CN110459751B - Spherical Li4Ti5O12/ZnS composite negative electrode material - Google Patents
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a spherical Li4Ti5O12the/ZnS composite negative electrode material is prepared by taking a titanium source, a lithium source, a zinc source and a carbon source as raw materials, preparing a precursor by adopting a ball-milling auxiliary-sol-gel method, and then sintering the precursor at high temperature to obtain spherical Li4Ti5O12the/ZnS composite negative electrode material. Li prepared by the invention4Ti5O12the/ZnS composite negative electrode material is uniform and spherical, has the particle size of about 100-200 nm, and has good dispersibility. The spherical shape increases the contact among material particles and shortens the diffusion coefficient of lithium ions, thereby improving the conductivity and the diffusion coefficient of the lithium ions of the electrode material; meanwhile, the uniform dispersion of the spherical shape can also improve the tap density of the material, thereby improving the energy density of the material. By ZnS and Li4Ti5O12The specific capacity and the cycling stability of the material are improved by the synergistic effect of the components, the specific capacity is improved from 190mAh/g of the material without ZnS to 215mAh/g after ZnS is added, and meanwhile, the good cycling stability is still maintained. The preparation method disclosed by the invention is simple in process flow, easy to control and operate automatically, suitable for large-scale production and good in application prospect.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to spherical Li4Ti5O12the/ZnS composite negative electrode material.
Background
The new energy industry conforms to the trend of the era development and conforms to the sustainable development of human beingsAnd has vigorous vitality and development prospect. The bottleneck limiting the development of new energy industry is not in the development of new energy but in the energy storage and transformation of new energy. Lithium ion batteries have many advantages in their own right, for example: high energy density, good adaptability and the like are considered as the most ideal tools for energy storage and conversion, and become one of the main research hotspots in the new energy industry. The lithium ion battery comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte and related auxiliary equipment, wherein the positive electrode material and the negative electrode material directly determine the basic performance of the whole battery and are the key points of the lithium ion battery. At present, the improvement of the performance of the anode material reaches the bottleneck, and researchers are interested in improving the performance of the anode material, so that the performance of the anode material can be fully exerted. Lithium ion battery cathode material Li4Ti5O12The material has excellent cycle stability, stable charge-discharge voltage platform and zero strain characteristic in the charge-discharge process, and is one of popular materials for the research of the current cathode material. But Li4Ti5O12Belongs to a transition metal oxide group, has lower electronic conductivity (about 10-9S/cm at normal temperature) as a battery cathode material; and compared with metallic lithium, Li4Ti5O12Has a higher potential and a lower capacity, which limits Li4Ti5O12The application of the lithium ion negative electrode material leads to the insufficiency of the battery performance by taking the material as a raw material.
In order to promote Li4Ti5O12The electrochemical performance of the carbon-coated carbon. For example, patent CN 105470490A discloses a method for preparing a spherical lithium titanate electrode material, which adopts titanium sulfate as a titanium source to prepare spherical Li4Ti5O12Prepared spherical Li4Ti5O12Although the structure is spherical-like, the spherical particle size is 1-2 μm micron, the spherical particle size is larger, the effect of shortening the lithium ion diffusion path is weak, and the prepared Li4Ti5O12Specific capacity phase of electrode materialThe theoretical specific capacity is not obviously improved; the invention patent CN201210436508.7 discloses a preparation method of a carbon-coated nano microsphere lithium titanate electrode material, which uses a lithium source and nano TiO2The method comprises the following steps of preparing a carbon-coated nano microsphere lithium titanate electrode material by using a high-molecular hydrocarbon compound pre-coated nano microsphere lithium titanate precursor prepared by spray drying as a raw material and then performing high-temperature sintering, wherein the spherical material prepared by the spray drying method has the problems of large particle size, nonuniform carbon coating and the like; wuxianzen et al disclose Li4Ti5O12Preparation and electrochemical performance of/CuO composite material to self-make Li4Ti5O12Powder, Cu (CH)3COO)2·H2Solid-phase synthesis of Li with O as raw material4Ti5O12A CuO composite; although the method improves the conductivity of the lithium titanate to a certain extent, the specific capacity of the lithium titanate is lower than 200mA · h/g, and compared with the theoretical specific capacity of 227mA · h/g, the method has no obvious performance improvement.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention is directed to providing a spherical Li4Ti5O12the/ZnS composite negative electrode material solves the problems of the existing Li4Ti5O12The composite negative electrode material still has the problems of larger spherical particle size, low capacity, low electronic conductivity and low lithium ion diffusion coefficient.
