CN107768635B - Preparation method of barium sodium titanate composite negative electrode material for lithium ion battery - Google Patents

Preparation method of barium sodium titanate composite negative electrode material for lithium ion battery Download PDF

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CN107768635B
CN107768635B CN201710968609.1A CN201710968609A CN107768635B CN 107768635 B CN107768635 B CN 107768635B CN 201710968609 A CN201710968609 A CN 201710968609A CN 107768635 B CN107768635 B CN 107768635B
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朱彦荣
伊廷锋
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Anhui University of Technology AHUT
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    • H—ELECTRICITY
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    • 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
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Abstract

The invention discloses a preparation method of a barium sodium titanate composite negative electrode material for a lithium ion battery, and belongs to the technical field of lithium ion batteries. The method comprises the following specific steps: dissolving sodium nitrate and barium nitrate in an aqueous solution of alcohol, and adding an organic acid, and marking as a solution A; mixing TiCl4Dissolving in alcohol solution, and marking as solution B; mixing A and B, stirring, and evaporating to dryness; then placing the mixture into a muffle furnace for pre-sintering, cooling to room temperature, and ball-milling to obtain BaNa2Ti6O14A material; putting the mixture into a beaker, adding a surfactant and deionized water, performing ultrasonic treatment, and stirring; then adding pyrrole and acid solution, adding oxidant, stirring in ice water bath, and washing to obtain BaNa2Ti6O14@ PPy composite anode material. The negative electrode material has uniform particle size, stable and compact structure, considerable reversible capacity of a wide potential window, excellent rate capability and stable cycle life.

Description

Preparation method of barium sodium titanate composite negative electrode material for lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, particularly relates to a titanate negative electrode material of a lithium ion battery, and particularly relates to a preparation method of a barium sodium titanate composite negative electrode material.
Background
The traditional fossil energy is facing the crisis of shortage and even exhaustion, and brings huge pressure to environmental protection, and the novel industrialization development direction of circular economy and low-carbon economy can promote the rapid development of the new energy automobile industry. The lithium ion power battery is used as a new-generation environment-friendly and high-energy battery and has become a mainstream product of the power battery for the new energy automobile at present. Although the protection circuit of the lithium ion battery is mature, for the power battery, the selection of the cathode material is very critical to really ensure the safety. Most of the negative electrode materials of the current commercial lithium ion batteries are lithium intercalation type carbon materials, the oxidation-reduction potential of the carbon materials is close to that of metal lithium, and when the batteries are overcharged, the metal lithium can generate dendrite on the surface of the carbon negative electrode, so that the dendrite penetrates through a diaphragm to cause short circuit and thermal runaway of the batteries. The titanate-based material has higher lithium intercalation potential, can effectively avoid the precipitation of metal lithium, has certain oxygen absorption function at high temperature, has obvious safety characteristic and is considered to replace carbon material to be used as lithium ionIdeal selection of the cathode material of the sub-battery. Wherein Li4Ti5O12The titanium anode material is a successfully commercialized titanium anode material, and has the biggest advantages of basically no change in volume in the lithium removal/insertion process, good cycle performance, difficult formation of lithium dendrite in the charging and discharging process and high safety. However, Li is constrained by relatively low lithium ion diffusion rates, low electrical conductivity, and low theoretical capacity4Ti5O12More extensive application; in addition, relatively high voltage plateau (1.55V vs. li)+/Li), significantly reduces Li4Ti5O12The full cell voltage as the negative electrode further reduces the energy density of the full cell. Therefore, there is a great need to develop a novel titanate negative electrode material with a reliable potential plateau lower.