CN112978790B - Preparation method of lithium titanate with electrochemical oscillation effect - Google Patents
Preparation method of lithium titanate with electrochemical oscillation effect Download PDFInfo
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- CN112978790B CN112978790B CN202110213847.8A CN202110213847A CN112978790B CN 112978790 B CN112978790 B CN 112978790B CN 202110213847 A CN202110213847 A CN 202110213847A CN 112978790 B CN112978790 B CN 112978790B
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- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
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- 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
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- 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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Abstract
The invention provides a preparation method of lithium titanate with an electrochemical oscillation effect, which comprises the following steps: the invention modulates the formula of lithium titanate with stronger electrochemical oscillation effect to prepare a lithium titanate sample with electrochemical oscillation effect, and compared with other similar products, the sample has the characteristics of high particle dispersion degree and small particles; and when charging, there is electrochemical oscillation effect, that is, regular voltage oscillation can be generated on the charging platform.
Description
Technical Field
The invention relates to the field of electrochemistry, and particularly relates to a preparation method of lithium titanate with an electrochemical oscillation effect.
Background
The lithium ion battery has the advantages of rapid charge and discharge, good low-temperature performance, high specific energy, small self-discharge rate, small volume, light weight and the like, can bring revolutionary changes to the field of energy storage, and is widely applied to various portable electronic devices and electric automobiles. The anode and cathode materials are core parts determining the performance of the lithium ion battery, and as the cathode material of the lithium ion battery, lithium titanate is always concerned, the charge-discharge speed of the lithium titanate material can be more than 10 ℃, and the lithium titanate material can still exert more ideal capacity at the temperature of-30 ℃, because the lithium titanate material particles have poor conductivity and larger internal resistance of the battery after the battery is assembled, the common pressed and sintered lithium titanate has no electrochemical oscillation effect, because the sample is not small particles with high dispersion degree, and the sample with the lithium content of more than 115 percent has no electrochemical oscillation effect, because the electrochemical oscillation effect is generally reduced along with the increase of the lithium content.
Disclosure of Invention
Therefore, the invention provides a preparation method of lithium titanate with electrochemical oscillation effect to solve the problems, and the technical scheme of the invention is realized as follows:
a preparation method of lithium titanate with electrochemical oscillation effect is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a lithium titanate precursor solution: adding 8-15 ml of hydrogen peroxide into 30-60 ml of deionized water, adding 2.20-3.52 g of 0.004-0.015 mol of tetrabutyl titanate into the deionized water, and stirring for 10-20min to obtain a solution A; adding 0.00256-0.00301 mol of lithium hydroxide powder into 20-30 ml of deionized water, and stirring for 5-10min to obtain a solution B; adding the solution B into the solution A, and then adding 30-50 ml of deionized water to a constant volume of 100-200 ml;
s2, spray drying: heating a tubular furnace, adding a lithium titanate precursor solution into an atomizer, starting an electrostatic generator, introducing a current-carrying gas, and obtaining powder adsorbed by static electricity on the surface of a stainless steel sheet after 1-3 hours;
s3, calcination process: and calcining the powder for 20-30 hours at 700-900 ℃ in an air atmosphere to obtain a sample.
Further, a preparation method of lithium titanate with electrochemical oscillation effect comprises the following steps:
s1, preparing a lithium titanate precursor solution: adding 10ml of hydrogen peroxide into 50ml of deionized water, adding 3.062g of 0.009mol of tetrabutyl titanate into the deionized water, and stirring for 10-20min to obtain a solution A; adding 0.00756mol of lithium hydroxide into 25ml of deionized water, and stirring for 5-10min to obtain a solution B; adding the solution B into the solution A, and then adding 40ml of deionized water to the volume of 125 ml;
s2, spray drying: heating a tubular furnace to 400-800 ℃, adding a lithium titanate precursor solution into an atomizer, starting an electrostatic generator, introducing a current-carrying gas, and obtaining powder adsorbed by static electricity on the surface of a stainless steel sheet after 2 hours;
s3, calcination process: calcining the powder at 800 ℃ for 24h in the air atmosphere to obtain a sample, wherein the aim of calcining at 800 ℃ is to form lithium titanate. The temperature is too low to form a complete crystal phase, so that the electrochemical oscillation phenomenon disappears.
Further, the carrier gas is argon and helium; the carrier gas is an inert gas to eliminate the gas from participating in the reaction.
Further, the tubular furnace heaies up to 200 ~ 600 ℃, and the purpose makes the rapid dehydration of atomized particles dry, and the temperature is crossed lowly and can be made the atomized particles dry and become slow, forms the hydrops, and the high temperature can make stainless steel collection device precipitate out impurity.
Further, the tube furnace was heated to 400 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention has the advantages of simple equipment, extremely low cost, high collection efficiency and simple process, and can prepare various powder samples.
(2) Compared with other similar products, the lithium titanate sample with the electrochemical oscillation effect has the characteristics of high particle dispersion degree and small particles, the morphological characteristic is a factor of the electrochemical oscillation effect, the pressed and sintered sample has no electrochemical oscillation effect, and the electrochemical oscillation effect is realized during charging, namely regular voltage oscillation is generated on a charging platform.