In order to achieve the purpose, the invention adopts the following technical scheme: spherical Li4Ti5O12the/ZnS composite negative electrode material is prepared by adopting the following method:
1) diluting the titanium source by adding a diluent, dropwise adding the diluted titanium source into the hydrolysate, and hydrolyzing at the constant temperature of 35-50 ℃ for 2-3 h; the hydrolysate comprises absolute ethyl alcohol, water and hexadecyl trimethyl ammonium bromide;
2) transferring the hydrolysate obtained in the step 1) into a ball milling tank, adding a lithium source, a zinc source and a carbon source into the ball milling tank to obtain a mixed solution, and then ball milling and vacuum drying the mixed solution to obtain a precursor;
3) grinding the precursor obtained in the step 2) into powder, sintering the powder in an inert atmosphere, cooling to room temperature after the reaction is finished, and fully grinding the sintered product into fine powder to obtain the spherical Li4Ti5O12the/ZnS composite negative electrode material.
Further, the molar ratio of the titanium source to the absolute ethyl alcohol, the water and the hexadecyl trimethyl ammonium bromide in the hydrolysate is 1: 60-70: 4-10: 1/10000-1/9000. The anhydrous ethanol can reduce the hydrolysis speed of the titanium source; water is used as a hydrolysis component to participate in hydrolysis reaction; cetyl trimethyl ammonium bromide can inhibit agglomeration of hydrolyzed particles.
Further, the diluent is absolute ethyl alcohol, and the volume ratio of the absolute ethyl alcohol to the titanium source is 1-3: 1.
further, the titanium source is tetrabutyl titanate; the carbon source is glucose, soluble starch or sucrose; the lithium source is lithium acetate, lithium carbonate or lithium hydroxide; the zinc source is zinc sulfate.
Further, the molar ratio of the Ti, Li and Zn elements in the mixed solution is 1.25:1: 0.5-2.
Further, the ball milling speed is 300-400 r/min, and the ball milling time is 6-8 h.
Further, the inert atmosphere is nitrogen or argon, and the flow rate of the inert atmosphere is 100-300 mL/min.
Further, the sintering temperature is 700-800 ℃, and the sintering time is 6-8 h.
Further, the vacuum drying temperature is 80-100 ℃.
Further, the residual carbon content of the carbon source after sintering accounts for Li4Ti5O12The mass of the/ZnS composite negative electrode material is 1-3%, and the carbon source is cracked and then coated on the surface of the composite material particles in an amorphous carbon form.
Compared with the prior art, the invention has the following beneficial effects:
1. spherical Li of the invention4Ti5O12a/ZnS composite negative electrode material which comprises,titanium source, lithium source, zinc source and carbon source are used as raw materials, a precursor is prepared by adopting a ball-milling auxiliary-sol-gel method, and then the precursor is sintered at high temperature to prepare spherical Li with uniform nano size and particle morphology4Ti5O12the/ZnS composite negative electrode material. Li4Ti5O12After being compounded with ZnS, the ZnS can inhibit Li4Ti5O12The agglomeration of the material can obtain spherical composite particles with better dispersibility, and ZnS has a structure more beneficial to lithium ion deintercalation and can improve Li4Ti5O12The diffusion capacity of the lithium ions is improved, and the specific capacitance of the material is further improved; and Li4Ti5O12Has stable crystal structure and excellent cycling stability, and can improve the capacity fading phenomenon of the ZnS cathode material in the cycling process, so the ZnS cathode material and the ZnS cathode material have synergistic interaction after being compounded, and Li is ensured to be in a lithium state4Ti5O12the/ZnS composite negative electrode material has high specific capacity, good rate capability and good cycle performance. The preparation method disclosed by the invention is simple in process flow, easy to control and operate automatically, and suitable for large-scale production.