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a barium sodium titanate composite negative electrode material for a high-performance lithium ion battery, so that the raw material source is wide, the operation is simple and convenient, the controllability is good, the reproducibility is high, the obtained material particles are small, the particle size distribution is uniform, and the crystallinity is high, thereby improving the electrochemical performance of the material while reducing the preparation cost of the material.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a barium sodium titanate composite negative electrode material comprises the following steps:
dissolving 0.02mol of sodium nitrate and 0.01mol of barium nitrate in an aqueous solution of alcohol, adding an organic acid, wherein the ratio of the organic acid to metal cations is (3-4) to 1, and stirring for 2-3h to obtain a solution A; 0.06mol of TiCl is added4Dissolving in alcohol solution, stirring for 1-2h, and marking as solution B. And rapidly mixing the solution A and the solution B, vigorously stirring, heating to 80 ℃, and after the liquid is evaporated to dryness, putting the liquid into a vacuum drying oven for vacuum drying at the temperature of 90-120 ℃ for 12 hours. Then presintering the precursor in a muffle furnace at the temperature of 400-2Ti6O14A material.1g of the obtained BaNa was taken2Ti6O14The material is put into a beaker, 100mg of surfactant is added, 400mL of deionized water is added, ultrasonic treatment is carried out for 10min, and then stirring is carried out for 10-16 h. Then 0.3-0.9mL of pyrrole and 10mL of 1 mol. L were added-1Adding 10-15g of oxidant, stirring for 2-4h in ice water bath, and washing for 3-5 times with mixed solution of deionized water and ethanol to obtain high-performance BaNa2Ti6O14@ PPy composite anode material.
The alcohol aqueous solution is ethanol aqueous solution, and the volume ratio of water to ethanol is 2: 1.
The organic acid is citric acid.
The surfactant is sodium dodecyl sulfate.
The acid solution is hydrochloric acid.
The oxidant is (NH)4)2S2O8。
Compared with the prior art, the invention has the following technical effects:
1. BaNa prepared by the invention2Ti6O14The composite cathode material has uniform particle size, stable structure and compactness. Wherein PPy plays a role in supporting a framework in the composite material, and BaNa2Ti6O14Is filled in a three-dimensional cavity constructed by PPy, and improves BaNa2Ti6O14Gaps among the particles further enable the whole composite material to be uniformly and compactly dispersed, and the stability and high conductivity of the electrode structure are maintained.
2. The material synthesized by the method has uniform and consistent particles and good dispersibility, and the obtained material has micron-sized particle size, thereby being beneficial to improving the electrochemical performance of the material.
3. The material obtained by the invention has considerable reversible capacity of a wide potential window, excellent rate capability and stable cycle life, so that the material has high practical use value and can effectively meet the practical requirements of various applications of lithium ion batteries.
4. The lithium ion battery cathode material prepared by the invention has higher theoretical capacity and rapid charge and discharge performance, and improves the energy density and power density of the lithium ion battery.
Drawings
FIG. 1 shows BaNa obtained in example 1 of the present invention2Ti6O14And @ PPy SEM image of the composite negative electrode material.
FIG. 2 shows BaNa obtained in example 1 of the present invention2Ti6O14The rate performance graph of the @ PPy composite anode material.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments, but the present invention is not limited to the embodiments.
