CN109336169B - Controllable synthesis method and application of lithium titanate micron-sized spherical secondary structure - Google Patents
Controllable synthesis method and application of lithium titanate micron-sized spherical secondary structure Download PDFInfo
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Abstract
The invention discloses a controllable synthesis method of a lithium titanate micron-sized spherical secondary structure, which comprises the steps of dissolving a titanium source and a surfactant in water, performing ultrasonic dispersion to obtain a titanium source dispersion liquid, adding a lithium source, performing further ultrasonic dispersion, adding a buffering agent, and adjusting the pH value to be>And (3) uniformly stirring at a constant temperature of 11 ℃ to 30 ℃ to obtain a mixed solution, reacting the mixed solution at 100 ℃ to 180 ℃ for 4-24 h, washing and drying the obtained product to obtain a lithium titanate precursor secondary structure, and finally calcining the lithium titanate precursor secondary structure at 400 ℃ to 1000 ℃ for 6-48 h in an inert atmosphere to obtain the lithium titanate precursor. The preparation method provided by the invention regulates the concentration of the raw material through the surfactant, and simultaneously regulates the pH of the reaction solution by using the buffer solvent, so that the controllability of the size of the lithium titanate micron-sized spherical secondary structure is realized, the product lithium titanate micron-sized spherical secondary structure has uniform particle size and stable structure when the pH and the raw material concentration are fixed, the obtained lithium titanate micron-sized spherical secondary structure is used as a high-specific volume capacity electrode material to be applied to a lithium ion battery, and the specific volume capacity can reach 120 ion-doped 232mAh/cm3And has good cycle stability.
Description
Technical Field
The invention relates to a controllable synthesis method and application of a lithium titanate micron-sized spherical secondary structure, and belongs to the field of battery material science.
Background
Lithium titanate material (Li)4Ti5O12LTO for short) as electrode material in Li+The lithium titanate material has the advantages that the volume change is basically avoided in the charge and discharge cycle process, the structure is stable, and the material is called as a zero-strain material, so that the lithium titanate material has excellent cycle performance. In addition, the charge and discharge platform of lithium titanate is stable, and the operating voltage is 1.55V (vs. Li/Li)+) Therefore, potential safety hazards caused by growth of lithium dendrites and decomposition of the electrolyte can be avoided. Adding Li in lithium titanate material+The diffusion coefficient of the lithium titanate material is large, so that the lithium titanate material is a hot candidate of the lithium ion battery cathode material. However, lithium titanate has an inherent low electronic conductivity (10)-13S/cm) resulting in poor performance at high rates. In order to solve the problem of conductivity of lithium titanate materials, most of research focuses on the nanocrystallization of lithium titanate materials. The nano-scale material can greatly shorten Li+And the migration distance of electrons, thereby improving the rate capability of the lithium titanate. However, the tap density of the nano material is too low, the gaps among particles are large, and the nano material cannot be compacted at all as an electrode material of a lithium ion battery.
The specific volume capacity of an electrode material of a lithium ion battery refers to the capacity that the electrode material can provide per unit volume. The more active material per unit volume, the greater the capacity that can be provided, that is to say the greater the tap density of the material, the higher the specific volume capacity. The specific volume capacity is an important index for measuring the electrode material of the lithium ion battery besides the specific mass capacity. Because the space left for lithium ion batteries is very limited in both portable electronic products and electric vehicles, the ability to provide more energy (i.e., high specific volume capacity) in a limited space becomes a very important factor. And the nano material has too low tap density, so that the requirement of high specific volume capacity is difficult to meet.
