CN109473670A - The preparation method and product of ion secondary battery cathode material lithium fluorine richness lithium titanate and application - Google Patents
The preparation method and product of ion secondary battery cathode material lithium fluorine richness lithium titanate and application Download PDFInfo
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- CN109473670A CN109473670A CN201811553408.6A CN201811553408A CN109473670A CN 109473670 A CN109473670 A CN 109473670A CN 201811553408 A CN201811553408 A CN 201811553408A CN 109473670 A CN109473670 A CN 109473670A
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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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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides preparation method of a kind of lithium ion battery negative material fluorine richness lithium titanate and products thereof and application, and the molecular formula of fluorine richness lithium titanate anode material is Li4+xTi5O12‑yFy, the fluorine richness lithium titanate that has excellent performance is made by freeze-drying micro emulsion method, distilled water dissolution is added in the soluble compound and LiF of Li, and chitosan is added in glacial acetic acid solution, and ultrasound is to being completely dissolved as uniform weak yellow liquid；Titania powder is added into chitosan solution, epoxychloropropane is added, solution is transferred in culture dish, is freezed at -80 DEG C, the sample freezed vacuum drying calcining is obtained into the lithium titanate anode material applied to lithium ion battery.The lithium titanate of this method preparation has excellent big rate discharge characteristic, is suitable for power battery use.
Description
Technical field
The present invention relates to a kind of preparation method of battery electrode material, especially a kind of ion secondary battery cathode material lithium
Fluorine richness lithium titanate Li4+xTi5O12-yFyThe preparation method of (0 < x≤0.03,0.01 < y≤1) and products thereof and application.
Background technique
With the fast development of traffic, communication and information industry, energy of more and more electronic products to electrochmical power source
More stringent requirements are proposed for density and power.It is excellent that lithium ion battery has that energy density is high, power density is high, has extended cycle life etc.
Point, rapidly developing becomes one of currently the most important ones secondary cell.Lithium ion battery used currently on the market, is substantially with carbon
Material is cathode, but carbon material is that there are also some weakness for being difficult to overcome in practical applications for cathode, for example, discharging for the first time
Cheng Zhongyu electrolyte reacts to form surface passivated membrane, leads to the consumption of electrolyte and coulombic efficiency is lower for the first time；Carbon electrode
Current potential and lithium metal current potential very close to, when the battery is overcharged, the easy precipitating metal lithium of carbon electrodes, consequently, it is possible to shape
Cause short circuit at Li dendrite, and then leads to battery explosion.In order to solve the safety problem of lithium battery, people, which have done, largely to be ground
Study carefully.
Lithium titanate has good cycle, security performance height, charge and discharge platform steady as a kind of novel negative electrode material
The advantages that, it is most excellent one of the lithium ion battery negative material being concerned in recent years.But due to Li4Ti5O12's
Electric conductivity is poor, and in high current charge-discharge, capacity attenuation is fast, limits its application.And pass through doped metal ion and carbon
Cladding can effectively improve its electronic conductivity, or by preparing nano particle, reduce the diffusion path of lithium ion to mention
The high rate performance of high lithium titanate material.But surface and interfacial effect due to nanoparticle, surface can be higher, surface-active
It is very big, it is extremely unstable, it attracts each other between particle and reunites and reduce its surface energy and surface-active, to gradually lose nanoparticle
The characteristic of son, long-term cycle performance are not ideal enough.
Summary of the invention
For existing preparation Li4Ti5O12The shortcomings that, it is an object of that present invention to provide a kind of lithium ion secondary battery negative pole materials
Expect the preparation method of fluorine richness lithium titanate.
Another object of the present invention is: the ion secondary battery cathode material lithium fluorine for providing a kind of above method preparation changes
Property lithium titanate product.
Another object of the present invention is to: a kind of application of the said goods is provided.
The object of the invention is realized by following proposal: a kind of system of ion secondary battery cathode material lithium fluorine richness lithium titanate
Preparation Method, the molecular formula of the fluorine richness lithium titanate anode material are Li4+xTi5O12-yFy, it is made by freeze-drying micro emulsion method,
Include the following steps:
A, the distilled water dissolution of 10ml is added in the soluble compound and 0.025-0.085g LiF for first weighing the Li of 0.7-1g；
The chitosan for weighing 0.2-0.35g again is added in the glacial acetic acid solution of 40-80ml, and ultrasound is uniform yellowish to being completely dissolved
Color liquid；
B, 0.6-0.9g titania powder, ultrasound, 10 ~ 60min of magnetic agitation are added into chitosan solution；It is molten to chitosan
It is added in liquid in the Li solution dissolved in a step, 10 ~ 60min is stirred by ultrasonic；
C, the epoxychloropropane of 0.4-0.7ml is added into step b solution, continuing magnetic force stirs 5 ~ 15h mixed solution；
D, mixed solution is transferred in culture dish, is covered with preservative film, freezed at -80 DEG C, the sample freezed is put into cold
Lyophilizer vacuumizes, and dry 10 ~ 48h, dried sample is put into crucible, is sent into 600 ~ 900 DEG C of calcining 8- under tube furnace
15h。
The soluble compound of the Li be lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate,
Lithium formate, lithium lactate, isopropyl lithium alkoxide or Organic Alcohol, acid, ester type compound containing lithium.
