CN111785955A - High-capacity VNb9O25Nano-sheet lithium ion battery cathode material and preparation method thereof - Google Patents
High-capacity VNb9O25Nano-sheet lithium ion battery cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-capacity VNb9O25The nano-sheet lithium ion battery cathode material and the preparation method thereof comprise the following steps: dissolving niobium pentachloride in ethanol, adding a certain amount of vanadyl acetylacetonate powder into the solution, carrying out ultrasonic oscillation on the mixed solution to completely dissolve the mixed solution, then dropwise adding aqueous solution of tetramethyl ammonium hydroxide into the mixed solution, and stirring at a constant speed to completely dissolve the aqueous solution. Then putting the obtained solution into a high-pressure reaction kettle for heating reaction; cooling, washing, drying and roasting to obtain VNb9O25A nano-sheet negative electrode material for lithium ion batteries. VNb prepared according to the invention9O25Nano meterThe cathode material of the sheet lithium ion battery is in nanoscale and has good dispersibility, and when the cathode material of the sheet lithium ion battery is applied as the cathode material of the lithium ion battery, the cathode material has the advantages of high specific capacity, good cycle performance and the like.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a high-capacity VNb9O25A nano-sheet lithium ion battery cathode material and a preparation method thereof.
Background
Along with the enhancement of environmental awareness of people, electric automobiles are more and more concerned by people. The lithium ion battery has the characteristics of high energy density, high working voltage, small volume, long service life, environmental friendliness and the like, and is considered as an ideal power source of the electric automobile. However, the current commercialized lithium ion battery cannot meet the requirements of the electric vehicle on charging speed, endurance mileage, safety and the like. Therefore, the development of high-performance power lithium ion batteries is always a pursuit target of people. The electrode material is the core and key of the lithium ion battery and has a decisive influence on the performance of the battery, so the center of gravity of the research and development of the high-performance lithium ion battery lies in the development of the high-performance electrode material.
As an important component of lithium ion batteries, a satisfactory negative electrode material is necessary because it plays a key role in enhancing its electrochemical performance. However, conventional anode material graphite cannot fully meet these requirements because it is relatively poor. Kinetics of high power due to its poor lithium ion conductivity and safety issues, which stem from the low operating potential (relative to Li/Li)+) Lithium dendrites are formed. In order to solve the above problems, other types of negative electrodes have been explored and developed. For example, titanium-based compounds exhibit good performance in some respects. However, their low storage capacityThe amount severely limits their widespread use. Therefore, development of a novel anode material having a larger capacity and better safety is strongly desired.
In order to enable better adaptation of lithium ion batteries to market demands, further improvements are of vital importance in terms of high capacity, high electronic conductivity and excellent capacity retention. In recent years, niobium-based compounds (e.g., Nb)2O5) The lithium ion anode material has received high scientific attention, and shows high power density, good structural stability, low cost and environmental friendliness. Unfortunately, however, its poor conductivity and capacity retention inherent in the charging/discharging process limits its practical use in lithium ion batteries. Therefore, it is important to develop a negative electrode material having similar advantages to niobium pentoxide but having higher electrical conductivity.
Compared with niobium pentoxide, the niobium pentoxide doped with vanadium can realize larger specific discharge capacity, higher lithium ion diffusion coefficient, better cycle performance and stability.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-capacity VNb for a lithium ion battery cathode material, which has simple process and low cost and aims at overcoming the defects of the prior art9O25Preparation method of nanosheet and VNb prepared by adopting preparation method9O25The nano-sheet lithium ion battery cathode material has excellent electrochemical performance, discharge specific capacity, higher lithium ion diffusion coefficient, better cycle performance and stability.