Chinese patent CN 101000960A discloses a composite lithium titanate electrode material and a preparation method thereof, the patent is that inorganic lithium salt, titanium dioxide and carbon source/dopant after ball milling are dispersed in an organic solvent and dried instantly, then secondary particles consisting of lithium titanate and carbon/dopant are obtained through high-temperature heat treatment, and the tap density of the finally obtained composite lithium titanate electrode material is 0.7-1.5g/cm3. Chinese patent CN 104979541A discloses a lithium titanate composite material and a preparation method thereof, wherein a lithium source, titanium dioxide, an aluminum source, a carbon source and water are mixed and ball-milled to obtain slurry, then the slurry is dried, crushed and calcined at high temperature to obtain secondary particles of composite lithium titanate, and the tap density is 0.9-1.2g/cm3. Although the above patents all form lithium titanate nanoparticles into agglomerates, thereby improving the tap density of lithium titanate to a certain extent, the mechanically obtained agglomerates have large particle size difference and uncontrollable particle size, which is difficult to control in production.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a controllable synthesis method capable of realizing the size of a micron-sized spherical secondary structure of lithium titanate aiming at the defects of the prior art, so that the problem of low tap density of the lithium titanate material is solved, and the lithium titanate material is suitable for industrial production.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a controllable synthesis method of a lithium titanate micron-sized spherical secondary structure comprises the following steps:
the method comprises the following steps: dissolving a titanium source and a surfactant in water, and performing ultrasonic dispersion to obtain a titanium source dispersion liquid;
step two: adding a lithium source into the dispersion liquid obtained in the step one, and further performing ultrasonic dispersion;
step three: adding a buffering agent into the dispersion liquid obtained in the step two, adjusting the pH to be more than 11, and uniformly stirring at a constant temperature of 10-30 ℃ to obtain a mixed solution;
step four: reacting the mixed solution obtained in the third step at 100-180 ℃ for 4-24 h, washing and drying the obtained product to obtain a lithium titanate precursor secondary structure;
step five: and D, calcining the lithium titanate precursor secondary structure obtained in the step four in an inert atmosphere at 400-1000 ℃ for 6-48 h to obtain the lithium titanate precursor.
In the first step, the titanium source is one or a mixture of more of titanium dioxide, metatitanic acid and titanium hydroxide; the concentration of titanium element in the titanium source dispersion liquid is more than 3mol/L, and more preferably 3 to 5mol/L, considering that too high a concentration makes it difficult to disperse the titanium source.
The surfactant is one or a mixture of more of ammonium dodecyl sulfate, secondary alkyl sodium sulfonate, dodecyl phosphate, coconut oil fatty acid diethanolamide, C12-16 alkyl glycoside, nonylphenol polyoxyethylene ether, octadecyl trimethyl ammonium chloride and cetearyl ether-20, and the usage amount of the surfactant is 2.5-5% of the total mass of the titanium source and the surfactant.
In the first step, ultrasonic treatment is carried out for 1-4 hours in a frequency range of 30-60 KHz.
In the second step, the lithium source is one or a mixture of more of lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate and lithium chloride; and in the dispersion liquid obtained in the step two, the molar ratio of the lithium element to the titanium element is controlled to be 4-4.5: 5.
And in the second step, ultrasonic treatment is carried out for 0.5-2 h in a frequency range of 20-60 KHz.
In the third step, the buffer is one or a mixture of more of disodium hydrogen phosphate-sodium hydroxide, glycine-sodium chloride-sodium hydroxide and potassium chloride-sodium hydroxide, and the pH of the dispersion is adjusted to be more than 11 by the buffer, and the preferable pH is 11.6-13.
In the third step, stirring is carried out for 4-12 hours at a rotating speed of 600-1000 revolutions.
And in the fourth step, the water washing is carried out for 3-5 times, and the drying is carried out for 6-24 hours in a vacuum oven at the temperature of 60-90 ℃.
In the fifth step, the inert atmosphere is any one atmosphere of argon, nitrogen and helium.
Further, the lithium titanate micron-sized spherical secondary structure can be coated with carbon, and the carbon coating method specifically comprises the following steps: adding a carbon source in addition to the buffering agent in the third step, and stirring to form a mixed solution; carrying out heat treatment on the mixed solution in the fourth step through a reaction kettle to form a carbon precursor-coated lithium titanate precursor secondary structure; the secondary structure is placed in a tubular furnace under inert atmosphere and calcined to obtain the carbon-coated lithium titanate micron-sized spherical secondary structure. The carbon source can be glucose, sucrose, starch, polyvinylpyrrolidone, epoxy resin and polyethylene glycol, and in consideration of environmental protection and cost, the carbon source is further preferably glucose, sucrose and starch; the adding amount of the carbon source is 0.025-0.1 g/mL of the mixed solution. In consideration of improving the graphitization degree of the carbon shell, the heat treatment temperature of the reaction kettle in the step four is preferably 120-180 ℃, and the reaction time is preferably 8-24 h; and fifthly, the calcination temperature of the tubular furnace is preferably 600-1000 ℃, and the calcination time is preferably 12-48 h.
The lithium titanate micron-sized spherical secondary structure prepared by the preparation method is also in the protection scope of the invention, and the lithium titanate micron-sized spherical secondary structure is micron-sized spherical particles formed by tightly self-assembling lithium titanate nano particles from the center of a sphere from inside to outside along the diameter of the sphere.