The molecular formula Li4+xTi5O12-yFyIn 0 < x≤0.03,0.01 < y≤1.
The present invention provides a kind of ion secondary battery cathode material lithium fluorine richness lithium titanate, according to any of the above-described the method
It is prepared.
The present invention provides a kind of fluorine richness lithium titanate for application of the lithium ion secondary battery as negative electrode material.
Certain mesoporous characteristic, the lithium titanate anode are shown using lithium titanate anode material prepared by method of the invention
Material has excellent big rate discharge characteristic.
Detailed description of the invention
Fig. 1 is the cyclic curve of 1 product of the embodiment of the present invention.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
A kind of preparation method of ion secondary battery cathode material lithium fluorine richness lithium titanate, the fluorine richness lithium titanate anode material
Molecular formula be Li4+xTi5O12-yFy, it is made by freeze-drying micro emulsion method, as follows:
A, 0.92g lithium nitrate and 0.025g lithium fluoride are weighed, the distilled water dissolution of 10ml is added；The shell for weighing 0.2375g again is poly-
Sugar is added in the glacial acetic acid solution of 43.5ml, and ultrasound is to being completely dissolved as uniform weak yellow liquid；
B, 0.87g titania powder, ultrasound, magnetic agitation 20min are added into chitosan solution；Add into chitosan solution
Enter the lithium acetate solution dissolved, stirs 10min；
C, in the epoxychloropropane that 0.4ml is added into above-mentioned b step solution, continuing magnetic force stirring 15h obtains mixed solution；
D, mixed solution is transferred in culture dish, is covered with preservative film, freezed at -80 DEG C, the sample freezed is put into cold
Lyophilizer vacuumizes, dry for 24 hours to obtain that sample is put at 800 DEG C of formula furnace and calcines 10h in spongiform white pigmented samples,
It is prepared into final product.Fig. 1 is the cyclic curve of gained sample.
Embodiment 2
A kind of preparation method of ion secondary battery cathode material lithium fluorine richness lithium titanate, it is identical as 1 step of embodiment, by as follows
Step:
A, 0.8685g lithium acetate and 0.06g lithium fluoride are weighed, the distilled water dissolution of 10ml is added；The shell for weighing 0.248g again is poly-
Sugar is added in the glacial acetic acid solution of 50ml, and ultrasound is to being completely dissolved as uniform weak yellow liquid；
B, 0.68g titania powder, ultrasound, magnetic agitation 40min are added into chitosan solution;Into chitosan solution
The lithium acetate solution dissolved is added, stirs 20min；
C, in the epoxychloropropane that 0.5ml is added into above-mentioned solution, continuing magnetic force stirring 5h obtains mixed solution；
D, will mixed solution is transferred in culture dish, covered with preservative film, freezed at -80 DEG C, the sample freezed is put into
Freeze drier vacuumizes, and dry 30, it obtains that sample is put at 800 DEG C of formula furnace and calcines 15h in spongiform white pigmented samples,
It is prepared into final product.
Embodiment 3
A kind of preparation method of ion secondary battery cathode material lithium fluorine richness lithium titanate, it is identical as 1 step of embodiment, by as follows
Step:
A, 0.74g lithium citrate and 0.076g lithium fluoride are weighed, the distilled water dissolution of 10ml is added；The shell for weighing 0.315g again is poly-
Sugar is added in the glacial acetic acid solution of 80ml, and ultrasound is to being completely dissolved as uniform weak yellow liquid；
B, 0.8g titania powder, ultrasound, magnetic agitation 40min are added into chitosan solution;Add into chitosan solution
Enter the lithium acetate solution dissolved, stirs 40min；
C, in the epoxychloropropane that 0.7ml is added into above-mentioned solution, continuing magnetic force stirring 8h obtains mixed solution；
D, mixed solution is transferred in culture dish, is covered with preservative film, freezed at -80 DEG C, the sample freezed is put into cold
Lyophilizer vacuumizes, dry 10h, obtains that sample is put at 600 DEG C of formula furnace and calcines 15h in spongiform white pigmented samples,
It is prepared into final product.