In order to solve the technical problems, the invention adopts the following technical scheme:
high-capacity VNb9O25The preparation method of the nano-sheet lithium ion battery cathode material comprises the following steps:
(1) dissolving niobium pentachloride in absolute ethyl alcohol, and stirring for 0.5-1 hour to completely dissolve the niobium pentachloride;
(2) adding vanadyl acetylacetonate powder as a vanadium source into the solution prepared in the step (1), and then carrying out ultrasonic oscillation for 0.5-1 hour to completely dissolve the vanadyl acetylacetonate powder;
(3) adding 20 mL of tetramethylammonium hydroxide aqueous solution into the solution obtained in the step (2) at a constant rate, and stirring to completely dissolve the tetramethylammonium hydroxide aqueous solution;
(4) transferring the solution obtained in the step (3) into a stainless steel reaction kettle lined with polytetrafluoroethylene, and placing the stainless steel reaction kettle in a constant-temperature drying box for heating reaction;
(5) washing the reaction precipitate obtained in the step (4) with acetone, ethanol and deionized water for several times respectively until the solution is neutral, and then placing the solution in a vacuum drying oven for drying;
(6) placing the powder obtained in the step (5) in a muffle furnace for roasting to obtain VNb9O25A nano-sheet negative electrode material for lithium ion batteries.
Further, the molar ratio of the vanadium ions to the niobium ions in the step (2) is 1:9-1: 5.
Further, in the step (3), the concentration of the aqueous solution of tetramethylammonium hydroxide is 25%, and the ratio of the total amount of vanadyl acetylacetonate and niobium pentachloride to the amount of tetramethylammonium hydroxide is 1:20 to 1:40, preferably 1:25.6 to 1: 32.
Further, the dropping rate of the aqueous tetramethylammonium hydroxide solution in the step (3) is 0.6 mL/min.
Further, the heating reaction temperature in the step (4) is 240 ℃, and the reaction time is 12-15 hours.
Further, the vacuum drying temperature in the step (5) is 60-90 ℃, and the drying time is 20-24 hours.
Further, the roasting temperature in the step (6) is 400 ℃, and the roasting time is 4-5 hours.
High-capacity VNb prepared by the preparation method9O25A nano-sheet negative electrode material for lithium ion batteries.
Further, the VNb9O25The negative electrode material of the nano-sheet lithium ion battery consists of VNb9O25The thickness of the nano-sheet is 3-4 nanometers.
The invention has the advantages of: the niobium pentachloride is used as a niobium source, the vanadyl acetylacetonate is used as a vanadium source, and the preparation method adopts a hydrothermal method, so that the preparation method is simple in process, low in cost and suitable for industrial production; the particle size and the dispersion degree of the material are controlled by optimizing the molar ratio of vanadium ions to niobium ions, the roasting temperature and the roasting time, and the high-capacity VNb with good dispersibility and controllable morphology is prepared9O25A nanoplate lithium ion battery negative electrode material; VNb prepared by the invention9O25The nano sheet material is used as the negative electrode of the lithium ion battery, and has extremely high discharge specific capacity and good cycle performance.
Drawings
FIG. 1 is a VNb prepared in example 19O25An X-ray diffraction pattern of the nanoplatelets;
FIG. 2 is a VNb prepared in example 19O2Scanning Electron Microscope (SEM) photographs of 5 nanoplatelets;
FIG. 3 is a VNb prepared in example 19O25Transmission Electron Microscope (TEM) photographs of the nanoplatelets;
FIG. 4 is a VNb prepared in example 19O25Multiplying power performance diagrams of button cells with the nanosheet material as the negative electrode under different currents;
FIG. 5 is a VNb prepared in example 19O25A cycling stability performance diagram of the button cell with the nanosheet material as the negative electrode under the current of 2A/g;
FIG. 6 is a VNb prepared in example 29O25An X-ray diffraction pattern of the nanorod material;
FIG. 7 is a VNb prepared in example 29O25Scanning Electron Microscope (SEM) photographs of the nanorod material;
FIG. 8 is a VNb prepared in example 29O25Transmission Electron Microscope (TEM) photographs of the nanorod material;
FIG. 9 is VNb prepared in example 29O25Multiplying power performance diagrams of button cells with the nano-rod material as the cathode under different currents;
FIG. 10 is a VNb prepared in example 39O25With nanosheet material as the negative electrodeMultiplying power performance diagram of button cell under different current.
