CN106531997A - Preparation method of lithium titanate composite negative electrode material - Google Patents
Preparation method of lithium titanate composite negative electrode material Download PDFInfo
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- CN106531997A CN106531997A CN201611010970.5A CN201611010970A CN106531997A CN 106531997 A CN106531997 A CN 106531997A CN 201611010970 A CN201611010970 A CN 201611010970A CN 106531997 A CN106531997 A CN 106531997A
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- lithium
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- titanate composite
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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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- 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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 relates to a preparation method of a lithium titanate composite negative electrode material. The method comprises the steps of (1) weighing a lithium salt and titanium dioxide with a mole ratio of Li:Ti being (4.2-4.6):5 according to a matching ratio, placing the lithium salt and the titanium dioxide in a ball-milling tank, adding a dispersion agent and zirconium spheres, performing wet ball milling and uniform mixing, and drying the material after ball-milling; (2) placing a dried material in a CVD (Chemical Vapor Deposition) furnace, adding graphite and silicon oxide, and introducing an inert gas, wherein the weight matching ratio of the dried material, the graphite and the silicon oxide is as follows: 75-80 parts of dried material, 9-12 parts of graphite and 9-12 parts of silicon oxide; and (3) adjusting a parameter and a sintering condition of the introduced gas, and synthesizing the lithium titanate composite negative electrode material. The preparation method has the advantages of reasonable process, low cost, stable product performance and excellent electrochemical performance.
Description
Technical field
A kind of the invention belongs to technical field of lithium ion, more particularly to preparation side of lithium titanate composite anode material
Method.
Background technology
Lithium ion battery develops rapidly the exploitation and polytechnic progress for depending on novel energy material, wherein new
Especially the exploration of negative material and research are just particularly important electrode material, since commercial li-ion battery occurs,
Graphite cathode just firmly in occupation of the dominant position of lithium ion battery negative material, from Delanium, native graphite, then to centre
Phase graphite, already close to graphite material theoretical capacity 372mAh/g, this seriously constrains the raising of lithium ion battery energy density,
Compared with graphite material, lithium titanate has obvious advantage, and lithium titanate is zero strain material, and good cycle, discharge voltage are put down
Surely, have a safety feature；And silicon, when as lithium ion battery negative material, each atom at most can be with reference to 4.4 lithium atoms, its
Middle silicon atom forms Li22Si5 alloys, and theoretical specific capacity is up to 4200mAh/g, and relatively low to lithium point position, but this material
There is a shortcoming, in deintercalation circulation, silicon crystal lattice and microstructure change are larger, it may appear that serious volumetric expansion and receipts
Contracting；Therefore it provides a kind of rational technology, with low cost, product property be stable, excellent electrochemical performance lithium titanate composite negative pole
The preparation method of material is necessary.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, and provide a kind of rational technology, with low cost, product
Can the stable, preparation method of the lithium titanate composite anode material of excellent electrochemical performance.
The technical scheme is that：A kind of preparation method of lithium titanate composite anode material, the concrete steps of the method：
（1）Mol ratio Li is weighed according to proportioning：Ti is 4.2-4.6:5 lithium salts and titanium dioxide are placed in ball grinder, are added and are divided
Powder and zirconium ball, carry out wet ball grinding mixing, and the material after ball milling is dried；
（2）Dried feed is put in CVD stoves, adds graphite and the sub- silicon of oxidation, the weight proportion of the sub- silicon of dried feed, graphite and oxidation
For：Dried feed 75-80 part, graphite 9-12 parts, the sub- silicon 9-12 parts of oxidation are passed through noble gases；
（3）Regulation is passed through parameter and the sintering condition of gas, synthesizes lithium titanate composite anode material.
Described step（1）In lithium salts be lithium carbonate, Lithium hydrate, lithium chloride, lithium sulfate, lithium nitrate, lithium acetate, fluorine
Change one or more in lithium.
Described step（1）In titanium dioxide be rutile-type or anatase titanium dioxide.
