Preparation method of single-crystal lithium manganate positive electrode material for lithium ion battery
Technical Field
The invention belongs to the field of energy storage materials and electrochemistry, and relates to a preparation method of a single crystal lithium manganate positive electrode material for a lithium ion battery.
Background
Lithium ion batteries have become the first choice for power batteries because of their advantages of high energy density, excellent cycle life, no memory effect, low self-discharge rate, low pollution, etc. In the development process of lithium ion batteries, the positive electrode material is always a critical factor. In recent years, lithium manganate has come to its priceThe advantages of low cost, no toxicity, good safety and the like become the most promising substitute of lithium cobaltate. However, the capacity fading of lithium manganate in charge-discharge cycle, especially the cycle performance at high temperature (55 ℃), is an important problem for hindering the application of lithium manganate, aiming at causing spinel LiMn2O4A series of researches are carried out at home and abroad on the capacity fading mechanism, and the currently accepted reasons for causing the capacity fading of spinel type lithium manganate mainly comprise: (1) spinel structure LiMn2O4The Jahn-Teller effect occurs in the circulation process, which causes the distortion of spinel crystal lattices and the impedance of an electrode is increased along with the great volume change, thereby causing capacity fading, (2) in the circulation process, under the action of electrolyte, LiMn2O4Disproportionation reaction occurs on the electrode surface so that manganese is slowly dissolved in the electrolyte, resulting in a decrease in cycle performance. Therefore, the crystallinity, the crystal grain morphology, the crystal grain size, the grain size distribution and other characteristics of the spinel LiMn2O4 are opposite to those of LiMn2O4The performance of the positive electrode material has a great influence.
In order to improve the performance of spinel lithium manganate, a great deal of research is put into, and certain effect is achieved. The single-crystal lithium manganate is a new product launched in the years of the lithium manganate industry, and has greatly improved cycle performance. However, the monocrystalline lithium manganate has not been applied in the lithium battery industry on a large scale, and the preparation technology of the monocrystalline lithium manganate is yet to be further innovated.
Disclosure of Invention
The invention aims to overcome the defects of the existing lithium manganate cathode material, and synthesizes single-crystal lithium manganate by improving the preparation process, compared with the traditional lithium manganate material, the single-crystal lithium manganate has the appearance of primary particles, the appearance of regular octahedrons and smaller particles, the D50 is about 3 microns, the structure is a spinel structure, and the compaction density can reach 3.1g/cm3The capacity can reach 110-120 mAh/g, and the cycle number can reach 1000-2000 times. The single crystal structure can further improve the capacity of the lithium manganate material, reduce internal resistance, reduce polarization loss and prolong the cycle life of the battery; at the same time, a high compaction can be obtained, which avoids secondary particle-like compactionThe particles are rolled in the battery manufacturing process to cause the particle crushing phenomenon, and the cycle performance of the material is further improved.
The invention provides a preparation method of single crystal lithium manganate for a lithium ion battery, which is characterized in that a small-particle manganese source is adopted as a raw material, a fine-grain lithium manganate seed crystal is used as a crystal nucleation and growth inducer, a low-melting-point sintering aid is used as a crystal nucleus growth promoter to prepare dynamic single crystal lithium manganate.
A preparation method of a single-crystal lithium manganate positive electrode material for a lithium ion battery comprises the following steps:
step A: ball-milling and mixing a small-particle manganese source, lithium carbonate and an additive according to a proportion;
and B: sintering the ball-milled mixed material at low temperature;
and C: ball-milling and mixing the low-temperature sintered material, the fine-grained lithium manganate crystal seeds and the sintering aid in proportion;
step D: the mixture containing the fine-grained lithium manganate after ball milling and mixing is filled into a pot for sintering, the sintering temperature is 700-900 ℃, and the sintering time is 10-20 hours;
step E: crushing the materials after high-temperature sintering, and then adding a coating agent for coating and sintering, wherein the sintering temperature is 500-700 ℃, and the sintering time is 5-10 hours;
step F: and (3) carrying out post-treatment processes of process classification, demagnetization, batch mixing, packaging and the like on the coated and sintered material to prepare a finished product.
Preferably, the small-particle manganese source in the step A mainly refers to at least one of manganous-manganic oxide, manganese dioxide, manganous oxide, manganese monoxide, manganese hydroxide and manganese carbonate with D50 of 1.7-4.7 microns.