FIG. 11 shows Nb prepared in example 52O5Multiplying power performance diagram of button cell with nano sheet material as negative pole under different current.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
High-capacity VNb of the present embodiment9O25The preparation method of the nano-sheet lithium ion battery cathode material comprises the following steps:
(1) 2.7 millimole of niobium pentachloride (0.73 g) is dissolved in 36ml of absolute ethyl alcohol and stirred for 0.5 to 1 hour to be completely dissolved;
(2) adding 0.3 millimole of vanadyl acetylacetonate powder as a vanadium source into the solution, wherein the ratio of V to Nb is 1:9, and then carrying out ultrasonic oscillation for 0.5-1 hour to completely dissolve the vanadyl acetylacetonate powder;
(3) dropwise adding 20 mL of 25% tetramethylammonium hydroxide aqueous solution into the mixed solution at the rate of 0.6 mL/min for reaction, and stirring until a clear solution is formed, wherein the molar ratio of (vanadyl acetylacetonate + niobium pentachloride) to tetramethylammonium hydroxide is 1: 25.6;
(4) then transferring the obtained solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, and placing the stainless steel reaction kettle in a constant-temperature drying oven for heating reaction at the temperature of 240 ℃ for 12 hours;
(5) washing the obtained reaction precipitate with acetone, ethanol and deionized water for several times respectively until the solution is neutral, and then drying in a vacuum drying oven at 60 deg.C for 24 hr;
(6) roasting the dried powder in a muffle furnace at 400 ℃ for 4 hours, taking out, cooling and grinding to obtain VNb9O25A nano-sheet negative electrode material for lithium ion batteries.
The VNb prepared in this example was subjected to X-ray diffractometry and electron scanning electron microscopy, respectively9O25The nano-sheet lithium ion battery negative electrode material is characterized, and the results are shown in fig. 1 and fig. 2. As can be seen from FIG. 1, the diffraction peak of the material sample is compared with VNb in a standard PDF card9O25The diffraction peaks of the compound are completely consistent, and no other impurity peaks are found, so that the synthesized sample is relatively pure. As shown in fig. 2, the sample has better morphology and better dispersibility, and the size of the microspheres is about 1-2 microns. As shown in fig. 3, the microsphere surface nanoplatelets have a thickness of about 3-4 nanometers.
VNb prepared in this example9O25The nanosheet material is used as a negative electrode material of a lithium ion battery to prepare a button battery, wherein VNb9O25The nano sheet material is an active substance, the conductive agent is Keqin black, the binder is polyvinylidene fluoride, and the proportion of the nano sheet material to the conductive agent to the binder is 8:1:1 (mass ratio). And then testing the electrochemical performance of the button cell, wherein the cell testing interval is 1.0-3.0V. As shown in FIG. 4, the cycle performance of the sample is tested under different rates, and the graph shows that the sample has better rate cycle performance, the specific discharge capacities at rates of 0.2A/g, 0.4A/g, 1A/g and 2A/g are respectively about 500 mAh/g, 445 mAh/g, 325 mAh/g and 300 mAh/g, and even at a rate of 10A/g, the sample still has high specific discharge capacity (about 140 mAh/g). FIG. 5 shows that after the button cell prepared by the material is cycled 2000 times under the current of 2A/g, the specific discharge capacity of the button cell still has 290 mAh/g.