2. Li prepared by the invention4Ti5O12the/ZnS composite negative electrode material is uniform and spherical, the particle size is about 100-200 nm, and Li4Ti5O12the/ZnS particles have good dispersibility, the spherical shape increases the contact among the material particles and shortens the diffusion coefficient of lithium ions, so that the conductivity and the diffusion coefficient of the lithium ions of the electrode material are improved, and the electrochemical performance of the material is improved; meanwhile, the uniform dispersion of the spherical shape can also improve the tap density of the material, thereby improving the energy density of the material. Li prepared by the invention4Ti5O12The specific capacitance of the/ZnS composite negative electrode material is improved from 190mAh/g without adding ZnS to 215mAh/g after adding, and meanwhile, the good circulation stability is still maintained, so that the material has a good application prospect.
Drawings
FIG. 1 is a schematic diagram of the preparation of spherical Li according to the present invention4Ti5O12A Scanning Electron Microscope (SEM) picture of/ZnS; FIG. a is pure phase Li4Ti5O12FIG. b is Li4Ti5O12/ZnS；
FIG. 2 is Li prepared by the present invention4Ti5O12XRD pattern of/ZnS composite negative electrode material;
FIG. 3 is a spherical Li prepared by the present invention4Ti5O12And the cycle performance diagram of the/ZnS composite negative electrode material.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The experimental procedures are not specifically described in the following examples, and are carried out in a conventional manner using reagents which are generally commercially available.
One, one kind of spherical Li4Ti5O12/ZnS composite negative electrode material
Example 1
1) Weighing 0.1g of hexadecyl trimethyl ammonium bromide into a 500mL beaker, adding 80mL of ethanol and 5mL of deionized water, and placing the mixed solution into a 45 ℃ water bath kettle for magnetic stirring for 30min to obtain a hydrolysate for later use;
2) adding 10mL of tetrabutyl titanate into 20mL of absolute ethyl alcohol, fully stirring, dropwise adding the mixture into the hydrolysate, and hydrolyzing for 2h at 45 ℃;
3) transferring the hydrolysate obtained in the step 2) into a ball milling tank, adding lithium acetate and zinc sulfate into the ball milling tank to ensure that the molar ratio of Ti, Li and Zn elements is 1.25:1:0.5, adding 0.1975g of glucose, ball milling the mixture for 4 hours at the ball milling speed of 350r/min, and carrying out vacuum drying at 80 ℃ after the ball milling is finished to obtain a precursor;
4) grinding the precursor obtained in the step 3) into powder, sintering at 750 ℃ for 6h in a nitrogen (200mL/min) protective atmosphere, then continuously cooling to room temperature in the nitrogen protective atmosphere, fully grinding the sintered product into fine powder to obtain spherical Li4Ti5O12and/ZnS finished product.
Example 2
1) Weighing 0.05g of hexadecyl trimethyl ammonium bromide into a 500mL beaker, adding 80mL of ethanol and 5mL of deionized water, and placing the mixed solution into a 50 ℃ water bath kettle for magnetic stirring for 30min to obtain a hydrolysate for later use;
2) adding 10mL of tetrabutyl titanate into 30mL of absolute ethyl alcohol, fully stirring, dropwise adding the mixture into the hydrolysate, and hydrolyzing for 2h at 50 ℃;
3) transferring the hydrolysate obtained in the step 2) into a ball milling tank, adding lithium acetate and zinc sulfate into the ball milling tank to ensure that the molar ratio of Ti, Li and Zn elements is 1.25:1:1, adding 0.1975g of glucose, ball milling the mixture for 6 hours at the ball milling speed of 400r/min, and carrying out vacuum drying at 80 ℃ after the ball milling is finished to obtain a precursor;
4) grinding the precursor obtained in the step 3) into powder, sintering at 700 ℃ for 6h in the protective atmosphere of nitrogen (200mL/min), cooling to room temperature in the protective atmosphere of nitrogen, fully grinding the sintered product into fine powder to obtain the spherical Li4Ti5O12and/ZnS finished product.
