CN109546102B - Lithium titanate negative electrode material and preparation method thereof - Google Patents

Lithium titanate negative electrode material and preparation method thereof Download PDF

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CN109546102B
CN109546102B CN201811217853.5A CN201811217853A CN109546102B CN 109546102 B CN109546102 B CN 109546102B CN 201811217853 A CN201811217853 A CN 201811217853A CN 109546102 B CN109546102 B CN 109546102B
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lithium
lithium titanate
negative electrode
electrode material
preparation
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CN109546102A (en
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张世超
宋歌
邢雅兰
赵爽
吴昊
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Beihang University
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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
    • 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
    • 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
    • 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
    • H01M4/626—Metals
    • 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 lithium titanate negative electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: the preparation method comprises the steps of taking foamed nickel as a carrier, taking a titanium source and a lithium source as raw materials, preparing a lithium titanate precursor by a solvothermal method, and calcining to obtain the lithium titanate negative electrode material, wherein a solvent used in the solvothermal method is a mixed solution of n-propanol/isopropanol and glycerol. According to the preparation method, the mixed solution of the propanol and the glycerol is used as the solvent in the solvothermal method, so that the morphology and the size of the material can be effectively controlled, and the foamed nickel is used as the carrier, so that a channel is provided for the electron transmission of the material, and the conductivity of the material is improved. The lithium titanate negative electrode material prepared by the invention has a spherical structure similar to rambutan, is uniformly loaded on foamed nickel and has a two-phase structure, and when the lithium titanate negative electrode material is used as a lithium ion battery negative electrode material, the discharge capacity of the battery is high, the rate capability of the battery is good, and a reference basis is provided for the development of the lithium ion battery in the field of industrial batteries.

Description

Lithium titanate negative electrode material and preparation method thereof
Technical Field
The invention relates to the field of preparation of lithium ion battery cathode materials, in particular to a lithium titanate cathode material and a preparation method thereof.
Background
Lithium ion batteries are considered to be an energy storage device with ideal development prospects due to their wide application in the field of energy storage (such as electronic devices and hybrid electric vehicles). The negative electrode material has important influence on the safety, cycle life, rate capability and the like of the lithium ion battery.
Currently, the positive and negative electrode materials in commercial batteries are LiCoO, respectively2And graphitized carbon materials. Researchers in recent years have explored the synthesis of LiMn with a layered structure1/3Co1/3Ni1/3O2LiMn of spinel structure2O4，LiFePO4Isomaterial instead of LiCoO2. As for the negative electrode material, graphite is used for replacing lithium metal to be applied to the lithium ion battery, and the theoretical specific capacity is 372mAh g in the circulating process-1Commercial graphite has high energy density, low voltage plateau and long cycle life, but has low reversible capacity and is easy to generate polarization reaction, so that the exploration and synthesis of a negative electrode material with very high capacity are very important.
In recent years, titanium-based oxides such as Li4Ti5O12(LTO) is promising as a "zero strain" material for next generation power cells. The lithium titanate has high voltage platform, almost zero volume change as the negative electrode of the lithium ion battery and excellent cycle performance. However, the electron conductivity of lithium titanate materials is poor (10-23S cm)-1) Lithium ion mobility is low, creating a series of kinetic problems that cause capacity fade when the battery is charged and discharged at high rates. In order to improve the performance of lithium titanate materials, the currently adopted methods include increasing the electron transport capability by increasing the contact between an active material and a current collector, nano-crystallization of lithium titanate particles, surface coating, bulk phase doping, surface doping and the like, but the methods have the problems of complicated process or poor improvement effect and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a lithium titanate negative electrode material and a preparation method thereof.
The invention provides a preparation method of a lithium titanate negative electrode material, which comprises the following steps: the preparation method comprises the steps of taking foamed nickel as a carrier, taking a titanium source and a lithium source as raw materials, preparing a lithium titanate precursor by a solvothermal method, and calcining to obtain the lithium titanate negative electrode material, wherein a solvent used in the solvothermal method is a mixed solution of n-propanol/isopropanol and glycerol.
Compared with the traditional solvothermal method, in the technical scheme, glycerol is added on the basis of taking n-propanol/isopropanol as a solvent, and the hydrolysis of the titanium source and the nucleation process of the titanium source and the lithium source are controlled through the action of a mixed solvent, so that the morphology and the size of the material are controlled, and the material composition and the structure of the material are not influenced. The foamed nickel is used as a carrier, a channel is provided for electron transmission of the material, the conductivity of the material is improved, and when the lithium titanate negative electrode material is applied to a lithium ion battery, the foamed nickel can be used as a current collector and an active material to directly form a lithium ion battery electrode without the need of electrode preparation processes such as material coating.