Example 2
(1) 2.7 millimole of niobium pentachloride (0.73 g) is dissolved in 36ml of absolute ethyl alcohol and stirred for 0.5 to 1 hour to be completely dissolved;
(2) adding 0.3 millimole of vanadyl acetylacetonate powder as a vanadium source into the solution, wherein the ratio of V to Nb is 1:9, and then carrying out ultrasonic oscillation for 0.5-1 hour to completely dissolve the vanadyl acetylacetonate powder;
(3) then 30 mL of tetramethylammonium hydroxide aqueous solution is dropwise added into the mixed solution at the speed of 0.6 mL/min, and the mixed solution is stirred to be completely dissolved, wherein the molar ratio of (vanadyl acetylacetonate + niobium pentachloride) to tetramethylammonium hydroxide is 1: 38.3;
(4) then transferring the obtained solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, and placing the stainless steel reaction kettle in a constant-temperature drying oven for heating reaction at the temperature of 240 ℃ for 12 hours;
(5) washing the obtained reaction precipitate with acetone, ethanol and deionized water for several times respectively until the solution is neutral, and then drying in a vacuum drying oven at 60 deg.C for 24 hr;
(6) roasting the dried powder in a muffle furnace at 700 ℃ for 4 hours, taking out, cooling and grinding to obtain VNb9O25A nanorod lithium ion battery cathode material. Due to high roasting temperature, the nanosheet precursor synthesized by hydrothermal method is converted into VNb9O25And (4) nanorods.
The VNb prepared in this example was subjected to X-ray diffractometry and electron scanning electron microscopy, respectively9O25The nanorod lithium ion battery negative electrode material is characterized, and the results are shown in fig. 6 and 7. As can be seen from FIG. 6, the diffraction peaks of the material sample and VNb in the standard PDF card9O25The diffraction peaks of the compound are completely consistent, and no other impurity peaks are found, so that the synthesized sample is relatively pure. As shown in FIG. 7, the sample has better morphology and better dispersibility, the diameter of the nanorod is about 20-50 nm, and the length is about 200-400 nm. For example, VNb in FIG. 89O25Transmission Electron Microscope (TEM) photograph of nanorods; .
VNb prepared in this example9O25The nano-rod material is used as the cathode material of the lithium ion battery to prepare the button cell, wherein VNb9O25The nano-rod material is an active substance, the conductive agent is Keqin black, the adhesive is polyvinylidene fluoride, the mass ratio of the nano-rod material to the conductive agent is 8:1:1, and then the electrochemical performance of the button cell is tested. As shown in FIG. 9, the test samples have cycling performance at different rates, and the specific discharge capacities at 0.2, 0.4, 1 and 2A/g rates are about 250 mAh/g, 200 mAh/g, 125 mAh/g, 100 mAh/g, respectively, but are compared with VNb9O25Prepared by using nano sheet material as negative electrode materialThe button cell has obviously reduced specific discharge capacity under the same current.
Example 3
High-capacity VNb of the present embodiment9O25The preparation method of the nano-sheet lithium ion battery cathode material comprises the following steps:
(1) dissolving 3 mmol of niobium pentachloride (0.81 g) in 36ml of absolute ethanol, and stirring for 0.5-1 hour to completely dissolve;
(2) adding 0.6 millimole of vanadyl acetylacetonate powder as a vanadium source into the solution, wherein the ratio of V to Nb is 1:5, and then carrying out ultrasonic oscillation for 0.5-1 hour to completely dissolve the vanadyl acetylacetonate powder;
(3) dropwise adding 35 mL of 25% tetramethylammonium hydroxide aqueous solution into the mixed solution at the rate of 0.6 mL/min, and stirring to completely dissolve the tetramethylammonium hydroxide aqueous solution, wherein the molar ratio of (vanadyl acetylacetonate + niobium pentachloride) to tetramethylammonium hydroxide is 1: 37.3;
(4) then transferring the obtained solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, and placing the stainless steel reaction kettle in a constant-temperature drying oven for heating reaction at the temperature of 240 ℃ for 12 hours;
(5) washing the obtained reaction precipitate with acetone, ethanol and deionized water for several times respectively until the solution is neutral, and then drying in a vacuum drying oven at 60 deg.C for 24 hr;
(6) placing the dried powder in a muffle furnace for roasting at 500 ℃ for 4 hours, taking out, cooling and grinding to obtain the VNb9O25A crystalline phase nano-sheet lithium ion battery cathode material.