Preferably, the additive is one or two of niobium oxide, titanium oxide, silicon oxide, aluminum oxide, magnesium oxide and aluminum fluoride, and the content of the additive is 0.1-1% of the mass fraction of the whole single-crystal lithium manganate.
Preferably, the molar ratio of lithium/manganese in the step A is 1: 1.9-2.0.
Preferably, the sintering temperature in the step B is 400-700 ℃, the heating rate is 1-5 ℃/min, the sintering time is 5-10 hours, and the atmosphere is air or oxygen.
Preferably, in the step C, the fine-grained lithium manganate seed crystal is single-grained lithium manganate with a grain size of 1 micron, the content of the single-grained lithium manganate seed crystal is 1-5% of the mass of the system, and the sintering aid is one or two of yttrium oxide, aluminum fluoride, aluminum metaphosphate and lithium fluoride, and the mass content of the sintering aid accounts for 0.2% -1% of the mass of the system. The sintering aid has the functions of reducing the sintering temperature and promoting the growth of crystal grains.
Preferably, in the step D, the sintering temperature is 700-850 ℃, the sintering time is 10-20 hours, and the sintering atmosphere is air or oxygen.
Preferably, in the step E, one or two of alumina, titanium oxide and aluminum metaphosphate is used as the coating agent, and the amount of the coating agent is 0.2-1% of the mass of the system.
According to the method, a small-particle manganese source and lithium carbonate are used as raw materials, fine-grain lithium manganate seed crystals are used as an induced forming agent, a low-melting-point sintering aid is used as a crystal nucleus growth promoter to prepare the dynamic single-crystal lithium manganate, compared with the traditional process, the preparation method is simple, the process is more environment-friendly, and the obtained lithium manganate product is high in capacity and long in service life.
Drawings
FIG. 1 is a surface topography of a single-crystal lithium manganate positive electrode material according to an embodiment of the present invention.
FIG. 2 is a surface topography diagram of a common lithium manganate cathode material.
FIG. 3 is a surface topography diagram of a common lithium manganate cathode material.
FIG. 4 is a graph showing the charge and discharge performance of a single-crystal lithium manganate positive electrode material according to an example of the present invention.
FIG. 5 is a graph showing cycle characteristics of a single-crystal lithium manganate positive electrode material according to an example of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in further detail below with reference to the accompanying drawings:
example 1
Step (1): and mixing trimanganese tetroxide and lithium carbonate with the particle size D50 of 1.7-3 microns according to the lithium/manganese molar ratio of 1:1.9, adding niobium oxide accounting for 0.1 percent of the mass fraction of the system, and carrying out ball milling for 2 hours;
step (2): sintering the ball-milled mixed material at the low temperature of 400 ℃ for 5 hours in the air atmosphere, wherein the heating speed is 1-5 ℃/min;
and (3): ball-milling and mixing the low-temperature sintered material with 1 mass percent of fine-grained lithium manganate with the grain size of 1 micron, 1 mass percent of system and 0.2 mass percent of sintering aid yttrium oxide according to a proportion for 2 hours;
and (4): loading the ball-milled mixture into a pot, sintering at the sintering temperature of 700 ℃ for 10 hours;
and (5): crushing the materials after high-temperature sintering, and then adding a coating agent titanium oxide with the mass of 0.2% of the system for coating and sintering, wherein the sintering temperature is 500 ℃, and the sintering time is 10 hours;
and (6): and (3) carrying out post-treatment processes of process classification, demagnetization, batch mixing, packaging and the like on the coated and sintered material to prepare a finished product.
Example 2
Step (1): manganese dioxide and lithium oxide with the particle size D50 of 2-4.7 microns are mixed according to the molar ratio of lithium/manganese of 1: 2, then adding titanium oxide accounting for 1 percent of the mass fraction of the system, and carrying out ball milling for 4 hours;
step (2): sintering the ball-milled mixed material at a low temperature of 700 ℃ for 10 hours in the air atmosphere, wherein the heating speed is 1-5 ℃/min;
and (3): ball-milling and mixing the low-temperature sintered material with 5 mass percent of fine-grained lithium manganate with the grain size of 1 micron, 5 mass percent of system and 1 mass percent of sintering aid alumina according to a proportion for 4 hours;
and (4): loading the ball-milled mixture into a pot, sintering at the sintering temperature of 900 ℃ for 20 hours;
and (5): crushing the materials after high-temperature sintering, and then adding a coating agent alumina with the mass of 1% of the system for coating and sintering, wherein the sintering temperature is 700 ℃, and the sintering time is 5 hours;
and (6): and (3) carrying out post-treatment processes of process classification, demagnetization, batch mixing, packaging and the like on the coated and sintered material to prepare a finished product.
