CN104332604A - Preparation method of negative electrode material lithium titanate of lithium battery - Google Patents
Preparation method of negative electrode material lithium titanate of lithium battery Download PDFInfo
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- CN104332604A CN104332604A CN201410614733.4A CN201410614733A CN104332604A CN 104332604 A CN104332604 A CN 104332604A CN 201410614733 A CN201410614733 A CN 201410614733A CN 104332604 A CN104332604 A CN 104332604A
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- lithium
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- lithium titanate
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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 provides a preparation method of a negative electrode material lithium titanate of a lithium battery. The preparation method comprises the following steps of adding distilled water into a dissolvable lithium compound for dissolving; adding chitosan into a glacial acetic acid solution, carrying out ultrasound until dissolving completely to obtain a homogeneous light yellow liquid; adding titanium dioxide powder into a chitosan solution, carrying out ultrasound, and carrying out magnetic stirring for 10-60 minutes; adding the dissolved solution in the step a into the chitosan solution, and carrying out ultrasonic stirring for 10-60 minutes; adding epoxy chloropropane, and carrying out magnetic stirring continuously for 5-15 minutes; transferring the obtained solution into a petri dish, covering by a preservative film well, refrigerating at -80 DEG C, putting the refrigerated sample into a refrigeration dryer, vacuumizing, drying for 10-48 hours, putting the dried sample into a crucible, delivering into a tubular furnace at 600-900 DEG C, and forging for 8-15 hours, thereby obtaining the negative electrode material lithium titanate. The lithium titanate prepared by the method has an excellent high-rate discharge property, and is suitable for power batteries.
Description
Technical field
The present invention relates to a kind of preparation method of battery electrode material, particularly a kind of preparation method of lithium ion secondary battery cathode material lithium titanate.
Background technology
Lithium titanate is as a kind of novel negative material, and having the advantages such as good cycle, security performance is high, charge and discharge platform is steady, is one of the most excellent lithium ion battery negative material received much concern in recent years.But, due to Li
4ti
5o
12conductivity poor, when high current charge-discharge, capacity attenuation is fast, limits its application.And by doped metal ion and coated its electronic conductivity that can effectively improve of carbon, or by preparing nano particle, the evolving path reducing lithium ion improves the high rate performance of lithium titanate material.But due to the surface and interface effect of nano particle, surface energy is higher, surface activity is very large, and extremely unstable attracts each other between particle and reunites and reduce its surface energy and surface activity, thus losing the characteristic of nano particle gradually, long-term cycle performance is not ideal enough.
Summary of the invention
For existing preparation Li
4ti
5o
12shortcoming, the invention provides a kind of preparation method being applied to the lithium titanate anode material of lithium ion battery.
A preparation method for lithium cell negative pole material lithium titanate, is characterized in that, concrete steps are:
The soluble compound of a, weighing lithium, adds distilled water and dissolves;
B, weighing shitosan join in glacial acetic acid solution, ultrasonic to being dissolved as homogeneous weak yellow liquid completely;
C, in chitosan solution, add titania powder, ultrasonic, magnetic agitation 10 ~ 60 minutes; Add in the solution dissolved in a step in chitosan solution, ultrasonic agitation 10 ~ 60 minutes;
D, in the obtained solution of step c, add epoxychloropropane, continuing magnetic force stirs 5 ~ 15 hours; Gained solution is transferred in culture dish, build with preservative film, freezing at-80 DEG C, the sample freezed is put into freeze drier, vacuumize, dry 10 ~ 48 hours, crucible put into by dried sample, under feeding tube furnace, 600 ~ 900 DEG C of calcining 8-15 hour, obtain lithium cell negative pole material lithium titanate.
The soluble compound of described lithium is the one or its combination that lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, isopropyl lithium alkoxide are heavy, or containing the Organic Alcohol of lithium, acid, ester type compound.
Mol ratio in the soluble compound of described lithium and titanium dioxide is Li:Ti=0.8 ~ 1.2.
The solubility that in described step c, titanium dioxide adds is 0.1 ~ 0.7mol/L.
The volume of described acetic acid is 80 ~ 220 times of chitosan mass.
The volume of the solution that described step c obtains is epoxychloropropane volume is 40 ~ 300 times.
The lithium titanate anode material adopting method of the present invention to prepare shows certain mesoporous characteristic, and this lithium titanate anode material has excellent large rate discharge characteristic.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the embodiment of the present invention 1 product.
