CN112952081A - Lithium ion battery layered perovskite structure negative electrode material and preparation method thereof - Google Patents
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Abstract
The invention relates to a lithium ion battery layered perovskite structure cathode material and a preparation method thereof, which are characterized in that the cathode material has a chemical formula of Li0.1La0.3NbO3(ii) a The preparation process specifically comprises the following steps: (1) weighing a lithium source, a lanthanum source and a niobium source, and ball-milling and uniformly mixing to obtain a mixed material; (2) and pre-sintering the obtained mixed material, cooling to room temperature, continuing ball milling, sintering again, and cooling to room temperature to obtain the target product. The lithium ion battery cathode material provided by the invention has the advantages of high coulombic efficiency, good rate capability, excellent cyclic charge-discharge stability and the like; in addition, the preparation method is simple, mainly faces to the field of rapid charge and discharge equipment, has wide application prospect in the field of lithium ion batteries, and provides a lithium ion battery cathode materialMore choices are provided, which is helpful for the development and further development of the electrode material of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and relates to a layered perovskite structure cathode material of a lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries have been widely used in various fields of our lives, from electronic products used in daily life to electric vehicles used everywhere. Currently, graphite and spinel structured Li are commercially used4Ti5O12Are two most popular lithium ion battery cathode materials, but they have some defects, thereby hindering the further development of the lithium ion battery. The graphite has low cost, higher reversible capacity and long cycle life, and the theoretical specific capacity is 375mAh g-1. However, graphite has great potential safety hazard when used as a lithium ion negative electrode material, the working potential of graphite is extremely low, and the voltage platform of graphite is close to the potential of lithium metal deposition, which easily causes lithium dendrite to be formed during high-rate charge and discharge, and the growth of lithium dendrite can pierce a diaphragm to cause short circuit of a battery, thereby causing safety accidents. Lithium ion battery cathode material Li used in another way in commercialization compared with graphite4Ti5O12The lithium ion battery has safer working potential which is about 1.55V, thereby effectively avoiding potential safety hazard caused by the formation of lithium dendrite in the charging and discharging process. However, Li4Ti5O12Has a theoretical capacity of only 175mAh g-1On the other hand, the low reversible capacity restricts the further development of the lithium ion battery in the field. Therefore, the search for negative electrode materials with safe operating potentials and high reversible capacities is essential for the development of lithium ion batteries.
For the high-performance lithium ion battery cathode material, besides the safe working potential and the high reversible capacity, the high rate performance and the long-term cycling stability are two important performances. In view of these performance requirements, the electrochemical performance of the niobium-based negative electrode material in the lithium ion battery is excellent at present, mainly because the niobium-based negative electrode material generally has a high specific capacity, a safe working potential (approximately 0.8-2.0V) and an excellent rate performance. Mainly because of the niobium-based negative electrode material in the charging and discharging processIn the presence of two-step redox Nb5+/Nb4+And Nb4+/Nb3+Thus, a larger capacity can be provided. In addition, an effective approach to improving the cycling stability of anode materials is to search for "zero strain" or low strain anode materials, which typically have suitable Li insertion+Sites and large Li+Channels, thereby Li+The damage to the structure of the cathode material is very small in the embedding and releasing process, so that the long-term circulation stability is ensured.
At present, the perovskite structure material is rarely applied to the negative electrode of the lithium ion battery, and the general structural formula of the perovskite structure material is ABX3While the negative electrode material having an A-site vacancy layered perovskite structure proved to be very suitable for Li+Mainly because of the ordered distribution of many lamellar vacancies and the large interlayer spacing in the structure, and therefore can be provided with a high Li insertion+Sites and large Li+A channel. In the niobium-based oxide material, La1/3NbO3Has an A-site vacancy layered perovskite structure, and La atomic layers and La atomic vacancy layers of the perovskite structure are alternately distributed, NbO6Octahedral co-apical junctions, vacancy layers in the structure are very suitable for Li insertion+Sites and Li+Channels, but low Li+The conductivity is detrimental to its performance in lithium ion batteries.