Example 1
Dissolving 0.02mol of sodium nitrate and 0.01mol of barium nitrate in 300mL of ethanol water solution, adding citric acid, wherein the ratio of the citric acid to the metal cations is 3.5:1, stirring for 3h, and marking as solution A; 0.06mol of TiCl is added4Dissolve in alcohol solution and stir for 2h, record as solution B. And (3) rapidly mixing the solution A and the solution B, stirring vigorously, heating to 80 ℃, and after the liquid is evaporated to dryness, putting the liquid into a vacuum drying oven for vacuum drying for 12 hours at the temperature of 100 ℃. Then presintering the precursor in a muffle furnace at 450 ℃ for 6h, cooling to room temperature, ball-milling in a ball mill for 4h, sieving, then putting the precursor in the muffle furnace at 1000 ℃ for 12h, cooling to room temperature, and ball-milling for 24h to obtain the lithium ion battery cathode material BaNa2Ti6O14A material. 1g of the obtained BaNa was taken2Ti6O14The material was placed in a clean beaker, 100mg sodium dodecyl sulfate was added, 400mL deionized water was added and the mixture was sonicated for 10min and then stirred for 12 h. Then 0.5mL of pyrrole and 10mL of 1 mol. L were added-1Adding 12g (NH)4)2S2O8Stirring for 3h in ice water bath, and washing for 5 times with mixed solution of deionized water and ethanol to obtain high-performance BaNa2Ti6O14@ PPy composite anode material. The obtained BaNa2Ti6O14The @ PPy negative electrode material had uniform particles and a uniform particle size distribution, with a particle size of about 1 μm (FIG. 1). The obtained product is used as a research electrode, and a metal lithium sheet is used as a pairThe electrodes are assembled into a CR2016 type button lithium ion battery in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V according to different current densities. When the lithium removal capacity is 152.2mAh/g (figure 2) at the first time of 50mA/g charge and discharge, the reversible lithium removal capacity is 87.3mAh/g (figure 2) at the 500mA/g charge and discharge, and when the lithium removal capacity is recovered to 50mA/g charge and discharge after 70 cycles, the reversible lithium removal capacity is 117.2mAh/g (figure 2), and the excellent rate performance and the cycle stability are shown.
Example 2
Dissolving 0.02mol of sodium nitrate and 0.01mol of barium nitrate in 300mL of ethanol water solution, adding citric acid, wherein the ratio of the citric acid to the metal cations is 3:1, stirring for 2h, and marking as solution A; 0.06mol of TiCl is added4Dissolve in alcohol solution and stir for 1h, record as solution B. And (3) rapidly mixing the solution A and the solution B, stirring vigorously, heating to 80 ℃, and after the liquid is evaporated to dryness, putting the liquid into a vacuum drying oven for vacuum drying at 90 ℃ for 12 hours. Then presintering the precursor in a muffle furnace at 400 ℃ for 4h, cooling to room temperature, ball-milling in a ball mill for 3h, sieving, then putting the precursor in the muffle furnace at 900 ℃ for 10h, cooling to room temperature, and ball-milling for 24h to obtain the lithium ion battery cathode material BaNa2Ti6O14A material. 1g of the obtained BaNa was taken2Ti6O14The material was placed in a clean beaker, 100mg sodium dodecyl sulfate was added, 400mL deionized water was added and the mixture was sonicated for 10min and then stirred for 10 h. Then 0.3mL of pyrrole and 10mL of 1 mol. L were added-1Then 10g of (NH) is added4)2S2O8Stirring for 2h in ice water bath, and washing for 3 times with mixed solution of deionized water and ethanol to obtain high-performance BaNa2Ti6O14@ PPy composite anode material. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. The first lithium removal capacity is 141.1mAh/g at the time of 50mA/g charge and discharge, the reversible lithium removal capacity is 78.6mAh/g at the time of 500mA/g charge and discharge, and the reversible lithium removal capacity is 109.8mAh/g when the charge and discharge are recovered to 50mA/g after 70 cycles, thereby showing excellent multiplying powerThe energy and the cycling stability.