Embodiment
Below embodiments of the invention are elaborated: the present embodiment is implemented under premised on technical solution of the present invention, give detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1: weigh 0.8685g lithium acetate, the distilled water adding 10ml dissolves; The shitosan weighing 0.2375g again adds in the glacial acetic acid solution of 43.5ml, ultrasonic to being dissolved as homogeneous weak yellow liquid completely; 0.87g titania powder is added in chitosan solution, ultrasonic, magnetic agitation 20min; In chitosan solution, add the lithium acetate solution dissolved, stir 10min; Adding the epoxychloropropane of 0.4ml in above-mentioned solution, continuing magnetic force stirs 15h, solution is transferred in culture dish, builds with preservative film, freezing at-80 DEG C, the sample freezed is put into freeze drier, vacuumize, dry 24h, obtain in spongiform white pigmented samples, calcine 10h at sample being put into 800 DEG C, formula stove, be prepared into end product.Fig. 1 is the XRD figure of gained sample.Visible, the XRD of synthetic product schemes the position of each diffraction maximum and relative intensity is equal and Li
4ti
5o
12standard card match, without any dephasign.
Embodiment 2: weigh 0.92g lithium nitrate, the distilled water adding 10ml dissolves; The shitosan weighing 0.248g again adds in the glacial acetic acid solution of 50ml, ultrasonic to being dissolved as homogeneous weak yellow liquid completely; 0.68g titania powder is added in chitosan solution, ultrasonic, magnetic agitation 40min; In chitosan solution, add the lithium acetate solution dissolved, stir 20min; Adding the epoxychloropropane of 0.5ml in above-mentioned solution, continuing magnetic force stirs 5h, solution is transferred in culture dish, builds with preservative film, freezing at-80 DEG C, the sample freezed is put into freeze drier, vacuumize, dry 10h, obtain in spongiform white pigmented samples, calcine 15h at sample being put into 600 DEG C, formula stove, be prepared into end product.
Embodiment 3: weigh 0.74g lithium citrate, the distilled water adding 10ml dissolves; The shitosan weighing 0.315g again adds in the glacial acetic acid solution of 80ml, ultrasonic to being dissolved as homogeneous weak yellow liquid completely; 0.8g titania powder is added in chitosan solution, ultrasonic, magnetic agitation 50min; In chitosan solution, add the lithium acetate solution dissolved, stir 40min; Adding the epoxychloropropane of 0.6ml in above-mentioned solution, continuing magnetic force stirs 15h, solution is transferred in culture dish, builds with preservative film, freezing at-80 DEG C, the sample freezed is put into freeze drier, vacuumize, dry 48h, obtain in spongiform white pigmented samples, calcine 8h at sample being put into 900 DEG C, formula stove, be prepared into end product.
Embodiment 4:: weigh 0.87g lithium formate, the distilled water adding 10ml dissolves; The shitosan weighing 0.2856g again adds in the glacial acetic acid solution of 100ml, ultrasonic to being dissolved as homogeneous weak yellow liquid completely; 0.68g titania powder is added in chitosan solution, ultrasonic, magnetic agitation 40min; In chitosan solution, add the lithium acetate solution dissolved, stir 40min; Adding the epoxychloropropane of 0.7ml in above-mentioned solution, continuing magnetic force stirs 8h, solution is transferred in culture dish, builds with preservative film, freezing at-80 DEG C, the sample freezed is put into freeze drier, vacuumize, dry 30, obtain in spongiform white pigmented samples, calcine 15h at sample being put into 800 DEG C, formula stove, be prepared into end product.
Claims (6)
1. a preparation method for lithium cell negative pole material lithium titanate, is characterized in that, concrete steps are:
The soluble compound of a, weighing lithium, adds distilled water and dissolves;
B, weighing shitosan join in glacial acetic acid solution, ultrasonic to being dissolved as homogeneous weak yellow liquid completely;
C, in chitosan solution, add titania powder, ultrasonic, magnetic agitation 10 ~ 60 minutes; Add in the solution dissolved in a step in chitosan solution, ultrasonic agitation 10 ~ 60 minutes;
D, in the obtained solution of step c, add epoxychloropropane, continuing magnetic force stirs 5 ~ 15 hours; Gained solution is transferred in culture dish, build with preservative film, freezing at-80 DEG C, the sample freezed is put into freeze drier, vacuumize, dry 10 ~ 48 hours, crucible put into by dried sample, under feeding tube furnace, 600 ~ 900 DEG C of calcining 8-15 hour, obtain lithium cell negative pole material lithium titanate.
2. the preparation method of a kind of lithium cell negative pole material lithium titanate according to claim 1, it is characterized in that, the soluble compound of described lithium is the one or its combination that lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, isopropyl lithium alkoxide are heavy, or containing the Organic Alcohol of lithium, acid, ester type compound.