Example 3
1) Weighing 0.15g of hexadecyl trimethyl ammonium bromide into a 500mL beaker, adding 80mL of ethanol and 5mL of deionized water, and placing the mixed solution into a 40 ℃ water bath kettle for magnetic stirring for 30min to obtain a hydrolysate for later use;
2) adding 10mL of absolute ethyl alcohol into 10mL of tetrabutyl titanate, fully stirring, dropwise adding the mixture into the hydrolysate, and hydrolyzing for 2h at 40 ℃;
3) transferring the hydrolysate obtained in the step 2) into a ball milling tank, adding lithium acetate and zinc sulfate into the ball milling tank to ensure that the molar ratio of Ti, Li and Zn elements is 1.25:1:2, adding 0.1975g of glucose, ball milling the mixture for 8 hours at the ball milling speed of 300r/min, and carrying out vacuum drying at 80 ℃ after the ball milling is finished to obtain a precursor;
4) grinding the precursor obtained in the step 3) into powder, sintering at 800 ℃ for 6h in a nitrogen (200mL/min) protective atmosphere, then continuously cooling to room temperature in the nitrogen protective atmosphere, fully grinding the sintered product into fine powder to obtain spherical Li4Ti5O12and/ZnS finished product.
Second, performance verification
1. The spherical Li prepared by the invention4Ti5O12ZnS and pure phase Li4Ti5O12The results of scanning analysis by electron microscope are shown in FIG. 1.
As can be seen from FIG. 1, the spherical Li prepared by the present invention4Ti5O12the/ZnS composite negative electrode material is spherical particles with the particle size of about 100-200 nm and pure-phase Li4Ti5O12In contrast, Li4Ti5O12the/ZnS particles have good dispersibility, the agglomeration degree is mild, and the large-scale agglomeration phenomenon does not occur, which shows that after compounding ZnS, the agglomeration of the material can be further inhibited, and spherical particles with better dispersibility can be obtained.
2. Li prepared by the invention4Ti5O12XRD powder diffraction analysis is carried out on the/ZnS composite negative electrode material to determine the phase of the prepared sample, and the result is shown in figure 2.
As can be seen from FIG. 2, Li prepared by the present invention4Ti5O12Characteristic peak and Li of/ZnS composite negative electrode material4Ti5O12The standard characteristic peaks of (PDF #49-0207) and ZnS (PDF #89-2152) can be in one-to-one correspondence, which shows that the method successfully synthesizes ZnS composite Li4Ti5O12And (3) a negative electrode material.
3. Li prepared in examples was separately prepared4Ti5O12/ZnS composite negative electrode material and pure-phase Li4Ti5O12The cathode materials, the aqueous binder and the conductive agent are mixed according to the mass ratio of 8:1:1, the mixture is placed in a mortar to be ground to prepare slurry with moderate viscosity, the slurry is uniformly coated on copper foil to prepare electrode plates, the electrode plates are assembled into a CR2032 button cell in a glove box, then the assembled CR2032 button cell is subjected to constant current charge and discharge test under the current density of 200mA/g, the cycle number is 100 times, and the electrochemical performance is tested, and the result is shown in figure 3.