Example 3
Dissolving 0.02mol of sodium nitrate and 0.01mol of barium nitrate in 300mL of ethanol water solution, adding citric acid, wherein the ratio of the citric acid to the metal cations is 4:1, and stirring for 3h to obtain solution A; 0.06mol of TiCl is added4Dissolve in alcohol solution and stir for 2h, record as solution B. And (3) rapidly mixing the solution A and the solution B, stirring vigorously, heating to 80 ℃, and after the liquid is evaporated to dryness, putting the liquid into a vacuum drying oven for vacuum drying at 120 ℃ for 12 hours. And then presintering the precursor in a muffle furnace at 600 ℃ for 6h, cooling to room temperature, ball-milling in a ball mill for 4h, sieving, then putting in the muffle furnace at 1100 ℃ for 15h, cooling to room temperature, and ball-milling for 24h to obtain the lithium ion battery cathode material BaNa2Ti6O14A material. 1g of the obtained BaNa was taken2Ti6O14The material was placed in a clean beaker, 100mg sodium dodecyl sulfate was added, 400mL deionized water was added and the mixture was sonicated for 10min and then stirred for 16 h. Then 0.9mL of pyrrole and 10mL of 1 mol. L were added-1Then 15g of (NH) is added4)2S2O8Stirring for 4h in ice water bath, and washing for 5 times with mixed solution of deionized water and ethanol to obtain high-performance BaNa2Ti6O14@ PPy composite anode material. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium ion battery is charged and discharged at 50mA/g, the first lithium removal capacity is 150.8mAh/g, the reversible lithium removal capacity is 87.1mAh/g when the lithium ion battery is charged and discharged at 500mA/g, and when the lithium ion battery is recovered to be charged and discharged at 50mA/g after 70 cycles, the reversible lithium removal capacity is 116.12mAh/g, so that the lithium ion battery shows excellent rate performance and cycling stability.
Example 4
Dissolving 0.02mol of sodium nitrate and 0.01mol of barium nitrate in 300mL of ethanol water solution, adding citric acid, wherein the ratio of the citric acid to the metal cations is 3.2:1, stirring for 2-3h, and marking as solution A; adding 0.06mol TiCl4Dissolve in alcohol solution and stir for 1h, record as solution B. The solutions A and B were mixed rapidly and vigorouslyStirring, heating to 80 deg.C, evaporating to dry, and vacuum drying at 110 deg.C for 12 hr. Then presintering the precursor in a muffle furnace at 500 ℃ for 5h, cooling to room temperature, ball-milling in a ball mill for 4h, sieving, then putting the precursor in the muffle furnace at 1000 ℃ for 11h, cooling to room temperature, and ball-milling for 24h to obtain the lithium ion battery cathode material BaNa2Ti6O14A material. 1g of the obtained BaNa was taken2Ti6O14The material was placed in a clean beaker, 100mg sodium dodecyl sulfate was added, 400mL deionized water was added and the mixture was sonicated for 10min and then stirred for 11 h. Then 0.6mL of pyrrole and 10mL of 1 mol. L were added-1Then 11g of (NH) is added4)2S2O8Stirring for 2-4h in ice water bath, and washing with mixed solution of deionized water and ethanol for 4 times to obtain high-performance BaNa2Ti6O14@ PPy composite anode material. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium ion battery is charged and discharged at 50mA/g, the first lithium removal capacity is 146.3mAh/g, the reversible lithium removal capacity is 82.9mAh/g when the lithium ion battery is charged and discharged at 500mA/g, and when the lithium ion battery is recovered to 50mA/g after 70 cycles, the reversible lithium removal capacity is 115.5mAh/g, so that the lithium ion battery shows excellent rate performance and cycling stability.