Disclosure of Invention
The invention aims to provide a lithium ion battery negative electrode material with a layered perovskite structure and a preparation method thereof, and the prepared lithium ion battery negative electrode material Li0.1La0.3NbO3The lithium ion battery has the advantages of safe working potential, higher reversible capacity, excellent rate capability, long-term cycling stability and the like.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a lithium ion battery negative electrode material with a layered perovskite structure, and the chemical formula of the negative electrode material is Li0.1La0.3NbO3。
Further, the negative electrode material has a layered perovskite structure.
The second technical scheme of the invention provides a preparation method of a layered perovskite structure cathode material of a lithium ion battery, which comprises the following steps:
(1) weighing a lithium source, a lanthanum source and a niobium source, and ball-milling and uniformly mixing to obtain a mixed material;
(2) and pre-sintering the obtained mixed material, cooling to room temperature, continuing ball milling, sintering again, and cooling to room temperature to obtain the target product.
Further, in the step (1), the lithium source, the lanthanum source and the niobium source are added in an amount such that the molar ratio of the lithium element, the lanthanum element and the niobium element is 1:3: 10.
Further, in the step (1), the lithium source is lithium carbonate; the lanthanum source is lanthanum oxide; the niobium source is niobium pentoxide.
Further, in the step (1), the rotation speed of ball milling is 800-.
Further, in the step (2), the pre-sintering temperature is 700-.
Further, in the step (2), the temperature of the secondary sintering is 1000-.
Further, in the step (2), the heating rates of the pre-sintering and the secondary sintering are both 3-5 ℃.
Further, in the step (2), the time for continuing ball milling is 3-5h, and the rotating speed is 800-.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a layered perovskite structure cathode material of a lithium ion battery, and widens the selection of the cathode material of the lithium ion battery.
(2) The lithium ion battery cathode material provided by the invention has the advantages of safe working voltage, higher reversible capacity, excellent rate capability, good long-term cycling stability and the like.
(3) The electrode material provided by the invention is simple in preparation method, is suitable for the field of rapid charge and discharge equipment, and has wide application prospects in the field of lithium ion batteries.
Drawings
FIG. 1 shows a lithium ion battery cathode material Li provided by the invention0.1La0.3NbO3The preparation method of (1) is a flow chart.
FIG. 2 shows the layered perovskite structure Li prepared by the present invention0.1La0.3NbO3X-ray diffraction spectrum of the powder.
FIG. 3 shows Li prepared by the present invention0.1La0.3NbO3Scanning electron micrograph (c).
FIG. 4 shows Li prepared by the present invention0.1La0.3NbO3The charge and discharge curves for the first five cycles at 0.1C current density.
FIG. 5 shows Li prepared by the present invention0.1La0.3NbO3Graph of rate performance at different current densities.
FIG. 6 shows Li prepared by the present invention0.1La0.3NbO3Cycling performance plot at 1C current density.
FIG. 7 shows Li prepared by the present invention0.1La0.3NbO3Cycling performance plot at 10C current density.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The lithium ion battery negative electrode material with a layered perovskite structure of the present invention will be described in detail.
The invention provides a lithium ion battery layered perovskite structure cathode material, the chemical formula of which is Li0.1La0.3NbO3. Further, the negative electrode material has a layered perovskite structure. Meanwhile, the powder particles are irregular in size and shape, and the size of a single particle is about 2-10 μm.