Preferably, the volume ratio of the n-propanol/isopropanol to the glycerol is 1: 0.2-0.6.
Preferably, the method further comprises adding polyvinylpyrrolidone (PVP) in the solvothermal method.
In the technical scheme, PVP is added as a surfactant, so that the reaction system is dispersed more uniformly, and in the solvothermal reaction process, the decomposed titanium source and the lithium source can be combined on the surface of the foamed nickel to form nuclei uniformly, so that the material is distributed uniformly on the surface of the foamed nickel and has uniform thickness, the transmission path of lithium ions is reduced, and the electron and ion conduction rate of the material is improved.
More preferably, the addition amount of the polyvinylpyrrolidone is 3wt% to 5wt% of the total mass of the added lithium source and titanium source.
Preferably, the calcination process employs staged sintering.
In the technical scheme, the lithium titanate precursor can be converted from an amorphous state to a crystalline state by adopting the sectional sintering, and finally a titanium dioxide-lithium titanate composite two-phase structure is obtained, so that the synergistic effect is exerted and the electrochemical performance of the material is improved.
More preferably, the step sintering is carried out for 4-6 h at 400-600 ℃, and then for 4-10 h at 650-900 ℃.
Preferably, in the solvothermal method, the reaction temperature of the reaction system is 150-250 ℃, and the reaction time is 6-24 h.
During the solvothermal process, control of temperature and time can affect the uniformity and thickness of the distribution of lithium titanate on the nickel foam, as well as the size of the lithium titanate particles. With the increase of the temperature and the prolongation of the time, the uniformity degree of the distribution of the lithium titanate on the foamed nickel is better, but when the temperature is increased to a certain degree, the temperature is increased, the growth thickness of the lithium titanate on the foamed nickel is increased, the transmission distance of lithium ions and electrons is increased, and the electrochemical performance of the material is reduced. A large number of experiments show that the temperature and the time are controlled within the ranges, and the obtained material has the best effect.
Preferably, the lithium source is lithium acetate and/or lithium carbonate.
Preferably, the titanium source is one or more of tetrabutyl titanate, titanium tetrachloride and titanium isopropoxide.
Preferably, according to experimental verification, in the range of the experimental conditions, the generation rate of the product after the hydrolysis of the titanium source is 16% -20%, and the molar ratio of the lithium source and the titanium source is 1: 1-1.25, so that the molar ratio of the lithium source and the titanium source actually added in the reaction is 2.5-3: 1.
As a preferred embodiment, the above preparation method specifically comprises the steps of:
(1) mixing n-propanol/isopropanol and glycerol in a volume ratio of 1: 0.2-0.6 to obtain a mixed solution A;
(2) adding polyvinylpyrrolidone into the mixed solution A, then continuously adding a lithium source and a titanium source in a molar ratio of 1: 1-1.25, and uniformly mixing to obtain a mixed solution B;
(3) transferring the mixed solution B into a reaction kettle, adding activated foam nickel, and reacting for 6-24 hours at 150-250 ℃;
(4) after the reaction is finished, cleaning, centrifuging and drying to obtain a lithium titanate precursor loaded with foamed nickel;
(5) carrying out sectional sintering on the lithium titanate precursor under protective gas: the lithium titanate negative electrode material is obtained by firstly reacting for 4-6 hours at 400-600 ℃, and then reacting for 4-10 hours at 650-900 ℃.
Preferably, the activation treatment of the foamed nickel is that the foamed nickel is cut into squares with the side length of 2 x 2, soaked in dilute hydrochloric acid or nitric acid for 15-30 min, then subjected to ultrasonic treatment in acetone for 15-30 min, finally washed by deionized water and dried; the protective gas is nitrogen or argon.
The second purpose of the invention is to provide a lithium titanate negative electrode material prepared by the preparation method. The lithium titanate negative electrode material is in a spherical structure similar to rambutan.
The third object of the invention is to provide a lithium ion battery, wherein the negative electrode material is made of the lithium titanate negative electrode material. The discharge capacity of the lithium ion battery reaches 210mAh/g under the charge-discharge current with the voltage of 0.01-3.0V and the voltage of 1A/g, and the capacity is kept above 99% after 500 times of circulation.