Example 5
Dissolving 0.02mol of sodium nitrate and 0.01mol of barium nitrate in 300mL of ethanol water solution, adding citric acid, wherein the ratio of the citric acid to the metal cations is 3.7:1, stirring for 2.8h, and marking as solution A; adding 0.06mol TiCl4Dissolve in alcohol solution and stir for 2h, record as solution B. And (3) rapidly mixing the solution A and the solution B, stirring vigorously, heating to 80 ℃, and after the liquid is evaporated to dryness, putting the liquid into a vacuum drying oven for vacuum drying at 110 ℃ for 12 hours. Then presintering the precursor in a muffle furnace at 550 ℃ for 5h, cooling to room temperature, ball-milling in a ball mill for 4h, sieving, then putting the precursor in the muffle furnace at 950 ℃ for 14h, cooling to room temperature, and ball-milling for 24h to obtain the lithium ion battery cathode material BaNa2Ti6O14A material. Taking 1g of the obtained BaNa2Ti6O14The material was placed in a clean beaker, 100mg sodium dodecyl sulfate was added, 400mL deionized water was added and the mixture was sonicated for 10min and then stirred for 14 h. Then 0.4mL of pyrrole and 10mL of 1 mol. L were added-1Adding 12g (NH)4)2S2O8Stirring for 3h in ice water bath, and washing for 4 times with mixed solution of deionized water and ethanol to obtain high-performance BaNa2Ti6O14@ PPy composite anode material. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium ion battery is charged and discharged at 50mA/g, the first lithium removal capacity is 147.6mAh/g, the reversible lithium removal capacity is 81.5mAh/g when the lithium ion battery is charged and discharged at 500mA/g, and when the lithium ion battery is recovered to be charged and discharged at 50mA/g after 70 cycles, the reversible lithium removal capacity is 111.7mAh/g, so that the lithium ion battery shows excellent rate performance and cycling stability.
Example 6
Dissolving 0.02mol of sodium nitrate and 0.01mol of barium nitrate in 300mL of ethanol water solution, adding citric acid, wherein the ratio of the citric acid to the metal cations is 3.3:1, stirring for 2h, and marking as solution A; 0.06mol of TiCl is added4Dissolve in alcohol solution and stir for 2h, record as solution B. And (3) rapidly mixing the solution A and the solution B, stirring vigorously, heating to 80 ℃, and after the liquid is evaporated to dryness, putting the liquid into a vacuum drying oven for vacuum drying for 12 hours at the temperature of 100 ℃. Then presintering the precursor in a muffle furnace at 500 ℃ for 4h, cooling to room temperature, ball-milling in a ball mill for 3h, sieving, then putting the precursor in the muffle furnace at 1050 ℃ for 12h, cooling to room temperature, and ball-milling for 24h to obtain the lithium ion battery cathode material BaNa2Ti6O14A material. 1g of the obtained BaNa was taken2Ti6O14The material was placed in a clean beaker, 100mg sodium dodecyl sulfate was added, 400mL deionized water was added and the mixture was sonicated for 10min and then stirred for 15 h. Then 0.45mL of pyrrole and 10mL of 1 mol. L were added-1Then 13g of (NH) is added4)2S2O8Stirring for 3h in ice water bath, and then using a mixed solution of deionized water and ethanolWashing for 5 times to obtain high-performance BaNa2Ti6O14@ PPy composite anode material. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When the lithium ion battery is charged and discharged at 50mA/g, the first lithium removal capacity is 148.9mAh/g, the reversible lithium removal capacity is 82.6mAh/g when the lithium ion battery is charged and discharged at 500mA/g, and when the lithium ion battery is recovered to be charged and discharged at 50mA/g after 70 cycles, the reversible lithium removal capacity is 113.1mAh/g, so that the lithium ion battery shows excellent rate performance and cycling stability.