In the actual test process, the secondary lithium ion battery negative electrode material Li with a layered perovskite structure0.1La0.3NbO3Working potentialSafe, about 1.5V. The reversible capacity is higher, and the specific capacity of the first circle of charge and discharge is 183mAh g respectively under the current density of 0.1C-1And 242mAh g-1The first turn coulombic efficiency was 75.6%. The multiplying power performance is excellent, and the reversible capacity is 164mAh g under the current density of 0.1C, 0.5C, 1C, 2C, 5C and 10C-1、152mAh g-1、143mAh g-1、135mAh g-1、123mAh g-1And 114mAh g-1The reversible capacity at a current density of 10C was retained at 69.5% relative to the reversible capacity at 0.1C. Excellent in cycle stability and an initial capacity of 145mAh g at a current density of 1C-1After 200 cycles of cyclic charge and discharge, 137mAh g of reversible capacity remains-1The capacity retention rate was 94.5%, and the initial capacity at a current density of 10C was 118mAh g-1After 2000 circles of cyclic charge and discharge, 114mAh g of reversible capacity remains-1The capacity retention rate was 96.6%.
Next, the method for producing the negative electrode material having a layered perovskite structure for a lithium ion battery according to the present invention will be described in detail.
The invention also provides a preparation method of the layered perovskite structure cathode material of the lithium ion battery, the flow of which is shown in figure 1, and the preparation method comprises the following steps:
(1) weighing a lithium source, a lanthanum source and a niobium source, and ball-milling and uniformly mixing to obtain a mixed material;
(2) pre-sintering the obtained mixed material, cooling to room temperature, continuing ball milling, sintering again, and cooling to room temperature to obtain the target product Li0.1La0.3NbO3It has a layered perovskite structure.
In some embodiments, the lithium source, lanthanum source, and niobium source are added in amounts such that the molar ratio of lithium, lanthanum, and niobium is 1:3:10 in step (1).
In some embodiments, in step (1), the lithium source is lithium carbonate; the lanthanum source is lanthanum oxide; the niobium source is niobium pentoxide.
In some embodiments, in step (1), the rotation speed of the ball mill is 800-.
In some embodiments, in the step (2), the temperature of the pre-sintering is 700-800 ℃, and the pre-sintering time is 3-6 h.
In some embodiments, in step (2), the temperature of the secondary sintering is 1000-1100 ℃ and the time is 8-10 h.
In some embodiments, in step (2), the temperature increase rate is 3-5 ℃ for both pre-sintering and secondary sintering.
In some embodiments, in step (2), the time for continuing the ball milling is 3-5h, and the rotation speed is 800-.
In the preparation process, the raw materials can be fully and uniformly mixed by the first ball milling, and the lithium carbonate is decomposed into lithium oxide and carbon dioxide by the pre-sintering at a relatively low temperature, so that decomposed or adsorbed carbon dioxide gas in the raw materials is discharged, and meanwhile, the pre-sintering can effectively prevent a lithium source from being directly heated to a high temperature to volatilize, so that a target product deviates from a stoichiometric ratio, and therefore, the pre-sintering temperature and time play an important role in the generation of the target product. Further ball milling to ensure that the lanthanum oxide, the niobium pentoxide and the lithium oxide generated by presintering decomposition can be uniformly mixed again, and the lithium oxide, the lanthanum oxide and the niobium pentoxide react at a high temperature according to a predetermined stoichiometric ratio to generate a target product Li0.1La0.3NbO3Likewise, the temperature and time of the secondary sintering play a crucial role in the purity of the desired product.
The above embodiments may be implemented individually, or in any combination of two or more.
The above embodiments will be described in more detail with reference to specific examples.
In the following examples, unless otherwise specified, all the conventional commercially available raw materials or conventional processing techniques in the art are indicated.
Example 1:
(1) putting lithium carbonate, lanthanum oxide and niobium pentoxide into a ball milling tank according to the molar ratio of 1:3:10, ball milling for 8 hours at the rotating speed of 900rpm, and uniformly mixing by high-energy ball milling;
(2) putting the uniformly mixed raw materials into a muffle furnace, pre-sintering for 5h at 750 ℃, wherein the heating rate is 5 ℃/min, naturally cooling to room temperature, and taking out;
(3) then putting the sintered powder into the ball milling tank again for ball milling for 5 hours at the rotating speed of 900 rpm;
(4) finally, putting the powder into a muffle furnace, sintering the powder for 10 hours at 1050 ℃, heating at the rate of 5 ℃/min, naturally cooling the powder to room temperature, and taking the powder out to obtain pure-phase Li0.1La0.3NbO3And (3) powder.