VNb prepared in this example9O25The nanosheet material is used as a negative electrode material of a lithium ion battery to prepare a button battery, wherein VNb9O25The nano-sheet material is an active substance, the conductive agent is Keqin black, and the adhesive is polyvinylidene fluoride, wherein the ratio of the nano-sheet material to the conductive agent to the adhesive is 8:1:1 (mass ratio). And then testing the electrochemical performance of the button cell, wherein the cell testing interval is 1.0-3.0V. As shown in FIG. 10, the samples were tested for their cycling performance at different rates, as measured byThe graph shows that the sample has better rate cycling performance, the specific discharge capacities at 0.2, 0.4, 1 and 2A/g rates are respectively about 400 mAh/g, 340 mAh/g, 250 mAh/g and 200 mAh/g, compared with VNb at 400 DEG C9O25The button cell prepared by taking the nanosheet material as the negative electrode material has obviously reduced discharge specific capacity under the same current. Compared to VNb9O25The button cell prepared by taking the nano-rod material (figure 9) as the cathode material has obviously improved discharge specific capacity under the same current.
Example 4
High-capacity VNb of the present embodiment9O25The preparation method of the nano-sheet lithium ion battery cathode material comprises the following steps:
(1) dissolving 3 mmol of niobium pentachloride (0.81 g) in 36ml of absolute ethanol, and stirring for 0.5-1 hour to completely dissolve;
(2) adding 0.6 millimole of vanadyl acetylacetonate powder as a vanadium source into the solution, wherein the ratio of V to Nb is 1:5, and then carrying out ultrasonic oscillation for 0.5-1 hour to completely dissolve the vanadyl acetylacetonate powder;
(3) then 25 mL of 25% tetramethyl ammonium hydroxide aqueous solution is added dropwise into the mixed solution at the speed of 0.6 mL/min, and the mixed solution is stirred to be completely dissolved, wherein the molar ratio of (vanadyl acetylacetonate + niobium pentachloride) to tetramethyl ammonium hydroxide is 1: 26.6;
(4) then transferring the obtained solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, and placing the stainless steel reaction kettle in a constant-temperature drying oven for heating reaction at the temperature of 240 ℃ for 12 hours;
(5) washing the obtained reaction precipitate with acetone, ethanol and deionized water for several times respectively until the solution is neutral, and then drying in a vacuum drying oven at 60 deg.C for 24 hr;
(6) roasting the dried powder in a muffle furnace at 400 ℃ for 4 hours, taking out, cooling and grinding to obtain VNb9O25A nano-sheet negative electrode material for lithium ion batteries.
Example 5
(1) Dissolving 3 mmol of niobium pentachloride (0.81 g) in 36ml of absolute ethanol, and stirring for 0.5-1 hour to completely dissolve;
(2) then 25 mL of tetramethylammonium hydroxide aqueous solution is dropwise added into the mixed solution at the speed of 0.6 mL/min, and the mixed solution is stirred to be completely dissolved, wherein the molar ratio of the niobium pentachloride to the tetramethylammonium hydroxide is 1: 32;
(4) then transferring the obtained solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, and placing the stainless steel reaction kettle in a constant-temperature drying oven for heating reaction at the temperature of 240 ℃ for 12 hours;
(5) washing the obtained reaction precipitate with acetone, ethanol and deionized water for several times respectively until the solution is neutral, and then drying in a vacuum drying oven at 60 deg.C for 24 hr;
(6) placing the dried powder in a muffle furnace for roasting at 400 ℃ for 4 hours, taking out, cooling and grinding to obtain the vanadium-free Nb2O5A nano-sheet negative electrode material for lithium ion batteries.
