54Ti5O12The preparation method of-TiN-TiC material, it is characterised in that: the metal
The additive amount of Ti is TiO2And Li2CO3The 3~5% of gross mass.
7. described in any item Li according to claim 1~64Ti5O12The preparation method of-TiN-TiC material, it is characterised in that: when
Material mass is roasted when within 5g, nitrogen flow 2m3/h。
8. described in any item Li according to claim 1~74Ti5O12The preparation method of-TiN-TiC material, it is characterised in that: rise
The heating rate of temperature to sintering temperature is 10 DEG C of min-1。
9. described in any item Li according to claim 1~84Ti5O12The preparation method of-TiN-TiC material, it is characterised in that: institute
Stating sintering time is 6~8h.
10. by Li according to any one of claims 1 to 94Ti5O12What the preparation method of-TiN-TiC material was prepared
Li4Ti5O12- TiN-TiC material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811399130.1A CN109473654A (en) | 2018-11-22 | 2018-11-22 | Li4Ti5O12- TiN-TiC material and preparation method thereof |
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| CN201811399130.1A CN109473654A (en) | 2018-11-22 | 2018-11-22 | Li4Ti5O12- TiN-TiC material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118507695A (en) * | 2024-07-16 | 2024-08-16 | 深圳市贝特瑞新能源技术研究院有限公司 | Solid electrolyte coated graphite negative electrode material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442695A (en) * | 2010-10-09 | 2012-05-09 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium titanate material of lithium ion battery |
| US20150017524A1 (en) * | 2013-07-15 | 2015-01-15 | Posco Chemtech Co., Ltd. | Electrode active material for rechargeable lithium battery, method for preparing the same, electrode including the same, and rechargeable lithium battery including the electrode |
| CN107808954A (en) * | 2017-10-19 | 2018-03-16 | 清华大学深圳研究生院 | A kind of lithium titanate cladding hard carbon composite and preparation method thereof |
-
2018
- 2018-11-22 CN CN201811399130.1A patent/CN109473654A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442695A (en) * | 2010-10-09 | 2012-05-09 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium titanate material of lithium ion battery |
| US20150017524A1 (en) * | 2013-07-15 | 2015-01-15 | Posco Chemtech Co., Ltd. | Electrode active material for rechargeable lithium battery, method for preparing the same, electrode including the same, and rechargeable lithium battery including the electrode |
| CN107808954A (en) * | 2017-10-19 | 2018-03-16 | 清华大学深圳研究生院 | A kind of lithium titanate cladding hard carbon composite and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| BEILEI YAN ET AL: "Towards ultrafast lithium-ion batteries: A novel atomic layer deposition-seeded preparation of Li4Ti5O12-TiN-TiC anodes", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118507695A (en) * | 2024-07-16 | 2024-08-16 | 深圳市贝特瑞新能源技术研究院有限公司 | Solid electrolyte coated graphite negative electrode material and preparation method and application thereof |
| CN118507695B (en) * | 2024-07-16 | 2024-09-13 | 深圳市贝特瑞新能源技术研究院有限公司 | Solid electrolyte coated graphite negative electrode material and preparation method and application thereof |
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