Example 2:
(1) putting lithium carbonate, lanthanum oxide and niobium pentoxide into a ball milling tank according to the molar ratio of 1:3:10, ball milling for 8 hours at the rotating speed of 900rpm, and uniformly mixing by high-energy ball milling;
(2) putting the uniformly mixed raw materials into a muffle furnace, pre-sintering for 4h at 700 ℃, wherein the heating rate is 5 ℃/min, naturally cooling to room temperature, and taking out;
(3) then putting the sintered powder into the ball milling tank again for ball milling for 5 hours at the rotating speed of 900 rpm;
(4) finally, putting the powder into a muffle furnace, sintering for 10h at 1100 ℃, heating at the rate of 5 ℃/min, naturally cooling to room temperature, and taking out the powder, wherein the obtained powder is Li0.1La0.3NbO3But impurities.
Example 3:
(1) putting lithium carbonate, lanthanum oxide and niobium pentoxide into a ball milling tank according to the molar ratio of 1:3:10, ball milling for 8 hours at the rotating speed of 900rpm, and uniformly mixing by high-energy ball milling;
(2) putting the uniformly mixed raw materials into a muffle furnace, pre-sintering for 5h at 800 ℃, wherein the heating rate is 5 ℃/min, naturally cooling to room temperature, and taking out;
(3) then putting the sintered powder into the ball milling tank again for ball milling for 5 hours at the rotating speed of 900 rpm;
(4) finally, putting the powder into a muffle furnace, sintering for 10h at 1100 ℃, heating at the rate of 5 ℃/min, naturally cooling to room temperature, and taking out the powder which is Li0.1La0.3NbO3But impurities.
Example 4:
(1) putting lithium carbonate, lanthanum oxide and niobium pentoxide into a ball milling tank according to the molar ratio of 1:3:10, ball milling for 8 hours at the rotating speed of 900rpm, and uniformly mixing by high-energy ball milling;
(2) putting the uniformly mixed raw materials into a muffle furnace, pre-sintering for 5h at 700 ℃, wherein the heating rate is 5 ℃/min, naturally cooling to room temperature, and taking out;
(3) then putting the sintered powder into the ball milling tank again for ball milling for 5 hours at the rotating speed of 900 rpm;
(4) finally, putting the powder into a muffle furnace, sintering for 8h at 1100 ℃, heating at the rate of 5 ℃/min, naturally cooling to room temperature, and taking out the powder which is Li0.1La0.3NbO3But impurities.
Example 5:
(1) putting lithium carbonate, lanthanum oxide and niobium pentoxide into a ball milling tank according to the molar ratio of 1:3:10, ball milling for 8 hours at the rotating speed of 900rpm, and uniformly mixing by high-energy ball milling;
(2) putting the uniformly mixed raw materials into a muffle furnace, pre-sintering for 5h at 750 ℃, wherein the heating rate is 5 ℃/min, naturally cooling to room temperature, and taking out;
(3) then putting the sintered powder into the ball milling tank again for ball milling for 5 hours at the rotating speed of 900 rpm;
(4) finally, putting the powder into a muffle furnace, sintering for 8h at 1000 ℃, heating at the rate of 5 ℃/min, naturally cooling to room temperature, and taking out the powder which is Li0.1La0.3NbO3But impurities;
example 6:
compared with example 1, the same is mostly true except that the presintering temperature is changed to 800 ℃, and the obtained product is Li0.1La0.3NbO3But impurities.
Example 7:
compared with example 1, the same is mostly true except that the presintering temperature is changed to 700 ℃, and the obtained product is Li0.1La0.3NbO3But impurities.
