CN108417809A - A kind of preparation method and application of lithium ion battery negative material - Google Patents
A kind of preparation method and application of lithium ion battery negative material Download PDFInfo
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- CN108417809A CN108417809A CN201810242466.0A CN201810242466A CN108417809A CN 108417809 A CN108417809 A CN 108417809A CN 201810242466 A CN201810242466 A CN 201810242466A CN 108417809 A CN108417809 A CN 108417809A
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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
- H01M4/366—Composites as layered products
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 discloses a kind of preparation method and applications of lithium ion battery negative material.A hydrothermal synthesis metatitanic acid presoma first, then with lithium source, the secondary hydro-thermal reaction of carbon source.Finally, by product high-temperature calcination under inert atmosphere protection, carbon coating lithium titanate nanometer rods negative material in situ is obtained.The preparation method is easy to operate, the period is short, at low cost, and has the characteristics that excellent specific capacity height, high rate performance, good cycle, security performance are high as lithium ion battery negative material.
Description
Technical field
The invention belongs to field of lithium ion battery material, and in particular to a kind of preparation method of lithium ion battery negative material
And application.
Background technology
Lithium titanate is as lithium ion battery negative material, because its raw material sources is extensive, cheap, environmental-friendly etc. excellent
Point is widely used in commercial Li-ion battery negative material field.Under the conditions of complete charge and discharge, the material volume change rate
No more than 1%, it is known as the good reputation of " zero strain " electrode material.In addition, the higher electrochemistry platform pressure of lithium titanate anode material
(1.55V or so), the significantly larger than decomposition voltage of electrolyte can effectively avoid the formation of SEI films, have better battery
Safety.It is it in power type high multiplying power lithium ion battery in conclusion the material structure advantage that lithium titanate electrode material has
Negative material scale application provides advantage.
The poor conductivity of same lithium titanate leads to its rate charge-discharge poor performance, the serious polarization under high current, limitation
Its commercialized application.Currently, most research work all uses the active material of high conductivity to coat lithium titanate material；Its
Main covering material and technique have ball milling material with carbon-coated surface, vapor deposition carbon coating, lithium titanate and reduced graphene, carbon nanometer
The composite material of the compositions such as pipe, graphitized carbon nano pipe.Carbon coating lithium titanate has simple for process, of low cost and sustainability
By force, become laboratory research and industrial prefered method, the present invention passes through cheap raw material and carbon coating skill in situ
Art prepares synthesis carbon coating lithium titanate anode material in situ, and is applied in energy storage.
Invention content
In view of this, it is an object of the invention to：（1）A kind of preparation side of carbon coating lithium titanate anode material in situ is provided
Method, the preparation method is easy to operate, the period is short, at low cost；（2）The carbon coating lithium titanate anode in situ prepared by the method
Material has many advantages, such as that unique pattern, chemical property are good；（3）Carbon coating lithium titanate anode material in situ is in lithium ion battery
The application of aspect.
In order to achieve the above objectives, the present invention provides the following technical solutions：
A kind of preparation method and application of lithium ion battery negative material, includes the following steps：
（1）It is prepared by metatitanic acid presoma：Titanium dioxide is added in sodium hydroxide solution and is stirred evenly, titanium is synthesized by hydro-thermal method
Hydrochloric acid is then added in above-mentioned metatitanic acid sodium solution and is stirred overnight by acid sodium solution, is then centrifuged for washing and collects, finally carries out cold
Freeze vacuum drying and obtains metatitanic acid presoma；
（2）It is prepared by carbon coating lithium titanate precursor in situ：By lithium source, carbon source and step（1）Obtained metatitanic acid presoma is added
To after being stirred evenly in the aqueous solution of ethyl alcohol, carbon coating lithium titanate precursor solution in situ is synthesized by hydro-thermal method, is finally carried out
It is dry, obtain carbon coating lithium titanate precursor in situ；
（3）Under an inert atmosphere, by step（2）Obtained carbon coating lithium titanate precursor in situ carries out high-temperature process and obtains original position
Carbon coating lithium titanate negative material.