Described step（2）In graphite be nanoscale graphite powder.
Described step（2）In oxidation Asia silicon be nanoscale Asia silicon.
Described step（2）In noble gases be nitrogen, argon, one or more in helium.
Described step（3）In gas parameter and sintering condition be：The pressure of described gas is 0.2-0.7Mpa,
Described sintering time is 5-10 hours, and sintering temperature is 500-800 DEG C.
The present invention has advantages below：The present invention adopts lithium salts and titanium dioxide production lithium titanate, adds graphite and oxidation
Sub- silicon, by the method for high temperature vapor phase deposition, generates lithium titanate composite anode material, and in the sub- silicon of oxidation, the intensity of si-o keys is
2 times of si-si bond strengths, for volumetric expansion has cushioning effect, cycle performance is superior more than silicon, using nanoscale graphite,
Good coating function can be formed to the sub- silicon of oxidation, further increase the cycle performance of material, the metatitanic acid that the present invention is provided
Lithium composite negative pole material not only has higher capacity characteristic, and structural stability is good, improves following in charge and discharge process
Ring performance, is excellent lithium cell cathode material；The present invention has that rational technology, with low cost, product property be stable, electrochemistry
The advantage of function admirable.
Specific embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
A kind of preparation method of lithium titanate composite anode material, the concrete steps of the method：
（1）Mol ratio Li is weighed according to proportioning：Ti is 4.2:5 lithium salts and titanium dioxide are placed in ball grinder, add dispersant
With zirconium ball, wet ball grinding mixing is carried out, the material after ball milling is dried；
（2）Dried feed is put in CVD stoves, adds graphite and the sub- silicon of oxidation, the weight proportion of the sub- silicon of dried feed, graphite and oxidation
For：75 parts of dried feed, 9 parts of graphite, sub- 9 parts of the silicon of oxidation are passed through noble gases；
（3）Regulation is passed through parameter and the sintering condition of gas, synthesizes lithium titanate composite anode material.
Described step（1）In titanium dioxide be rutile-type or anatase titanium dioxide.
Described step（2）In graphite be nanoscale graphite powder.
Described step（2）In oxidation Asia silicon be nanoscale Asia silicon.
Described step（2）In noble gases be nitrogen, argon, one or more in helium.
Described step（3）In gas parameter and sintering condition be：The pressure of described gas is 0.2Mpa, described
Sintering time be 5 hours, sintering temperature be 500 DEG C.
The present invention adopts lithium salts and titanium dioxide production lithium titanate, adds graphite and the sub- silicon of oxidation, by High Temperature Gas as heavy
Long-pending method, generates lithium titanate composite anode material, and in the sub- silicon of oxidation, the intensity of si-o keys is 2 times of si-si bond strengths, for
Volumetric expansion has cushioning effect, and cycle performance is superior more than silicon, using nanoscale graphite, the sub- silicon of oxidation can be formed very well
Coating function, further increase the cycle performance of material, the lithium titanate composite anode material that the present invention is provided not only has
Higher capacity characteristic, and structural stability is good, improves the cycle performance in charge and discharge process, is that excellent lithium battery is born
Pole material；The present invention has the advantages that rational technology, with low cost, product property be stable, excellent electrochemical performance.
Embodiment 2
A kind of preparation method of lithium titanate composite anode material, the concrete steps of the method：
（1）Mol ratio Li is weighed according to proportioning：Ti is 4.6:5 lithium salts and titanium dioxide are placed in ball grinder, add dispersant
With zirconium ball, wet ball grinding mixing is carried out, the material after ball milling is dried；
（2）Dried feed is put in CVD stoves, adds graphite and the sub- silicon of oxidation, the weight proportion of the sub- silicon of dried feed, graphite and oxidation
For：80 parts of dried feed, 12 parts of graphite, sub- 12 parts of the silicon of oxidation are passed through noble gases；
（3）Regulation is passed through parameter and the sintering condition of gas, synthesizes lithium titanate composite anode material.