Furthermore, the size of the micron-sized spherical particles is 1-15 mu m, and the specific surface area is 5-23 m2(iv) g, tap density of 0.7-1.4g/cm3。
The invention also provides application of the prepared lithium titanate micron-sized spherical secondary structure as an electrode material in a lithium ion battery.
Has the advantages that:
1. according to the preparation method, the concentration of the raw material is regulated and controlled by the surfactant, and the pH of the reaction solution is regulated and controlled by the buffer solvent, so that the size of the lithium titanate micron-sized spherical secondary structure can be controlled, and the product lithium titanate micron-sized spherical secondary structure has uniform particle size and stable structure when the pH and the concentration of the raw material are fixed; the obtained lithium titanate micron-sized spherical secondary structure is formed by tightly self-assembling lithium titanate nanoparticles from the sphere center from inside to outside along the sphere diameter, so that the tap density of a lithium titanate material is improved; the preparation method is simple and easy to operate, has good stability and high repeatability, and is suitable for industrial production;
2. the lithium titanate micron-sized spherical secondary structure prepared by the invention is applied to a lithium ion battery as an electrode material with high specific volume capacity, and the specific volume capacity can reach 120-plus-one 232mAh/cm3And has good cycle stability.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
Fig. 1 is an XRD pattern of micron-sized spherical secondary structure of lithium titanate, a product of example 1 of the present invention.
Fig. 2 is an SEM image of a micron-sized spherical secondary structure of lithium titanate as a product in example 1 of the present invention.
Fig. 3 is an SEM image of a micron-sized spherical secondary structure of the lithium titanate product of example 2 of the present invention.
Fig. 4 is an SEM image of a micron-sized spherical secondary structure of the lithium titanate product of example 3 of the present invention.
Fig. 5 is an SEM image of comparative example 1 product lithium titanate nanoparticles of the present invention.
Fig. 6 is an SEM image of the carbon-coated lithium titanate micron-sized spherical secondary structure of the product of example 4 of the present invention.
Fig. 7 is a 1 st-4 th charging and discharging curve diagram of the lithium titanate micron-sized spherical secondary structure as an electrode material of a lithium ion battery in example 3 of the present invention.
Fig. 8 is a charge-discharge cycle performance diagram of a lithium titanate micron-sized spherical secondary structure of a product of example 3 of the present invention and lithium titanate nanoparticles of a product of comparative example 1 as an electrode material of a lithium ion battery. (a) The figure is a cyclic comparison graph of the ratio of the mass capacity to the volume capacity, and the figure (b) is a cyclic comparison graph of the ratio of the mass capacity to the volume capacity.
Fig. 9 is a rate performance diagram of the carbon-coated lithium titanate micron-sized spherical secondary structure of the product of example 4 of the present invention as an electrode material of a lithium ion battery.
Detailed Description
The invention will be better understood from the following examples.
In the following examples and comparative examples, the phases of the products were tested using an X-ray powder diffractometer (XRD, Bruker D8); the morphology was tested using a field emission scanning electron microscope (SEM, Hitachi S-4800); the particle size distribution was measured using a laser particle size analyzer (MASTERSIZER 2000); the specific surface area was measured using a specific surface analyzer (Micromeritics, ASAP 2020); the tap density was measured using a tap densitometer (Quantachrome AT-4Autotap machine); the pH was measured using a pH meter (PHS-3C).
Example 1
In this embodiment, the titanium source is titanium dioxide, the surfactant is ammonium lauryl sulfate, the lithium source is lithium hydroxide, and the buffer is glycine-sodium chloride-sodium hydroxide (where the concentration of glycine and sodium chloride in the mixed solution is 0.049mol/L, and the concentration of sodium hydroxide in the mixed solution is 0.051 mol/L).
The preparation method comprises the following steps:
(1) dispersing 11.18g of titanium dioxide and 0.32g of ammonium dodecyl sulfate in 40mL of water, and carrying out ultrasonic treatment for 4 hours at the frequency of 30KHz to obtain a dispersion liquid with the concentration of the titanium dioxide of 3.5mol/L, wherein the ammonium dodecyl sulfate accounts for 2.8 wt.% of the total mass of the titanium dioxide and the ammonium dodecyl sulfate;
(2) adding 2.68g of lithium hydroxide into the dispersion liquid obtained in the step (1), and performing ultrasonic treatment at the frequency of 20KHz for 2 hours to disperse the lithium hydroxide;
(3) adding a buffering agent glycine-sodium chloride-sodium hydroxide into the dispersion liquid obtained in the step (2) to control the pH to be 11.6, and stirring at a constant temperature of 20 ℃ at a rotating speed of 600 revolutions for 12 hours;
(4) transferring the dispersion liquid obtained in the step (3) into a 100mL reaction kettle, heating at 100 ℃ for 20 hours, washing the obtained product for 3 times after the heat treatment is finished, and drying in a vacuum oven at 80 ℃ for 6 hours to obtain a lithium titanate precursor secondary structure;
(5) and (5) placing the lithium titanate precursor secondary structure obtained in the step (4) into a tube furnace, and calcining for 16 hours at 400 ℃ under the protection of argon to obtain the lithium titanate micron-sized spherical secondary structure.