(3) The invention modulates the formula of lithium titanate with stronger electrochemical oscillation effect, because the electrochemical oscillation effect of the lithium titanate is weakened along with the increase of the lithium content.
Drawings
FIG. 1 is an SEM photograph of example 4
FIG. 2 is a battery charge-discharge diagram of example 4
FIG. 3 is the XRD pattern of example 4
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention can be obtained commercially without specific description.
The following preparation methods were used in the above examples 1 to 6:
spray drying: heating a tubular furnace to 400 ℃, adding the lithium titanate precursor solution into an atomizer, starting an electrostatic generator, introducing argon and helium, and obtaining powder adsorbed by static electricity on the surface of a stainless steel sheet after 2 hours;
and (3) calcining: calcining the powder for 24 hours at the temperature of 800 ℃ in the air atmosphere to obtain a sample.
As can be seen from the SEM image, the morphology of the synthesized sample is below 1um spheroidal particles, see fig. 1;
as can be seen from a battery charging and discharging diagram, the lithium titanate charging battery has obvious electrochemical oscillation effect in the lithium titanate charging process, the amplitude is 3mV-10mV, and the diagram is shown in FIG. 2;
as can be seen from the XRD pattern, the synthesized product is lithium titanate (Li)4Ti5O12) And the sample was more crystalline, see figure 3.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (3)
1. A preparation method of lithium titanate with electrochemical oscillation effect is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing a lithium titanate precursor solution: adding 8-15 ml of hydrogen peroxide into 30-60 ml of deionized water, adding 2.20-3.52 g of 0.004-0.015 mol of tetrabutyl titanate into the deionized water, and stirring for 10-20min to obtain a solution A; adding 0.00256-0.00301 mol of lithium hydroxide powder into 20-30 ml of deionized water, and stirring for 5-10min to obtain a solution B; adding the solution B into the solution A, and then adding 30-50 ml of deionized water to a constant volume of 100-200 ml;
s2, spray drying: heating a tubular furnace to 400-800 ℃, adding the lithium titanate precursor solution into an atomizer, starting an electrostatic generator, introducing argon and helium, and obtaining powder adsorbed by static electricity on the surface of a stainless steel sheet after 1-3 hours;
s3, calcination process: and calcining the powder for 20-30 hours at 700-900 ℃ in an air atmosphere to obtain a sample.
2. The method of preparing lithium titanate with electrochemical oscillation effect as claimed in claim 1, wherein: the method comprises the following steps:
s1, preparing a lithium titanate precursor solution: adding 10ml of hydrogen peroxide into 50ml of deionized water, adding 3.062g of 0.009mol of tetrabutyl titanate into the deionized water, and stirring for 10-20min to obtain a solution A; adding 0.00756mol of lithium hydroxide into 25ml of deionized water, and stirring for 5-10min to obtain a solution B; adding the solution B into the solution A, and then adding 40ml of deionized water to the volume of 125 ml;
s2, spray drying: heating a tubular furnace to 400-800 ℃, adding a lithium titanate precursor solution into an atomizer, starting an electrostatic generator, introducing argon and helium, and obtaining powder adsorbed by static electricity on the surface of a stainless steel sheet after 2 hours;
s3, calcination process: and calcining the powder at 800 ℃ for 24 hours in an air atmosphere to obtain a sample.
3. The method of preparing lithium titanate with electrochemical oscillation effect as claimed in claim 1, wherein: the tube furnace was warmed to 600 ℃.
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| CN113816420B (en) * | 2021-10-16 | 2022-07-12 | 海南大学 | Li with discharge electrochemical oscillation phenomenon4Ti5-xZrxO12Method for producing a material |
| CN114314648B (en) * | 2021-12-31 | 2022-11-08 | 海南大学 | Preparation method of lithium titanate material with electrochemical oscillation phenomenon in charging and discharging stages |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1409409A1 (en) * | 2001-07-20 | 2004-04-21 | Altair Nanomaterials Inc. | Process for making lithium titanate |
| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene combination electrode material |
| CN102070186A (en) * | 2010-11-23 | 2011-05-25 | 南京航空航天大学 | Preparation method of spinel type nano lithium titanate |
| CN102153137A (en) * | 2011-05-18 | 2011-08-17 | 中南大学 | Method for preparing spherical lithium titanate from inorganic titanium sources |
| CN104752692A (en) * | 2013-12-30 | 2015-07-01 | 北京有色金属研究总院 | Preparation method for LiFePO4/C composite anode material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1409409A1 (en) * | 2001-07-20 | 2004-04-21 | Altair Nanomaterials Inc. | Process for making lithium titanate |
| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene combination electrode material |
| CN102070186A (en) * | 2010-11-23 | 2011-05-25 | 南京航空航天大学 | Preparation method of spinel type nano lithium titanate |
| CN102153137A (en) * | 2011-05-18 | 2011-08-17 | 中南大学 | Method for preparing spherical lithium titanate from inorganic titanium sources |
| CN104752692A (en) * | 2013-12-30 | 2015-07-01 | 北京有色金属研究总院 | Preparation method for LiFePO4/C composite anode material |
Non-Patent Citations (1)
| Title |
|---|
| Sb2O3对锂离子负极材料Li4Ti5O12电化学性能的影响;刘云霞等;《电源技术》;20190228;第213-216页 * |
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