Described step（1）In lithium salts be lithium carbonate, Lithium hydrate, lithium chloride, lithium sulfate, lithium nitrate, lithium acetate, fluorine
Change one or more in lithium.
Described step（1）In titanium dioxide be rutile-type or anatase titanium dioxide.
Described step（2）In graphite be nanoscale graphite powder.
Described step（2）In oxidation Asia silicon be nanoscale Asia silicon.
Described step（2）In noble gases be nitrogen, argon, one or more in helium.
Described step（3）In gas parameter and sintering condition be：The pressure of described gas is 0.7Mpa, described
Sintering time be 10 hours, sintering temperature be 800 DEG C.
The present invention adopts lithium salts and titanium dioxide production lithium titanate, adds graphite and the sub- silicon of oxidation, by High Temperature Gas as heavy
Long-pending method, generates lithium titanate composite anode material, and in the sub- silicon of oxidation, the intensity of si-o keys is 2 times of si-si bond strengths, for
Volumetric expansion has cushioning effect, and cycle performance is superior more than silicon, using nanoscale graphite, the sub- silicon of oxidation can be formed very well
Coating function, further increase the cycle performance of material, the lithium titanate composite anode material that the present invention is provided not only has
Higher capacity characteristic, and structural stability is good, improves the cycle performance in charge and discharge process, is that excellent lithium battery is born
Pole material；The present invention has the advantages that rational technology, with low cost, product property be stable, excellent electrochemical performance.
Embodiment 3
A kind of preparation method of lithium titanate composite anode material, the concrete steps of the method：
（1）Mol ratio Li is weighed according to proportioning：Ti is 4.4:5 lithium salts and titanium dioxide are placed in ball grinder, add dispersant
With zirconium ball, wet ball grinding mixing is carried out, the material after ball milling is dried；
（2）Dried feed is put in CVD stoves, adds graphite and the sub- silicon of oxidation, the weight proportion of the sub- silicon of dried feed, graphite and oxidation
For：78 parts of dried feed, 11 parts of graphite, sub- 11 parts of the silicon of oxidation are passed through noble gases；
（3）Regulation is passed through parameter and the sintering condition of gas, synthesizes lithium titanate composite anode material.
Described step（1）In lithium salts be lithium carbonate, Lithium hydrate, lithium chloride, lithium sulfate, lithium nitrate, lithium acetate, fluorine
Change one or more in lithium.
Described step（1）In titanium dioxide be rutile-type or anatase titanium dioxide.
Described step（2）In graphite be nanoscale graphite powder.
Described step（2）In oxidation Asia silicon be nanoscale Asia silicon.
Described step（2）In noble gases be nitrogen, argon, one or more in helium.
Described step（3）In gas parameter and sintering condition be：The pressure of described gas is 0.5Mpa, described
Sintering time be 8 hours, sintering temperature be 650 DEG C.
The present invention adopts lithium salts and titanium dioxide production lithium titanate, adds graphite and the sub- silicon of oxidation, by High Temperature Gas as heavy
Long-pending method, generates lithium titanate composite anode material, and in the sub- silicon of oxidation, the intensity of si-o keys is 2 times of si-si bond strengths, for
Volumetric expansion has cushioning effect, and cycle performance is superior more than silicon, using nanoscale graphite, the sub- silicon of oxidation can be formed very well
Coating function, further increase the cycle performance of material, the lithium titanate composite anode material that the present invention is provided not only has
Higher capacity characteristic, and structural stability is good, improves the cycle performance in charge and discharge process, is that excellent lithium battery is born
Pole material；The present invention has the advantages that rational technology, with low cost, product property be stable, excellent electrochemical performance.