Fig. 1 is an XRD pattern of micron-sized spherical secondary structure of lithium titanate, a product of example 1 of the present invention. By comparing with a standard powder diffraction pattern of lithium titanate, each diffraction peak in fig. 1 can correspond to a crystal face of spinel lithium titanate, and the crystallinity of the micron-sized spherical secondary structure of the product lithium titanate is proved to be good. Fig. 2 is an SEM image of the product lithium titanate micron-sized spherical secondary structure in example 1 of the present invention, which shows that the product lithium titanate micron-sized spherical secondary structure has a uniform particle size. The particle size of the product is about 2 microns after being analyzed by a laser particle size analyzer. Fig. 2 shows that the product lithium titanate micron-sized spherical secondary structure is formed by assembling a plurality of lithium titanate nano-particles, and pores among the particles are obvious. The tap density of the micron-sized spherical secondary structure of the lithium titanate of the product in example 1 is 0.90g/cm measured by a tap density instrument3。
Example 2
In this example, the titanium source was titanium hydroxide, the surfactant was coconut oil fatty acid diethanolamide, the lithium source was lithium nitrate, and the buffer was disodium hydrogen phosphate-sodium hydroxide (wherein the concentration of disodium hydrogen phosphate in the mixed solution was 0.025mol/L, and the concentration of sodium hydroxide in the mixed solution was 0.027 mol/L).
The preparation method comprises the following steps:
(1) dispersing 2.59g of titanium hydroxide and 0.09g of coconut oil fatty acid diethanolamide in 10mL of water, and carrying out ultrasonic treatment at the frequency of 50KHz for 2 hours to obtain a dispersion liquid with the concentration of the titanium hydroxide of 4mol/L, wherein the content of the coconut oil fatty acid diethanolamide accounts for 3.4 wt.% of the total mass of the titanium hydroxide and the coconut oil fatty acid diethanolamide;
(2) adding 2.48g of lithium nitrate into the dispersion liquid obtained in the step (1), and performing ultrasonic treatment at the frequency of 40KHz for 1 hour to disperse the lithium nitrate;
(3) adding a buffering agent disodium hydrogen phosphate-sodium hydroxide into the dispersion liquid obtained in the step (2) to control the pH value to be 12, and stirring at a constant temperature of 10 ℃ at a rotating speed of 800 revolutions for 8 hours;
(4) transferring the dispersion liquid obtained in the step (3) into a 50mL reaction kettle, heating at 160 ℃ for 12 hours, washing the obtained product for 4 times after the heat treatment is finished, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain a lithium titanate precursor secondary structure;
(5) and (5) placing the lithium titanate precursor secondary structure obtained in the step (4) in a tube furnace, and calcining for 6 hours at 700 ℃ under the protection of nitrogen to obtain the lithium titanate micron-sized spherical secondary structure.
The lithium titanate product obtained in example 2 has a micron-sized spherical secondary structure with a particle size of about 8 microns, which can be obtained by analysis of a laser particle size analyzer. Fig. 3 is an SEM image of a micron-sized spherical secondary structure of lithium titanate obtained in example 2 of the present invention, which shows that the micron-sized spherical secondary structure of lithium titanate obtained in example 2 is still assembled by a plurality of small lithium titanate nanoparticles, but compared with fig. 2, it is obvious that the pores between particles in fig. 3 are reduced, that is, the lithium titanate nanoparticles are arranged more tightly. The tap density of the micron-sized spherical secondary structure of the lithium titanate of the product in example 2 is 1.19g/cm measured by a tap density instrument3。
Example 3
In this example, the titanium source was metatitanic acid, the surfactant was octadecyl trimethyl ammonium chloride, the lithium source was lithium carbonate, and the buffer was potassium chloride-sodium hydroxide (where the concentration of potassium chloride in the mixed solution was 0.05mol/L, and the concentration of sodium hydroxide in the mixed solution was 1.32 mol/L).