Example 8:
compared with example 1, most of them are the same except thatThe process of pre-sintering is removed, namely the mixed raw materials are directly sintered for 15 hours at 1050 ℃, and the obtained product is Li0.1La0.3NbO3But impurities.
Example 9:
compared with example 1, the same is mostly true except that the temperature of the secondary sintering is changed to 1100 ℃, and the obtained product is Li0.1La0.3NbO3But impurities.
Example 10:
compared with example 1, the same is mostly true except that the temperature of the secondary sintering is changed to 1000 ℃, and the obtained product is Li0.1La0.3NbO3But impurities.
Negative electrode materials were prepared by a high temperature solid phase method, and examples 1 to 5 are shown in table 1.
TABLE 1
FIG. 2 shows Li obtained by the method described in example 10.1La0.3NbO3Analyzing the X-ray diffraction pattern of the powder to obtain Li prepared by a high-temperature solid phase method0.1La0.3NbO3The powder has good crystallinity, the crystal structure of the powder is a layered perovskite structure, the powder belongs to an orthorhombic system, the space group is Pmmmm, and the prepared Li0.1La0.3NbO3The powder phase is very pure without any impurity phases. FIG. 3 shows Li obtained in example 10.1La0.3NbO3Scanning electron micrograph of the powder shows that Li prepared by high temperature solid phase reaction0.1La0.3NbO3The powder has random size and shape, and the particle size is 2-10 μm. FIG. 4 shows Li obtained in example 10.1La0.3NbO3Used as the negative electrode material of the lithium ion battery and has the current of 0.1 DEG CThe charge-discharge curve chart under the density shows that the working voltage is about 1.5V, the reversible capacity is high, and the charge-discharge specific capacity of the first circle is 183mAh g-1And 242mAh g-1The first turn coulombic efficiency was 75.6%. FIG. 5 shows Li obtained in example 10.1La0.3NbO3The reversible capacity of the lithium ion battery cathode material under different current densities is 164mAh g under the current densities of 0.1C, 0.5C, 1C, 2C, 5C and 10C-1、152mAh g-1、143mAh g-1、135mAh g-1、123mAh g-1And 114mAh g-1The reversible capacity at 10C current density has a retention of 69.5% relative to 0.1C, and has very excellent rate capability. FIGS. 6 and 7 are Li obtained in example 1, respectively0.1La0.3NbO3The initial capacity of the lithium ion battery anode material at the current density of 1C is 145mAh g-1After 200 cycles of cyclic charge and discharge, 137mAh g of reversible capacity remains-1The capacity retention rate is as high as 94.5%; initial capacity at 10C current density 118mAh g-1After 2000 circles of cyclic charge and discharge, 114mAh g of reversible capacity remains-1The capacity retention rate is as high as 96.6 percent, which shows that Li prepared by a high-temperature solid-phase reaction method0.1La0.3NbO3The lithium ion battery cathode material has long-term cycling stability. Li with A-site vacancy layered perovskite structure0.1La0.3NbO3Has more Li insertion+Sites and large interlayer spacing, thereby enabling Li+Can be quickly and reversibly inserted and separated, reduces the damage to the crystal structure in the cyclic charge-discharge process, and ensures Li0.1La0.3NbO3Has excellent rate performance and cycling stability. All of the above advantages fully explain Li of the layered perovskite structure0.1La0.3NbO3The lithium ion battery cathode material has a good prospect, is very suitable for rapid charge and discharge equipment, and widens the selection of the lithium ion battery cathode material.
Layered calciumLi of titanium ore structure0.1La0.3NbO3The powder phase was measured using an X-ray diffractometer (XRD, Germany, Bruker D8-Advance diffractometer with Cu Ka radiation operated at 40kV and 40 mA). The microscopic morphology and dimensions were obtained by taking pictures with a field emission scanning electron microscope (FESEM, Japan, Hitachi S-4800 operated at 5 kV). The electrochemical performance of the cell is obtained by testing the assembled button cell on a Newware high-performance cell detection system, the voltage testing range is 0.8-3.0V, and the testing temperature is 25 ℃.