According to the preparation method, the mixed solution of the propanol and the glycerol is used as the solvent in the solvothermal method, so that the morphology and the size of the material can be effectively controlled, and the foamed nickel is used as the carrier, so that a channel is provided for the electron transmission of the material, and the conductivity of the material is improved. The lithium titanate negative electrode material prepared by the invention has a spherical structure similar to rambutan, is uniformly loaded on foamed nickel and has a two-phase structure, and when the lithium titanate negative electrode material is used as a lithium ion battery negative electrode material, the discharge capacity of the battery is high, the rate capability of the battery is good, and a reference basis is provided for the development of the lithium ion battery in the field of industrial batteries.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of the lithium titanate precursor of example 1;
FIG. 2 is a scanning electron microscope image of a lithium titanate precursor in example 1 at different magnification;
FIG. 3 is an X-ray diffraction pattern of the lithium titanate negative electrode material obtained in example 1;
FIG. 4 is a scanning electron microscope image of the lithium titanate negative electrode material obtained in example 1 at different magnification;
FIG. 5 is a scanning electron microscope image of a lithium titanate precursor in example 2 at different magnification;
FIG. 6 is an X-ray diffraction pattern of the lithium titanate negative electrode material obtained in example 3;
fig. 7 is a scanning electron microscope image of the lithium titanate negative electrode material obtained in example 3;
fig. 8 is a graph showing the results of the 1C cycle performance test of the battery in application example 1;
fig. 9 is a graph showing the results of rate performance tests of the battery in application example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a lithium titanate negative electrode material, and a preparation method thereof comprises the following steps: cutting foamed nickel into 2 x 2 squares, respectively performing ultrasonic treatment in 0.1M nitric acid and acetone solution for 15min, cleaning with deionized water for 3 times, and drying at 60 deg.C; weighing 35mL of n-propanol and 8mL of glycerol, mixing to obtain a mixed solution A, adding 200mg of PVP into the mixed solution A, uniformly stirring by magnetic force, adding 3mL of tetrabutyl titanate and 2.2g of lithium acetate dihydrate, and uniformly stirring by magnetic force to obtain a mixed solution B; transferring the mixed solution B and the foamed nickel into a 100mL reaction kettle, heating to 150 ℃, reacting for 15h, cooling a reaction system, centrifuging, and drying to obtain a lithium titanate precursor loaded with the foamed nickel; putting a lithium titanate precursor into a tube furnace, introducing argon, and setting temperature parameters as follows: heating to 450 ℃ at the speed of 5 ℃/min, preserving heat for 5h, then heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 8h, and finally obtaining the target product.
The lithium titanate precursor was characterized by an X-ray diffractometer and a scanning electron microscope, and the results are shown in fig. 1 and 2. As can be seen from the figure, the lithium titanate precursor synthesized by the solvothermal method is of an amorphous structure, is uniformly loaded on the nickel foam, is similar to a rambutan spherical structure in appearance, and has a diameter of about 2 μm. The lithium titanate precursor synthesized by the solvothermal method lays a foundation for obtaining a negative electrode material with high conductivity and a short lithium ion transmission channel by subsequent calcination.
The target product was characterized by X-ray diffractometer and scanning electron microscope, and the results are shown in fig. 3 and 4. As can be seen from the figure, the lithium titanate negative electrode material which has an anatase structure titanium dioxide and spinel structure lithium titanate two-phase composite structure and is uniformly loaded on the nickel foam and has a stable shape is obtained through solvothermal synthesis and sectional sintering.
Example 2
The embodiment provides a lithium titanate negative electrode material, and the preparation method thereof is different from that of embodiment 1 in that: the mixed solution A obtained by mixing 35mL of n-propanol and 8mL of glycerol with 43mL of n-propanol during the solvothermal method.
The lithium titanate precursor obtained in this example was characterized by a scanning electron microscope, and the result is shown in fig. 5. As can be seen from the figure, the solvothermal process using propanol as the solvent yielded a spherical structure with a relatively smooth surface. Compared with the material with the rambutan appearance, the lithium ion transmission path is longer and the specific surface area is larger.
Example 3
The embodiment provides a lithium titanate negative electrode material, and the preparation method thereof is different from that of embodiment 1 in that: the calcination process does not adopt sectional calcination, and the calcination temperature is 900 ℃ for treatment for 8 h.