The preparation method comprises the following steps:
(1) dispersing 19.58g of metatitanic acid and 0.92g of octadecyl trimethyl ammonium chloride in 40mL of water, and performing ultrasonic treatment at the frequency of 60KHz for 1 hour to obtain a dispersion liquid with the concentration of metatitanic acid of 5mol/L, wherein the octadecyl trimethyl ammonium chloride accounts for 4.5 wt.% of the total mass of the metatitanic acid and the octadecyl trimethyl ammonium chloride;
(2) adding 6.28g of lithium carbonate into the dispersion liquid obtained in the step (1), and performing ultrasonic treatment at the frequency of 60KHz for 0.5 hour to disperse the lithium carbonate;
(3) adding a buffering agent potassium chloride-sodium hydroxide into the dispersion liquid obtained in the step (2) to control the pH value to be 13, and stirring at a constant temperature of 30 ℃ and a rotating speed of 1000 revolutions for 4 hours;
(4) transferring the dispersion liquid obtained in the step (3) into a 100mL reaction kettle, heating at 180 ℃ for 4 hours, washing the obtained product for 5 times after the heat treatment is finished, and drying in a vacuum oven at 90 ℃ for 24 hours to obtain a lithium titanate precursor secondary structure;
(5) and (5) placing the lithium titanate precursor secondary structure obtained in the step (4) in a tube furnace, and calcining for 30 hours at 800 ℃ under the protection of helium to obtain the lithium titanate micron-sized spherical secondary structure.
The lithium titanate product obtained in example 3 has a micron-sized spherical secondary structure with a particle size of about 15 microns, which can be obtained by analysis of a laser particle size analyzer. Fig. 4 is an SEM image of a micron-sized spherical secondary structure of lithium titanate of a product in example 3 of the present invention, and compared with fig. 2 and fig. 3, the micron-sized spherical secondary structure of lithium titanate in fig. 4 is significantly more compact, and the arrangement of lithium titanate nanoparticles is more compact. The tap density of the micron-sized spherical secondary structure of the lithium titanate product in example 3 is 1.38g/cm measured by a tap density instrument3. Comparing examples 1 to 3, it can be concluded that the size and tap density of the lithium titanate micron-sized spherical secondary structure increase with the increase of the reaction solution pH and the raw material concentration.
Comparative example 1
In this comparative example, the titanium source was metatitanic acid and the lithium source was lithium carbonate.
The preparation method comprises the following steps:
(1) dispersing 7.83g of metatitanic acid in 40mL of water, and carrying out ultrasonic treatment at the frequency of 60KHz for 1 hour to obtain a dispersion liquid with the concentration of metatitanic acid of 2mol/L (because the metatitanic acid at the concentration has better dispersibility in water, no surfactant is added);
(2) adding 2.51g of lithium carbonate into the dispersion liquid obtained in the step (1), performing ultrasonic treatment at the frequency of 60KHz for 0.5 hour to disperse the lithium carbonate, measuring the pH value of the dispersion liquid by a pH meter to be 10, and stirring at the constant temperature of 30 ℃ for 4 hours at the rotating speed of 1000 revolutions;
(3) transferring the dispersion liquid obtained in the step (2) into a 100mL reaction kettle, heating at 180 ℃ for 4 hours, washing the obtained product with water for 5 times after the heat treatment is finished, and drying in a vacuum oven at 90 ℃ for 24 hours to obtain a lithium titanate nanoparticle precursor;
(4) and (4) placing the lithium titanate nanoparticle precursor obtained in the step (3) into a tube furnace, and calcining for 30 hours at 800 ℃ under the protection of helium to obtain the lithium titanate nanoparticle.
FIG. 5 is an SEM image of comparative example 1 product lithium titanate nanoparticles of the present invention, showing that high concentrations of titanium source are ensured without surfactant and that solution pH is ensured without buffer solvent>Under the condition of 11, the product is lithium titanate nano-particles with the particle size of 100-200nm, and the lithium titanate nano-particles can not be self-assembled into a compact lithium titanate micron-sized spherical secondary structure under the experimental condition. The tap density of the lithium titanate nano particles of the product in the comparative example 1 is 0.53g/cm measured by a tap density instrument3。
Example 4
This example 4 was the same as example 3 above in the basic conditions, except that 2g of glucose was added in addition to the buffer in step (3) in this example 4; carrying out hydrothermal reaction by heating at 180 ℃ for 8 hours in the step (4), washing and drying the product to obtain a carbon precursor-coated lithium titanate precursor secondary structure; and (5) calcining the carbon-coated lithium titanate micron-sized spherical secondary structure for 48 hours at 600 ℃ under the protection of nitrogen in the step (5).