Further, the step（1）In, the sodium hydroxide molar concentration used is 10mol/L, titanium dioxide and hydroxide
The mass ratio of sodium is 1：40~1：75, hydrochloric acid mass concentration is 34%, and centrifugation rate is 6000 revs/min, and centrifugation time is 10 points
Clock.
Further, the step（1）In, the reaction condition of hydro-thermal method synthesis metatitanic acid sodium solution is：Hydrothermal temperature be 110 ~
180 degrees Celsius, soaking time is 24 ~ 48 hours.
Further, the step（2）In, the molar ratio of lithium source and metatitanic acid presoma is 12：5~20：5, carbon source molar concentration
For 10 ~ 50mmol/L, the volume ratio of absolute ethyl alcohol and water is 1：1~1：3.
Further, the step（2）In, lithium source includes the one or more of lithium nitrate, lithium hydroxide, lithium chloride, carbon source
One or more including glucose, sucrose, fructose.
Further, the step（2）In, the reaction condition of hydro-thermal method synthesis carbon coating lithium titanate precursor solution in situ
For：Hydrothermal temperature is 140 ~ 190 degrees Celsius, and soaking time is 4 ~ 12 hours.
Further, the step（3）In, the temperature of high-temperature process is 400-750 degrees Celsius, and soaking time is 2 ~ 8 hours.
Carbon coating lithium titanate anode material in situ is prepared by any of the above item the method.
By application of the carbon coating lithium titanate anode material in situ of preparation recited above in terms of lithium ion battery.
The beneficial effects of the present invention are：The present invention provides the preparation method of carbon coating lithium titanate anode material in situ and
Product.Carbon coating lithium titanate precursor in situ mainly is made by secondary hydrothermal synthesis to be sintered under an inert atmosphere.The system
Preparation Method is simple for process, the period is short, at low cost, as lithium ion battery negative material is high with specific capacity, high rate performance is excellent, follows
The features such as ring performance is good, security performance is high.
Description of the drawings
In order to keep the purpose of the present invention, technical solution and advantageous effect clearer, the present invention provides following attached drawing and carries out
Explanation：
Fig. 1 is the field emission scanning electron microscope figure of 1 gained metatitanic acid presoma of embodiment.
Fig. 2 is the field emission scanning electron microscope figure of 1 gained of embodiment carbon coating lithium titanate anode material in situ.
Fig. 3 is the object phase XRD diagram of 1 gained of embodiment carbon coating lithium titanate anode material in situ.
Fig. 4 is the lithium ion battery constant current charge-discharge curve graph of original position carbon coating lithium titanate anode material described in embodiment 2.
Fig. 5 is the lithium ion battery cyclic curve figure of original position carbon coating lithium titanate anode material described in embodiment 2.
Fig. 6 is the lithium ion battery high rate performance figure of original position carbon coating lithium titanate anode material described in embodiment 2.
Specific implementation mode
Below in conjunction with attached drawing, the preferred embodiment of the present invention is described in detail.
The preparation of the carbon coating lithium titanate anode material in situ of embodiment 1
The sodium hydroxide solution for weighing 2g titanium dioxide and 300ml 10mol/L is stirred at room temperature 0.5 hour, after by above-mentioned liquid
Body is placed in the stainless steel cauldron that poly- the four of 500ml covers ethylene liner, anti-under being 15rpm with rotating speed at 110 ~ 180 degrees Celsius
Answer 24 ~ 48 hours, rear the hydrochloric acid that mass concentration is 34% is added to be adjusted to PH is 1, and after stirring 24 hours, with 6000 revs/min from
The heart is collected after washing 2 ~ 3 times, is finally carried out vacuum freezedrying, is obtained metatitanic acid presoma.The Flied emission of its pattern such as Fig. 1 scans
It is typical nanorod structure shown in electron microscope.
The water that the above-mentioned metatitanic acid presomas of 0.3g, 0.15g lithium hydroxides, 0.1g glucose are slowly added into ethyl alcohol is weighed respectively
In solution（The volume ratio of absolute ethyl alcohol and water is 1:1）, it stirs 0.5 hour be placed in 50mL reaction kettle liners at normal temperatures,
Keep the temperature 4 ~ 12 hours under 140 ~ 190 degrees Celsius, collected after being washed with secondary water and ethyl alcohol, 60 degrees Celsius drying, finally with
400-750 degrees Celsius keeps the temperature 2 ~ 8 hours under inert atmosphere protection, obtains carbon coating lithium titanate anode material in situ.Its pattern
As shown in the field emission scanning electron microscope figure of Fig. 2, there is nanorod structure；Resulting materials object mutually characterizes as shown in figure 3, illustrating to pass through
Such method can successfully prepare carbon coating lithium titanate anode material in situ.