Nb prepared in this example2O5The nanosheet material is used as a lithium ion battery cathode material for preparing a button cell, wherein Nb is2O5The nano-sheet material is an active substance, the conductive agent is Keqin black, and the adhesive is polyvinylidene fluoride, wherein the ratio of the nano-sheet material to the conductive agent to the adhesive is 8:1:1 (mass ratio). And then testing the electrochemical performance of the button cell, wherein the cell testing interval is 1.0-3.0V. As shown in FIG. 11, the cycling performance of the samples at different rates is tested, and the samples have better rate cycling performance, and the specific discharge capacities at rates of 0.1, 0.2, 0.4, 1, 2 and 5A/g are respectively about 162, 158, 151, 138, 103 and 53 mAh/g, compared with VNb at 400 DEG C9O25The button cell prepared by taking the nanosheet material (figure 4) as the negative electrode material has obviously reduced discharge specific capacity under the same current.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. High-capacity VNb9O25The preparation method of the nano-sheet lithium ion battery cathode material is characterized by comprising the following steps of:
(1) dissolving niobium pentachloride in absolute ethyl alcohol, and stirring for 0.5-1 hour to completely dissolve the niobium pentachloride;
(2) adding vanadyl acetylacetonate powder as a vanadium source into the solution prepared in the step (1), and then carrying out ultrasonic oscillation for 0.5-1 hour to completely dissolve the vanadyl acetylacetonate powder;
(3) adding tetramethyl ammonium hydroxide aqueous solution into the solution obtained in the step (2) at a constant speed, and stirring to completely dissolve the tetramethyl ammonium hydroxide aqueous solution;
(4) transferring the solution obtained in the step (3) into a stainless steel reaction kettle lined with polytetrafluoroethylene, and placing the stainless steel reaction kettle in a constant-temperature drying box for heating reaction;
(5) washing the reaction precipitate obtained in the step (4) with acetone, ethanol and deionized water for several times respectively until the solution is neutral, and then placing the solution in a vacuum drying oven for drying;
(6) placing the powder obtained in the step (5) in a muffle furnace for roasting at 400-500 ℃ to obtain VNb9O25A nano-sheet negative electrode material for lithium ion batteries.
2. The VNb of claim 19O25The preparation method of the nano-sheet lithium ion battery cathode material is characterized by comprising the following steps: the molar ratio of the vanadium ions to the niobium ions in the step (2) is 1:9-1: 5.
3. The VNb of claim 19O25The preparation method of the nano-sheet lithium ion battery cathode material is characterized by comprising the following steps: the tetramethylammonium hydroxide water in the step (3)The mass concentration of the solution is 25%, and the ratio of the total mass of vanadyl acetylacetonate and niobium pentachloride to the mass of tetramethylammonium hydroxide is 1:20-1: 40.
4. The VNb of claim 19O25The preparation method of the nano-sheet lithium ion battery cathode material is characterized by comprising the following steps: the dropping rate of the tetramethylammonium hydroxide aqueous solution is 0.6 mL/min.
5. The VNb of claim 19O25The preparation method of the nano-sheet lithium ion battery cathode material is characterized in that the heating reaction temperature in the step (4) is 240 ℃, and the reaction time is 12-15 hours.
6. The VNb of claim 19O25The preparation method of the nano-sheet lithium ion battery cathode material is characterized in that the vacuum drying temperature in the step (5) is 60-90 ℃, and the drying time is 20-24 hours.
7. The VNb of claim 19O25The preparation method of the nano-sheet lithium ion battery cathode material is characterized in that the roasting temperature in the step (6) is 400 ℃, and the roasting time is 4-5 hours.
8. A high capacity VNb produced by the production method of any one of claims 1 to 79O25A nano-sheet negative electrode material for lithium ion batteries.
9. The high-capacity VNb of claim 69O25The nano-sheet lithium ion battery cathode material is characterized in that: the VNb9O25The negative electrode material of the nano-sheet lithium ion battery consists of VNb9O25The thickness of the nano-sheet is 3-4 nanometers.
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| CN113461066A (en) * | 2021-07-05 | 2021-10-01 | 河南理工大学 | Nano Li1.25Mn0.5V0.25O2Preparation method of positive electrode material |
| CN113636563A (en) * | 2021-08-24 | 2021-11-12 | 郑州轻工业大学 | SiO (silicon dioxide)2Preparation method of incompletely-coated magnetic nanoparticles |
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