The carbon-coated lithium titanate micron-sized spherical secondary structure obtained in example 4 has a particle size of about 15 microns by analysis of a laser particle size analyzer. Fig. 6 is an SEM image of a carbon-coated lithium titanate micron-sized spherical secondary structure obtained in example 4 of the present invention, and compared with fig. 4, a carbon shell is coated on nanoparticles constituting the lithium titanate micron-sized spherical secondary structure, so that the surface of the carbon-coated lithium titanate micron-sized spherical secondary structure in fig. 6 is rougher. Since the particle size of the carbon-coated lithium titanate micro-scale spherical secondary structure of the product of example 4 is similar to that of the lithium titanate micro-scale spherical secondary structure of the product of example 3, it can be inferred that the thickness of the carbon coating layer in the product of example 4 should be very thin. The tap density of the carbon-coated lithium titanate micron-sized spherical secondary structure of the product of example 4 measured by a tap density instrument is 1.36g/cm3。
Example 5
The basic conditions of this example 5 are the same as those of the above example 1, except that in this example 5, the mass of the titanium dioxide added in step (1) is 9.58g, the surfactant added is secondary sodium alkylsulfonate, the mass added is 0.24g, and the obtained dispersion liquid with the concentration of titanium dioxide of 3mol/L, wherein the secondary sodium alkylsulfonate accounts for 2.5 wt.% of the total mass of the titanium dioxide and the secondary sodium alkylsulfonate; the lithium source added in the step (2) is lithium sulfate, and the added mass is 5.28 g.
The finally obtained lithium titanate micron-sized spherical secondary structure is analyzed by a laser particle size analyzer to obtain the lithium titanate micron-sized spherical secondary structure with the particle size of 1 micron. The tap density of the micron-sized spherical secondary structure of the lithium titanate obtained in example 5 is 0.72g/cm measured by a tap density instrument3。
Example 6
This example 6 was identical to the basic conditions of the above example 2 except that in this example 6, the mass of titanium hydroxide added in step (1) was 2.92g, the surfactant added was a C12-16 alkyl glycoside, and the mass added was 0.09g, to obtain a dispersion having a titanium hydroxide concentration of 4.5mol/L, wherein the C12-16 alkyl glycoside accounted for 3.0 wt.% of the total mass of the titanium hydroxide and the C12-16 alkyl glycoside; the lithium source added in the step (2) is lithium phosphate, and the added mass is 1.56 g; in the step (3), 1g of sucrose is added besides the buffering agent; obtaining a carbon precursor coated lithium titanate secondary structure after hydrothermal treatment in the step (4) and water washing and drying of the product; and (5) calcining the carbon-coated lithium titanate micron-sized spherical secondary structure for 40 hours at 700 ℃ under the protection of nitrogen in the step (5).
The finally obtained carbon-coated lithium titanate micron-sized spherical secondary structure is analyzed by a laser particle size analyzer to obtain a particle size of 10 microns. The tap density of the carbon-coated lithium titanate micron-sized spherical secondary structure of the product of example 6, measured by a tap density meter, was 1.23g/cm3。
Example 7
This example 7 is the same as example 3 above in basic conditions except that in this example 7, 13.71g of metatitanic acid was added in mass in step (1), 0.57g of dodecyl phosphate was added as a surfactant, and a dispersion having a metatitanic acid concentration of 3.5mol/L was obtained, wherein secondary dodecyl phosphate accounted for 4.0 wt.% of the total mass of metatitanic acid and dodecyl phosphate; the mass of lithium nitrate added in step (2) was 7.72 g.