The preparation process of the negative pole piece comprises the following steps: firstly, weighing active substances (Li) with the mass ratio of 7:2:10.1La0.3NbO3Powder), a conductive additive (carbon black) and a binder (polyvinylidene fluoride), mixing the materials, grinding the mixture uniformly by using an agate mortar, dispersing the mixed powder in an N-methylpyrrolidone solvent, stirring the mixture for 24 hours to prepare electrode slurry, uniformly coating the slurry on a copper foil by scraping, putting the slurry with the thickness of about 5 mu m into a vacuum oven at 80 ℃ for drying for 10 hours, taking out the slurry, and finally cutting the slurry into a circular pole piece with the diameter of 12 mm.
The assembly process of the button cell comprises the following steps: the whole assembling process of the button cell is carried out in a glove box in argon atmosphere, the model of the button cell is CR 2016, the counter electrode is a metal lithium sheet, and the electrolyte is 1mol L-1Lithium hexafluorophosphate (LiPF)6) Prepared by dissolving in a solvent of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) in a volume ratio of 1:1:1, and the diaphragm is Celgard 2325 microporous polypropylene film. Firstly, placing the prepared negative pole piece in the middle of a positive pole shell, dropwise adding 3 drops of electrolyte, placing a diaphragm, sequentially placing a metal lithium piece and a gasket on the diaphragm, dropwise adding 1mL of electrolyte, covering a negative pole cover, pressing the negative pole cover by using a button cell tablet press, finally taking the assembled button cell out of a glove box, and testing the electrochemical performance of the button cell by using a cell testing system.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The layered perovskite structure cathode material of the lithium ion battery is characterized in that the chemical formula is Li0.1La0.3NbO3。
2. The negative electrode material of the lithium ion battery with the layered perovskite structure is characterized by having the layered perovskite structure.
3. The preparation method of the negative electrode material with the layered perovskite structure of the lithium ion battery as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) weighing a lithium source, a lanthanum source and a niobium source, and ball-milling and uniformly mixing to obtain a mixed material;
(2) and pre-sintering the obtained mixed material, cooling to room temperature, continuing ball milling, sintering again, and cooling to room temperature to obtain the target product.
4. The preparation method of the negative electrode material with the layered perovskite structure of the lithium ion battery according to claim 3, wherein in the step (1), the addition amounts of the lithium source, the lanthanum source and the niobium source are such that the molar ratio of the lithium element to the lanthanum element to the niobium element is 1:3: 10.
5. The method for preparing the negative electrode material with the layered perovskite structure of the lithium ion battery according to claim 3, wherein in the step (1), the lithium source is lithium carbonate; the lanthanum source is lanthanum oxide; the niobium source is niobium pentoxide.
6. The preparation method of the negative electrode material with the layered perovskite structure for the lithium ion battery as claimed in claim 3, wherein in the step (1), the rotation speed of ball milling is 800-900rpm, and the ball milling time is 5-8 h.
7. The method for preparing the anode material with the layered perovskite structure for the lithium ion battery as claimed in claim 3, wherein in the step (2), the pre-sintering temperature is 700-.
8. The method for preparing the anode material with the layered perovskite structure for the lithium ion battery as claimed in claim 3, wherein in the step (2), the temperature of the secondary sintering is 1000-1100 ℃ and the time is 8-10 h.
9. The method for preparing the negative electrode material with the layered perovskite structure of the lithium ion battery according to claim 3, wherein in the step (2), the temperature rise rate of the pre-sintering and the temperature rise rate of the secondary sintering are both 3-5 ℃.
10. The method for preparing the anode material with the layered perovskite structure for the lithium ion battery as claimed in claim 3, wherein in the step (2), the time for continuing ball milling is 3-5h, and the rotation speed is 800-.
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