Preparation and electrochemical property test of the embodiment 2 by carbon coating lithium titanate anode material in situ for battery
（1）Carbon coating lithium titanate anode material in situ prepared by Example 1 is poly- inclined as active material, acetylene black and binder
Tetrafluoroethene（PVDF）By 8:1:1 mass ratio weigh being positioned in mortar and be ground uniformly, and suitable 1- first is then added dropwise
- 2 pyrrolidones of base（NMP）, it is about 1cm to be ground into after uniform pasty mass and be applied to area2Copper sheet substrate on, and
It is positioned in vacuum drying chamber, dries 12 hours at one hundred and twenty degrees centigrade to get negative plate.
（2）Half-cell assembles：By positive electrode（Lithium piece）, diaphragm and step（1）In manufactured negative plate carry out button
The assembling of battery, the button cell model used are CR2032, and diaphragm model Celgard2400, electrolyte is 1mol/L's
LiPF6Solution is electrolyte（Wherein solute is LiPF6, solvent is that volume ratio is 1:1 fluorinated ethylene carbonate (FEC) and carbonic acid
Dimethyl ester (DMC)）.After assembling, by battery removal glove box, 6 hours are stood under room temperature, after it is enterprising in Land tests system
The test of row chemical property, test voltage ranging from 1.0 ~ 2.5V.
From fig. 4, it can be seen that when the material is as negative electrode of lithium ion battery, possess longer voltage platform（Voltage platform
For 1.55V or so）, there is good commercial application value.
From fig. 5, it can be seen that when the material is as negative electrode of lithium ion battery, in 175 mAg-1It is first under the current density of (1C)
Secondary specific discharge capacity reaches 173.8 mAhg-1, charge specific capacity reaches 162.8 mAhg-1；And after the cycle of 200 circles
Its performance degradation very little shows that the lithium ion battery negative material cycle performance that preparation method obtains through the embodiment of the present invention is good
It is good.
From fig. 6, it can be seen that when the material is as negative electrode of lithium ion battery, even if the charge and discharge under different current densities
Performance is still stablized, and shows that the high rate performance of the lithium ion battery negative material is good；In 3.5 Ag-1The current density of (20C)
Under also possess 118.6 mAhg-1The specific capacity of left and right, and when current density is restored to 17.5 mAg-1After (0.1C), discharge ratio
Capacity still can reach 155.6 mAhg-1Left and right shows security performance height, the invertibity of the lithium ion battery negative material
It is good.
Finally illustrate, the foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all
All any modification, equivalent and improvement made by within the spirit and principles in the present invention etc. should be included in the guarantor of the present invention
Within the scope of shield.
Claims (9)
1. a kind of preparation method of lithium ion battery negative material, which is characterized in that including following preparation process：
（1）It is prepared by metatitanic acid presoma：Titanium dioxide is added in sodium hydroxide solution and is stirred evenly, titanium is synthesized by hydro-thermal method
Hydrochloric acid is then added in above-mentioned metatitanic acid sodium solution and is stirred overnight by acid sodium solution, is then centrifuged for washing and collects, finally carries out cold
Freeze vacuum drying and obtains metatitanic acid presoma；
（2）It is prepared by carbon coating lithium titanate precursor in situ：By lithium source, carbon source and step（1）Obtained metatitanic acid presoma is added
To after being stirred evenly in the aqueous solution of ethyl alcohol, carbon coating lithium titanate precursor solution in situ is synthesized by hydro-thermal method, is finally carried out
It is dry, obtain carbon coating lithium titanate precursor in situ；
（3）Under an inert atmosphere, by step（2）Obtained carbon coating lithium titanate precursor in situ carries out high-temperature process and obtains original position
Carbon coating lithium titanate negative material.