The finally obtained lithium titanate micron-sized spherical secondary structure is analyzed by a laser particle size analyzer to obtain the lithium titanate micron-sized spherical secondary structure with the particle size of 12 microns. The tap density of the micron-sized spherical secondary structure of the lithium titanate product in example 7 is 1.26g/cm measured by a tap density instrument3。
Example 8
This example 8 is the same as the basic conditions of the above example 3 except that in this example 8, 15.66g of metatitanic acid was added in mass in step (1), cetearyl ether-20 was added as a surfactant, and 0.82g of metatitanic acid was added to obtain a dispersion having a concentration of 4mol/L of metatitanic acid, wherein cetearyl ether-20 accounted for 5 wt.% of the total mass of metatitanic acid and cetearyl ether-20; the lithium source added in the step (2) is lithium hydroxide, and the added mass is 3.45 g; in the step (3), 1g of starch is added besides the buffering agent; obtaining a carbon precursor-coated lithium titanate precursor secondary structure through hydrothermal reaction of heating at 120 ℃ for 24 hours in the step (4) and water washing and drying of a product; and (5) calcining the carbon-coated lithium titanate micron-sized spherical secondary structure for 12 hours at 1000 ℃ under the protection of helium in the step (5).
The finally obtained carbon-coated lithium titanate micron-sized spherical secondary structure is analyzed by a laser particle size analyzer to obtain the particle size of 13 microns. The tap density of the carbon-coated lithium titanate micron-sized spherical secondary structure of the product of example 8, measured by a tap density meter, was 1.30g/cm3。
Table 1 comparison of synthesis conditions of micron-sized spherical secondary structure of lithium titanate
As can be seen from the comparative data in examples 1 to 8 and Table 1, the size and tap density of the micron-sized spherical secondary structure of lithium titanate increases as the pH of the reaction solution and the concentration of the raw material increase. Relative to the concentration of the raw materials, the pH of the reaction solution has a decisive influence on the size and tap density of the lithium titanate micron-sized spherical secondary structure.
Example 9
The products of examples 1 to 8 and the product of comparative example 1 were mixed with polyvinylidene fluoride (PVDF) and Super phosphorus black (Super P carbon black) in a mass ratio of 8: 1:1, and adding N-methylpyrrolidone (NMP) to make the mass-volume ratio of PVDF and NMP 50 mg/ml. The slurry was stirred for 12 hours and then coated on a double-sided smooth copper foil of 10 microns thickness, dried at 110 degrees under vacuum for 12 hours and then rolled with a two-roll tablet press. Cutting into pieces by a punching machine, placing the pieces into a glove box, taking a metal lithium piece as a counter electrode and taking 1mol/L LiPF6And the electrolyte is prepared from the electrolyte of/EC + DMC + EMC (the volume ratio is 1:1:1), the separator is prepared from polypropylene (PP) material, and the CR2032 type button cell is assembled. Performing performance detection by using a LAND CT2001A battery test system, wherein the test voltage is 1-2.5V vs+Li, test conditions were room temperature.
Fig. 7 is a 1 st-4 th charging and discharging curve diagram of the lithium titanate micron-sized spherical secondary structure as an electrode material of a lithium ion battery in example 3 of the invention, and it can be seen that the product lithium titanate micron-sized spherical secondary structure has high charging and discharging capacity, flat potential curve, high first efficiency and excellent cycle performance.
Fig. 8 is a charge-discharge cycle performance diagram of a lithium titanate micron-sized spherical secondary structure of a product of example 3 of the present invention and lithium titanate nanoparticles of a product of comparative example 1 as an electrode material of a lithium ion battery. (a) The figure is a cyclic comparison graph of the ratio of the mass capacity to the volume capacity, and the figure (b) is a cyclic comparison graph of the ratio of the mass capacity to the volume capacity. As can be seen from fig. 8(a), the specific mass capacity of the lithium titanate micron-sized spherical secondary structure is comparable to that of the lithium titanate nanoparticles at the previous 200 cycles. However, in 200-plus-500 cycles, the cycling stability of the lithium titanate micron-sized spherical secondary structure is superior to that of the lithium titanate nano-particles. The reason is that lithium titanate nanoparticles are low in tap density, cannot be compacted when used as an electrode material of a lithium ion battery, and cannot be tightly arranged, so that the lithium titanate nanoparticles gradually fall off from a conductive system in the battery circulation process, and capacity attenuation is caused. However, for the lithium titanate micron-sized spherical secondary structure, the secondary structure itself is composed of nano-sized particlesThe particles are tightly arranged and assembled, so that the secondary structure can bring higher tap density. In addition, a stable secondary mechanism can maintain the stability of the structure in the circulating process and prevent the nanoparticles from being separated from the structure. Therefore, the cycling stability of the lithium titanate micron-sized spherical secondary structure is superior to that of the lithium titanate nano-particles. Fig. 8(b) shows another advantage of high tap density — high specific volume capacity. Because of the tap density (1.38 g/cm) of the micron-sized spherical secondary structure of lithium titanate3) Tap density of almost lithium titanate nanoparticles (0.53 g/cm)3) Three times that of the lithium titanate nano-particles, and thus the specific volume capacity of the lithium titanate micron-sized spherical secondary structure is almost three times that of the lithium titanate nano-particles.