3. the preparation method of a kind of lithium cell negative pole material lithium titanate according to claim 1, is characterized in that, the mol ratio in the soluble compound of described lithium and titanium dioxide is Li:Ti=0.8 ~ 1.2.
4. the preparation method of a kind of lithium cell negative pole material lithium titanate according to claim 1, it is characterized in that, the solubility that in described step c, titanium dioxide adds is 0.1 ~ 0.7mol/L.
5. the preparation method of a kind of lithium cell negative pole material lithium titanate according to claim 1, it is characterized in that, the volume of described acetic acid is 80 ~ 220 times of chitosan mass.
6. the preparation method of a kind of lithium cell negative pole material lithium titanate according to claim 1, it is characterized in that, the volume of the solution that described step c obtains is epoxychloropropane volume is 40 ~ 300 times.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105118978A (en) * | 2015-07-10 | 2015-12-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of freeze-dried doped modified lithium titanate |
| CN107221647A (en) * | 2017-07-18 | 2017-09-29 | 华南师范大学 | A kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material |
| CN107863496A (en) * | 2017-07-19 | 2018-03-30 | 清华大学深圳研究生院 | Lithium ion battery negative material and preparation method thereof |
| CN109473670A (en) * | 2018-12-18 | 2019-03-15 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of ion secondary battery cathode material lithium fluorine richness lithium titanate and application |
| CN110518233A (en) * | 2019-09-16 | 2019-11-29 | 广东工业大学 | Graphite-doping lithium titanate anode material and preparation method thereof |
| CN110550654A (en) * | 2019-09-16 | 2019-12-10 | 广东工业大学 | Modified lithium titanate negative electrode material, preparation method thereof and battery |
| CN110571428A (en) * | 2019-09-16 | 2019-12-13 | 广东工业大学 | Pure-phase lithium titanate negative electrode material, preparation method thereof, negative electrode and battery |
| CN110563031A (en) * | 2019-09-16 | 2019-12-13 | 广东工业大学 | Lithium titanate negative electrode material, preparation method thereof and battery |
| CN111092219A (en) * | 2019-12-20 | 2020-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of modified lithium titanate negative electrode material applied to lithium ion battery |
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| CN103771500A (en) * | 2012-10-18 | 2014-05-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lithium ion secondary battery with nanometer lithium titanate simultaneously doped at A and B site |
| CN104022275A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Freeze-drying micro-emulsion method for preparing lithium titanate material for lithium-battery electrode |
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Patent Citations (3)
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| US20110084238A1 (en) * | 2008-05-30 | 2011-04-14 | Basf Se | Process for preparing lithium vanadium oxides and their use as cathode material |
| CN103771500A (en) * | 2012-10-18 | 2014-05-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of lithium ion secondary battery with nanometer lithium titanate simultaneously doped at A and B site |
| CN104022275A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Freeze-drying micro-emulsion method for preparing lithium titanate material for lithium-battery electrode |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105118978A (en) * | 2015-07-10 | 2015-12-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of freeze-dried doped modified lithium titanate |
| CN105118978B (en) * | 2015-07-10 | 2017-05-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of freeze-dried doped modified lithium titanate |
| CN107221647A (en) * | 2017-07-18 | 2017-09-29 | 华南师范大学 | A kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material |
| CN107221647B (en) * | 2017-07-18 | 2019-10-22 | 华南师范大学 | A kind of preparation method of nitrogen-doped titanic acid lithium/graphene nanocomposite material |
| CN107863496A (en) * | 2017-07-19 | 2018-03-30 | 清华大学深圳研究生院 | Lithium ion battery negative material and preparation method thereof |
| CN109473670A (en) * | 2018-12-18 | 2019-03-15 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of ion secondary battery cathode material lithium fluorine richness lithium titanate and application |
| CN110518233A (en) * | 2019-09-16 | 2019-11-29 | 广东工业大学 | Graphite-doping lithium titanate anode material and preparation method thereof |
| CN110550654A (en) * | 2019-09-16 | 2019-12-10 | 广东工业大学 | Modified lithium titanate negative electrode material, preparation method thereof and battery |
| CN110571428A (en) * | 2019-09-16 | 2019-12-13 | 广东工业大学 | Pure-phase lithium titanate negative electrode material, preparation method thereof, negative electrode and battery |
| CN110563031A (en) * | 2019-09-16 | 2019-12-13 | 广东工业大学 | Lithium titanate negative electrode material, preparation method thereof and battery |
| CN111092219A (en) * | 2019-12-20 | 2020-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of modified lithium titanate negative electrode material applied to lithium ion battery |
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