2. a kind of preparation method of lithium ion battery negative material according to claim 1, which is characterized in that the step
（1）In, the sodium hydroxide molar concentration that uses is 10mol/L, and the mass ratio of titanium dioxide and sodium hydroxide is 1：40~1：75,
Hydrochloric acid mass concentration is 34%, and centrifugation rate is 6000 revs/min, and centrifugation time is 10 minutes.
3. a kind of preparation method of lithium ion battery negative material according to claim 1, which is characterized in that the step
（1）In, the reaction condition of hydro-thermal method synthesis metatitanic acid sodium solution is：Hydrothermal temperature be 110 ~ 180 degrees Celsius, soaking time be 24 ~
48 hours.
4. a kind of preparation method of lithium ion battery negative material according to claim 1, which is characterized in that the step
（2）In, the molar ratio of lithium source and metatitanic acid presoma is 12：5~20：5, carbon source molar concentration is 10 ~ 50mmol/L, absolute ethyl alcohol
Volume ratio with water is 1：1~1：3.
5. a kind of preparation method of lithium ion battery negative material according to claim 1, which is characterized in that the step
（2）In, lithium source includes the one or more of lithium nitrate, lithium hydroxide, lithium chloride, carbon source include glucose, sucrose, fructose one
Kind is several.
6. a kind of preparation method and application of lithium ion battery negative material according to claim 1, which is characterized in that institute
State step（2）In, the reaction condition of hydro-thermal method synthesis carbon coating lithium titanate precursor solution in situ is：Hydrothermal temperature be 140 ~
190 degrees Celsius, soaking time is 4 ~ 12 hours.
7. a kind of preparation method and application of lithium ion battery negative material according to claim 1, which is characterized in that institute
State step（3）In, the temperature of high-temperature process is 400-750 degrees Celsius, and soaking time is 2 ~ 8 hours.
8. preparing carbon coating lithium titanate anode material in situ according to claim 1 ~ 7 any one of them method.
9. by application of the carbon coating lithium titanate anode material in situ according to any one of claims 8 on lithium ion half-cell.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551574A (en) * | 2020-12-11 | 2021-03-26 | 桐乡市鸿信科技合伙企业(有限合伙) | Sulfur-nitrogen doped porous carbon-coated Li4Ti5O12Lithium ion battery cathode material and preparation method thereof |
| CN113206250A (en) * | 2021-04-23 | 2021-08-03 | 南京邮电大学 | Semiconductor cathode material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900861A (en) * | 2015-04-02 | 2015-09-09 | 清华大学 | Hydrogen lithium titanate Li-H-Ti-O material and preparation method thereof |
| CN105070898A (en) * | 2015-07-16 | 2015-11-18 | 清华大学深圳研究生院 | Lithium titanate material and preparation method thereof, electrode plate using lithium titanate material, and battery |
-
2018
- 2018-03-23 CN CN201810242466.0A patent/CN108417809A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900861A (en) * | 2015-04-02 | 2015-09-09 | 清华大学 | Hydrogen lithium titanate Li-H-Ti-O material and preparation method thereof |
| CN105070898A (en) * | 2015-07-16 | 2015-11-18 | 清华大学深圳研究生院 | Lithium titanate material and preparation method thereof, electrode plate using lithium titanate material, and battery |
Non-Patent Citations (1)
| Title |
|---|
| EUN-KYUNG KIM ET AL.: "Synthesis and Electrochemical Characteristics of Li4Ti5O12 Nanofibers by Hydrothermal Method", 《JOURNAL OF THE KOREAN CERAMIC SOCIETY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551574A (en) * | 2020-12-11 | 2021-03-26 | 桐乡市鸿信科技合伙企业(有限合伙) | Sulfur-nitrogen doped porous carbon-coated Li4Ti5O12Lithium ion battery cathode material and preparation method thereof |
| CN113206250A (en) * | 2021-04-23 | 2021-08-03 | 南京邮电大学 | Semiconductor cathode material and preparation method thereof |
| CN113206250B (en) * | 2021-04-23 | 2022-07-26 | 南京邮电大学 | Semiconductor cathode material and preparation method thereof |
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Application publication date: 20180817 |