Example 7
Dissolving 0.02mol of sodium nitrate and 0.01mol of barium nitrate in 300mL of ethanol water solution, adding citric acid, wherein the ratio of the citric acid to the metal cations is 3.7:1, stirring for 2-3h, and marking as solution A; adding 0.06mol TiCl4Dissolve in alcohol solution and stir for 2h, record as solution B. And (3) rapidly mixing the solution A and the solution B, stirring vigorously, heating to 80 ℃, and after the liquid is evaporated to dryness, putting the liquid into a vacuum drying oven for vacuum drying at 110 ℃ for 12 hours. Then presintering the precursor in a muffle furnace at 500 ℃ for 4h, cooling to room temperature, ball-milling in a ball mill for 4h, sieving, then putting in the muffle furnace at 1100 ℃ for 14h, cooling to room temperature, and ball-milling for 24h to obtain the lithium ion battery cathode material BaNa2Ti6O14A material. 1g of the obtained BaNa was taken2Ti6O14The material was placed in a clean beaker, 100mg sodium dodecyl sulfate was added, 400mL deionized water was added and the mixture was sonicated for 10min and then stirred for 15 h. Then 0.8mL of pyrrole and 10mL of 1 mol. L were added-1Then adding 14g (NH)4)2S2O8Stirring for 3h in ice water bath, and washing for 4 times with mixed solution of deionized water and ethanol to obtain high-performance BaNa2Ti6O14@ PPy composite anode material. The obtained product is used as a research electrode, a metal lithium sheet is used as a counter electrode, and the CR2016 type button lithium ion battery is assembled in a glove box filled with argon, and charge and discharge cycles are carried out within a potential interval of 0.0-3.0V by different current densities. When 50mA/g is charged and discharged, the first lithium removal capacity is 147.9mAh/g, and 500mA/g is charged and dischargedThe reversible lithium removal capacity is 80.6mAh/g when electricity is used, and when the electricity is charged and discharged after 70 times of circulation and then is recovered to 50mA/g, the reversible lithium removal capacity is 110.8mAh/g, and excellent rate performance and circulation stability are shown.

Claims (6)

1. A preparation method of a barium sodium titanate composite negative electrode material for a lithium ion battery is characterized by comprising the following steps:
(1) dissolving 0.02mol of sodium nitrate and 0.01mol of barium nitrate in an aqueous solution of alcohol, adding an organic acid, stirring for 2-3 hours, and marking as a solution A, wherein the ratio of the organic acid to metal cations is 3-4: 1; 0.06mol of TiCl is added4Dissolving in an alcohol solution, stirring for 1-2h, and marking as a solution B; rapidly mixing the solution A and the solution B, violently stirring, heating to 80 ℃, and after the liquid is evaporated to dryness, putting the liquid into a vacuum drying oven for vacuum drying at the temperature of 90-120 ℃ for 12 hours; then presintering the precursor in a muffle furnace at 400-600 ℃ for 4-6h, cooling to room temperature, ball-milling in a ball mill for 3-4h, sieving, then placing in the muffle furnace at 900-1100 ℃ for 10-15h, cooling to room temperature, ball-milling for 24h, and obtaining BaNa2Ti6O14A material;
(2) taking 1g of BaNa prepared in the step (1)2Ti6O14Putting the material into a beaker, adding 100mg of surfactant, adding 400mL of deionized water, performing ultrasonic treatment for 10min, and stirring for 10-16 h; then adding 0.3-0.9mL of pyrrole and 10mL of 1 mol.L-1Adding 10-15g of oxidant into the acid solution, stirring for 2-4h in ice water bath, and washing for 3-5 times by using a mixed solution of deionized water and ethanol to obtain BaNa2Ti6O14@ PPy composite anode material.
2. The preparation method of the barium sodium titanate composite negative electrode material for the lithium ion battery according to claim 1, characterized by comprising the following steps: the alcohol aqueous solution in the step (1) is ethanol aqueous solution, and the volume ratio of water to ethanol is 2: 1.
3. The preparation method of the barium sodium titanate composite negative electrode material for the lithium ion battery according to claim 1, characterized by comprising the following steps: the organic acid in the step (1) is citric acid.
4. The preparation method of the barium sodium titanate composite negative electrode material for the lithium ion battery according to claim 1, characterized by comprising the following steps: the surfactant in the step (2) is sodium dodecyl sulfate.
5. The preparation method of the barium sodium titanate composite negative electrode material for the lithium ion battery according to claim 1, characterized by comprising the following steps: the acid solution in the step (2) is hydrochloric acid.
6. The preparation method of the barium sodium titanate composite negative electrode material for the lithium ion battery according to claim 1, characterized by comprising the following steps: the oxidant in the step (2) is (NH)4)2S2O8。
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