Claims (7)
1. a kind of preparation method of lithium titanate composite anode material, it is characterised in that：The concrete steps of the method：
（1）Mol ratio Li is weighed according to proportioning：Ti is 4.2-4.6:5 lithium salts and titanium dioxide are placed in ball grinder, are added and are divided
Powder and zirconium ball, carry out wet ball grinding mixing, and the material after ball milling is dried；
（2）Dried feed is put in CVD stoves, adds graphite and the sub- silicon of oxidation, the weight proportion of the sub- silicon of dried feed, graphite and oxidation
For：Dried feed 75-80 part, graphite 9-12 parts, the sub- silicon 9-12 parts of oxidation are passed through noble gases；
（3）Regulation is passed through parameter and the sintering condition of gas, synthesizes lithium titanate composite anode material.
2. a kind of preparation method of lithium titanate composite anode material as claimed in claim 1, it is characterised in that：Described step
（1）In lithium salts be lithium carbonate, Lithium hydrate, lithium chloride, lithium sulfate, lithium nitrate, lithium acetate, the one kind or many in lithium fluoride
Kind.
3. a kind of preparation method of lithium titanate composite anode material as claimed in claim 1, it is characterised in that：Described step
（1）In titanium dioxide be rutile-type or anatase titanium dioxide.
4. a kind of preparation method of lithium titanate composite anode material as claimed in claim 1, it is characterised in that：Described step
（2）In graphite be nanoscale graphite powder.
5. a kind of preparation method of lithium titanate composite anode material as claimed in claim 1, it is characterised in that：Described step
（2）In oxidation Asia silicon be nanoscale Asia silicon.
6. a kind of preparation method of lithium titanate composite anode material as claimed in claim 1, it is characterised in that：Described step
（2）In noble gases be nitrogen, argon, one or more in helium.
7. a kind of preparation method of lithium titanate composite anode material as claimed in claim 1, it is characterised in that：Described step
（3）In gas parameter and sintering condition be：The pressure of described gas is 0.2-0.7Mpa, and described sintering time is 5-
10 hours, sintering temperature was 500-800 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201611010970.5A CN106531997A (en) | 2016-11-17 | 2016-11-17 | Preparation method of lithium titanate composite negative electrode material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611010970.5A CN106531997A (en) | 2016-11-17 | 2016-11-17 | Preparation method of lithium titanate composite negative electrode material |
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| CN106531997A true CN106531997A (en) | 2017-03-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492640A (en) * | 2017-07-31 | 2017-12-19 | 天津巴莫科技股份有限公司 | Self-locking type coating type lithium titanate material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794761A (en) * | 2014-01-15 | 2014-05-14 | 合肥国轩高科动力能源股份公司 | Preparation method of silicon/lithium titanate composite negative electrode material of lithium ion battery |
| CN104854740A (en) * | 2012-12-06 | 2015-08-19 | 株式会社Lg化学 | Anode active material having high capacity for lithium secondary battery, preparation thereof and lithium secondary battery comprising the same |
| JP2016110917A (en) * | 2014-12-09 | 2016-06-20 | 株式会社日立製作所 | Lithium ion secondary battery and battery system |
-
2016
- 2016-11-17 CN CN201611010970.5A patent/CN106531997A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104854740A (en) * | 2012-12-06 | 2015-08-19 | 株式会社Lg化学 | Anode active material having high capacity for lithium secondary battery, preparation thereof and lithium secondary battery comprising the same |
| CN103794761A (en) * | 2014-01-15 | 2014-05-14 | 合肥国轩高科动力能源股份公司 | Preparation method of silicon/lithium titanate composite negative electrode material of lithium ion battery |
| JP2016110917A (en) * | 2014-12-09 | 2016-06-20 | 株式会社日立製作所 | Lithium ion secondary battery and battery system |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107492640A (en) * | 2017-07-31 | 2017-12-19 | 天津巴莫科技股份有限公司 | Self-locking type coating type lithium titanate material and preparation method thereof |
| CN107492640B (en) * | 2017-07-31 | 2020-01-31 | 天津巴莫科技股份有限公司 | Self-locking coated lithium titanate material and preparation method thereof |
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Effective date of abandoning: 20191022 |