The target product was characterized by X-ray diffractometer and scanning electron microscope, and the results are shown in fig. 6 and 7. As can be seen from the figure, the structure of the lithium titanate material which is not subjected to the sectional sintering is the lithium titanate with a pure spinel structure, but is not the two-phase structure of titanium dioxide and lithium titanate, but the morphology is not greatly different from that of the sectional sintering, because the morphology of the precursor is the same and stable, the morphology is not basically influenced by the heat treatment.
Application example 1
The lithium titanate negative electrode material obtained in example 1 is punched by a tablet press, and an active material is fully contacted with foamed nickel through a roller to improve the conductivity, so that a circular electrode with the radius of 0.5mm is finally obtained and used as a negative electrode of a lithium ion battery. In the process of assembling the battery, lithium hexafluorophosphate is used as electrolyte, and a lithium sheet is used as a positive electrode in a glove box to assemble the button battery. The cycle performance and the rate performance of the battery are tested by a blue electric system, and the specific test parameters are as follows: in the process of testing the cycle performance, the charging and discharging voltage range is 0.01-3.0V, and the cycle is performed for 500 circles under the current of 1A/g; in the process of testing the multiplying power performance, the current is respectively circulated for 100 circles under the current of 1A/g, 2A/g, 5A/g, 10A/g, 20A/g and 1A/g in the voltage range of 0.01-3.0V, the test result is shown in fig. 8 and fig. 9, and the vertical axis of the charging curve in fig. 8 is a scale on the right side. As can be seen from the figure, the capacity reaches 210mAh/g and the capacity retention rate reaches 99% after 500 cycles of circulation under the current of 1A/g, in the process of testing the rate capability, the capacity is 80mAh/g under the current of 20A/g, when the current returns to 1A/g, the capacity is basically recovered to the initial capacity, and the battery has good rate capability.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. A preparation method of a lithium titanate negative electrode material is characterized by comprising the following steps: taking foamed nickel as a carrier, taking a titanium source and a lithium source as raw materials, preparing a lithium titanate precursor by a solvothermal method, and calcining to obtain the lithium titanate negative electrode material, wherein a solvent used in the solvothermal method is a mixed solution of n-propanol/isopropanol and glycerol;
the volume ratio of the n-propanol/isopropanol to the glycerol is 1: 0.2-0.6;
the calcination process adopts segmented sintering, and the segmented sintering specifically comprises the steps of reacting for 4-6 hours at 400-600 ℃, and then reacting for 4-10 hours at 650-900 ℃.
2. The method of claim 1, further comprising adding polyvinylpyrrolidone to the solvothermal process.
3. The preparation method according to claim 2, wherein the polyvinylpyrrolidone is added in an amount of 3wt% to 5wt% based on the total mass of the titanium source and the lithium source.
4. The method according to any one of claims 1 to 3, wherein in the solvothermal method, the reaction temperature of the reaction system is 150 to 250 ℃ and the reaction time is 6 to 24 hours.
5. The method according to claim 4, wherein the lithium source is lithium acetate and/or lithium carbonate, and the titanium source is one or more of tetrabutyl titanate, titanium tetrachloride, and titanium isopropoxide.
6. The production method according to claim 5, wherein the molar ratio of the lithium source to the titanium source is 1:1 to 1.25.
7. The preparation method according to claim 1, comprising the following steps:
(1) mixing n-propanol/isopropanol and glycerol in a volume ratio of 1: 0.2-0.6 to obtain a mixed solution A;
(2) adding polyvinylpyrrolidone into the mixed solution A, then continuously adding a lithium source and a titanium source in a molar ratio of 1: 1-1.25, and uniformly mixing to obtain a mixed solution B;
(3) transferring the mixed solution B into a reaction kettle, adding activated foamed nickel, and reacting for 6-24 hours at 150-250 ℃;
(4) after the reaction is finished, performing post-treatment to obtain a lithium titanate precursor loaded with foamed nickel;
(5) carrying out sectional sintering on the lithium titanate precursor under protective gas: the lithium titanate negative electrode material is obtained by firstly reacting for 4-6 hours at 400-600 ℃, and then reacting for 4-10 hours at 650-900 ℃.
8. The lithium titanate negative electrode material prepared by the preparation method of any one of claims 1 to 7.
9. A lithium ion battery comprising the lithium titanate negative electrode material of claim 8.
CN201811217853.5A 2018-10-18 2018-10-18 Lithium titanate negative electrode material and preparation method thereof Active CN109546102B (en)

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