As can be seen from FIG. 3, Li prepared by the present invention4Ti5O12/ZnS compositeThe specific capacitance of the cathode material is improved from 190mAh/g without adding ZnS to 215mAh/g after adding the ZnS, and meanwhile, good cycle stability is still maintained. Shows that Li can be obviously improved after ZnS is compounded4Ti5O12Electrochemical properties of the material.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. Spherical Li4Ti5O12the/ZnS composite negative electrode material is characterized by being prepared by adopting the following method:
1) diluting the titanium source by adding a diluent, dropwise adding the diluted titanium source into the hydrolysate, and hydrolyzing at the constant temperature of 35-50 ℃ for 2-3 h; the hydrolysate comprises absolute ethyl alcohol, water and hexadecyl trimethyl ammonium bromide, wherein the titanium source is tetrabutyl titanate, the diluent is the absolute ethyl alcohol, and the volume ratio of the diluent to the titanium source is 1-3: 1;
2) transferring the hydrolysate obtained in the step 1) into a ball milling tank, adding a lithium source, a zinc source and a carbon source into the ball milling tank to obtain a mixed solution, and then carrying out ball milling and vacuum drying on the mixed solution to obtain a precursor, wherein the carbon source is glucose, soluble starch or sucrose; the lithium source is lithium acetate, lithium carbonate or lithium hydroxide; the zinc source is zinc sulfate;
3) grinding the precursor obtained in the step 2) into powder, sintering the powder in an inert atmosphere, cooling to room temperature after the reaction is finished, and fully grinding the sintered product into fine powder to obtain the spherical Li4Ti5O12the/ZnS composite negative electrode material.
2. Spherical Li according to claim 14Ti5O12the/ZnS composite negative electrode material is characterized in that the molar ratio of the titanium source to the absolute ethyl alcohol, the water and the hexadecyl trimethyl ammonium bromide in the hydrolysate is 1: 60-70: 4-10: 1/10000-1/9000.
3. Spherical Li according to claim 14Ti5O12the/ZnS composite negative electrode material is characterized in that a titanium source, a lithium source and a zinc source in the mixed solution are respectively in a molar ratio of Ti, Li and Zn of 1.25:1: 0.5-2.
4. Spherical Li according to claim 14Ti5O12the/ZnS composite negative electrode material is characterized in that the ball milling speed is 300-400 r/min, and the ball milling time is 6-8 h.
5. Spherical Li according to claim 14Ti5O12the/ZnS composite negative electrode material is characterized in that the inert atmosphere is nitrogen or argon, and the flow of the inert atmosphere is 100-300 mL/min.
6. Spherical Li according to claim 14Ti5O12the/ZnS composite negative electrode material is characterized in that the sintering temperature is 700-800 ℃, and the sintering time is 6-8 h.
7. Spherical Li according to claim 14Ti5O12the/ZnS composite negative electrode material is characterized in that the vacuum drying temperature is 80-100 ℃.
8. Spherical Li according to claim 14Ti5O12the/ZnS composite anode material is characterized in that the residual carbon content of the sintered carbon source accounts for Li4Ti5O12The mass of the/ZnS composite negative electrode material is 1% -3%.
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Citations (4)
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|---|---|---|---|---|
| EP1052714A4 (en) * | 1998-12-02 | 2005-03-30 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary cell and its charging method |
| CN101916854A (en) * | 2010-08-30 | 2010-12-15 | 上海交通大学 | Preparation method of zinc sulfide/carbon composite material for negative electrode of lithium ion battery |
| CN104037400A (en) * | 2014-07-09 | 2014-09-10 | 扬州大学 | Preparation method of copper-doped lithium titanate lithium ion battery cathode material |
| CN107069001A (en) * | 2017-04-01 | 2017-08-18 | 中南大学 | A kind of cellular zinc sulfide/carbon composite negative pole material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1052714A4 (en) * | 1998-12-02 | 2005-03-30 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary cell and its charging method |
| CN101916854A (en) * | 2010-08-30 | 2010-12-15 | 上海交通大学 | Preparation method of zinc sulfide/carbon composite material for negative electrode of lithium ion battery |
| CN104037400A (en) * | 2014-07-09 | 2014-09-10 | 扬州大学 | Preparation method of copper-doped lithium titanate lithium ion battery cathode material |
| CN107069001A (en) * | 2017-04-01 | 2017-08-18 | 中南大学 | A kind of cellular zinc sulfide/carbon composite negative pole material and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| "Li4Ti5O12/CuO复合材料的制备及电化学性能";吴贤文 等;《中国稀土学报》;20120831;第30卷;第324-327页 * |
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