Table 2 shows the specific mass capacity and the specific volume capacity of the lithium titanate micron-sized spherical secondary structure and the lithium titanate nanoparticles as the electrode material of the lithium ion battery. As can be seen from table 2, the specific mass capacity of the lithium titanate micron-sized spherical secondary structure is substantially in the same order of magnitude as that of the lithium titanate nanoparticles, but the cycling stability of the lithium titanate micron-sized spherical secondary structure as an electrode material of a lithium ion battery is superior to that of the lithium titanate nanoparticles. In addition, the tap density of the lithium titanate micron-sized spherical secondary structure is relatively large (0.7-1.4 g/cm)3) Therefore, the specific volume capacity of the lithium titanate micron-sized spherical secondary structure far exceeds that of the lithium titanate nano-particles.
Table 2 comparison of battery performance of lithium titanate micron-sized spherical secondary structure and lithium titanate nanoparticles
Fig. 9 is a rate performance graph of the carbon-coated lithium titanate micron-sized spherical secondary structure as an electrode material of a lithium ion battery in example 4 of the present invention, and it can be seen that the rate performance of the carbon-coated lithium titanate micron-sized spherical secondary structure is excellent. The specific mass capacity of 172.1mAh/g, 162.2mAh/g, 145.1mAh/g and 127.5mAh/g respectively under the current density of 1C, 3C, 6C and 10C.
The present invention provides a controllable synthesis method of a lithium titanate micron-sized spherical secondary structure, and an idea and a method for applying the same, and a plurality of methods and approaches for implementing the technical scheme are provided, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of improvements and embellishments may be made without departing from the principle of the present invention, and these improvements and embellishments should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (6)
1. A controllable synthesis method of a lithium titanate micron-sized spherical secondary structure is characterized by comprising the following steps:
the method comprises the following steps: dissolving a titanium source and a surfactant in water, and performing ultrasonic dispersion to obtain a titanium source dispersion liquid;
step two: adding a lithium source into the dispersion liquid obtained in the step one, and further performing ultrasonic dispersion;
step three: adding a buffering agent into the dispersion liquid obtained in the step two, adjusting the pH to be more than 11, and uniformly stirring at a constant temperature of 10-30 ℃ to obtain a mixed solution;
step four: reacting the mixed solution obtained in the third step at 100-180 ℃ for 4-24 h, washing and drying the obtained product to obtain a lithium titanate precursor secondary structure;
step five: calcining the lithium titanate precursor secondary structure obtained in the fourth step in an inert atmosphere at 400-1000 ℃ for 6-48 h to obtain the lithium titanate precursor;
in the first step, the titanium source is one or a mixture of more of titanium dioxide, metatitanic acid and titanium hydroxide; the concentration of titanium element in the titanium source dispersion liquid is more than 3 mol/L.
2. The controllable synthesis method according to claim 1, wherein in the first step, the surfactant is one or a mixture of several of ammonium lauryl sulfate, secondary alkyl sodium sulfonate, dodecyl phosphate, coconut oil fatty acid diethanolamide, C12-16 alkyl glycoside, nonylphenol polyoxyethylene ether, octadecyl trimethyl ammonium chloride and cetearyl ether-20, and the amount of the surfactant is 2.5-5% of the total mass of the titanium source and the surfactant.
3. The controllable synthesis method according to claim 1, wherein in the second step, the lithium source is one or a mixture of several of lithium hydroxide, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate and lithium chloride; in the dispersion liquid obtained in the second step, the molar ratio of the lithium element to the titanium element is 4-4.5: 5.
4. The controllable synthesis method according to claim 1, wherein in step three, the buffer is one or a mixture of disodium hydrogen phosphate-sodium hydroxide, glycine-sodium chloride-sodium hydroxide and potassium chloride-sodium hydroxide.
5. The controllable synthesis method according to claim 4, characterized in that in the third step, besides the buffer, a carbon source is added, wherein the carbon source is any one or a mixture of several of glucose, sucrose, starch, polyvinylpyrrolidone, epoxy resin and polyethylene glycol, and the addition amount of the carbon source is 0.025-0.1 g/mL of the mixed solution.
6. The controllable synthesis method according to claim 1, wherein in step five, the inert atmosphere is under any one atmosphere of argon, nitrogen and helium.
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