Embodiment 4
A kind of preparation method of ion secondary battery cathode material lithium fluorine richness lithium titanate, it is identical as 1 step of embodiment, by as follows
Step:
A, 0.87g lithium formate and 0.081g lithium fluoride are weighed, the distilled water dissolution of 10ml is added；The shell for weighing 0.2856g again is poly-
Sugar is added in the glacial acetic acid solution of 100ml, and ultrasound is to being completely dissolved as uniform weak yellow liquid；
B, 0.68g titania powder, ultrasound, magnetic agitation 50min are added into chitosan solution;Into chitosan solution
The lithium acetate solution dissolved is added, stirs 40min;
C, in the epoxychloropropane that 0.6ml is added into above-mentioned solution, continuing magnetic force stirring 15h obtains mixed solution；
D, mixed solution is transferred in culture dish, is covered with preservative film, freezed at -80 DEG C, the sample freezed is put into cold
Lyophilizer vacuumizes, dry 48h, obtains that sample is put at 900 DEG C of formula furnace and calcines 8h in spongiform white pigmented samples, makes
It is standby to obtain final product.
Claims (6)
1. a kind of preparation method of ion secondary battery cathode material lithium fluorine richness lithium titanate, the fluorine richness lithium titanate anode material
The molecular formula of material is Li4+xTi5O12-yFy, which is characterized in that it is made, is included the following steps: by freeze-drying micro emulsion method
A, the distilled water dissolution of 10ml is added in the soluble compound and 0.025-0.085g LiF for first weighing the Li of 0.7-1g；
The chitosan for weighing 0.2-0.35g again is added in the glacial acetic acid solution of 40-80ml, and ultrasound is uniform yellowish to being completely dissolved
Color liquid；
B, 0.6-0.9g titania powder, ultrasound, 10 ~ 60min of magnetic agitation are added into chitosan solution；It is molten to chitosan
It is added in liquid in the Li solution dissolved in a step, 10 ~ 60min is stirred by ultrasonic；
C, the epoxychloropropane of 0.4-0.7ml is added into step b solution, continuing magnetic force stirs 5 ~ 15h mixed solution；
D, mixed solution is transferred in culture dish, is covered with preservative film, freezed at -80 DEG C, the sample freezed is put into cold
Lyophilizer vacuumizes, and dry 10 ~ 48h, dried sample is put into crucible, is sent into 600 ~ 900 DEG C of calcining 8- under tube furnace
15h。
2. the preparation method of ion secondary battery cathode material lithium fluorine richness lithium titanate, feature exist according to claim 1
In the soluble compound of the Li is lithium nitrate, lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, formic acid
Lithium, lithium lactate, isopropyl lithium alkoxide or Organic Alcohol, acid, ester type compound containing lithium.
3. the preparation method of ion secondary battery cathode material lithium fluorine richness lithium titanate, feature exist according to claim 1
In, 0 < x≤0.03 in above-mentioned molecular formula, 0.01 < y≤1.
4. the preparation method of ion secondary battery cathode material lithium fluorine richness lithium titanate, feature exist according to claim 1
In the distilled water dissolution of 10ml is added in weighing 0.92g lithium nitrate and 0.025g lithium fluoride；The chitosan for weighing 0.2375g again adds
Enter in the glacial acetic acid solution of 43.5ml, ultrasound is to being completely dissolved as uniform weak yellow liquid；It is added into chitosan solution
0.87g titania powder, ultrasound, magnetic agitation 20min;The lithium acetate solution dissolved is added into chitosan solution, stirs
Mix 10min；In the epoxychloropropane that 0.4ml is added into above-mentioned solution, continuing magnetic force stirs 15h, solution is transferred to culture
It in ware, is covered with preservative film, is freezed at -80 DEG C, the sample freezed is put into freeze drier, is vacuumized, drying for 24 hours, obtains
To being in spongiform white pigmented samples, sample is put at 800 DEG C of tube furnace and calcines 10h, is prepared into final product.
5. a kind of ion secondary battery cathode material lithium fluorine richness lithium titanate, it is characterised in that -4 any institute according to claim 1
The method of stating is prepared.
6. a kind of fluorine richness lithium titanate according to claim 5 is used for application of the lithium ion secondary battery as negative electrode material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563031A (en) * | 2019-09-16 | 2019-12-13 | 广东工业大学 | Lithium titanate negative electrode material, preparation method thereof and battery |
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Application publication date: 20190315 |