Example 3
Step (1): mixing manganese sesquioxide with the particle size D50 of 2-4 microns and lithium carbonate according to the molar ratio of lithium to manganese of 1/1.95, and then adding silicon oxide accounting for 0.5 percent of the mass fraction of the system for ball milling for 3 hours;
step (2): sintering the ball-milled mixed material at a low temperature of 500 ℃ for 6 hours in an oxygen atmosphere at a heating speed of 1-5 ℃/min;
and (3): ball-milling and mixing the low-temperature sintered material with 2 mass percent of fine-grained lithium manganate with the grain size of 1 micron, 2 mass percent of system and 0.3 mass percent of sintering aid aluminum fluoride according to a proportion for 3 hours;
and (4): the mixture after ball milling is put into a pot for sintering, the sintering temperature is 800 ℃, and the sintering time is 15 hours;
and (5): crushing the materials after high-temperature sintering, and then adding a coating agent aluminum metaphosphate with the mass of 0.5% of the system for coating and sintering, wherein the sintering temperature is 600 ℃, and the sintering time is 8 hours;
and (6): and (3) carrying out post-treatment processes of process classification, demagnetization, batch mixing, packaging and the like on the coated and sintered material to prepare a finished product.
Example 4
Step (1): mixing manganese monoxide with the grain diameter D50 of 1.7-4 microns and lithium carbonate according to the molar ratio of lithium to manganese of 1/1.93, and then adding alumina with the mass fraction of 0.7% of the system for ball milling for 2.5 hours;
step (2): sintering the ball-milled mixed material at 600 ℃ for 7 hours in an oxygen atmosphere at a low temperature, wherein the heating speed is 1-5 ℃/min;
and (3): ball-milling and mixing the low-temperature sintered material with 3 mass percent of fine-grained lithium manganate with the grain size of 1 micron, 3 mass percent of system and 0.6 mass percent of sintering aid lithium metaphosphate in proportion for 2.5 hours;
and (4): loading the ball-milled mixture into a pot, sintering at 750 ℃ for 15 hours at high temperature;
and (5): crushing the materials after high-temperature sintering, and then adding a coating agent titanium oxide with the mass of 0.6% of the system for coating and sintering, wherein the sintering temperature is 550 ℃, and the sintering time is 9 hours;
and (6): and (3) carrying out post-treatment processes of process classification, demagnetization, batch mixing, packaging and the like on the coated and sintered material to prepare a finished product.
Example 5
Step (1): mixing manganese carbonate with the grain diameter D50 of 3-4.5 micro and lithium oxide according to the molar ratio of lithium to manganese of 1/1.98, and then adding magnesium oxide with the mass fraction of 0.4% of the system for ball milling for 3.8 hours;
step (2): sintering the ball-milled mixed material at the low temperature of 550 ℃ for 8 hours in the air atmosphere, wherein the heating speed is 1-5 ℃/min;
and (3): ball-milling and mixing the low-temperature sintered material with 4 mass percent of fine-grained lithium manganate with the grain size of 1 micron, 4 mass percent of system and 0.8 mass percent of sintering aid lithium fluoride according to a proportion for 3.5 hours;
and (4): the mixture after ball milling is put into a pot for sintering, the sintering temperature is 850 ℃, and the sintering time is 12 hours;
and (5): crushing the materials after high-temperature sintering, and then adding a coating agent alumina with the mass of 0.8% of the system for coating and sintering, wherein the sintering temperature is 650 ℃, and the sintering time is 6.5 hours;
and (6): and (3) carrying out post-treatment processes of process classification, demagnetization, batch mixing, packaging and the like on the coated and sintered material to prepare a finished product.
Fig. 1-2 are surface topography diagrams of a single-crystal lithium manganate positive electrode material according to an embodiment of the present invention. In the figure, the shape of the single-crystal lithium manganate is a primary particle, the single-crystal lithium manganate is an octahedron shape, the particle is small, the D50 has obvious crystal structure characteristics about 3 microns, and the structure of the D50 is a spinel structure; compared with the shape of the common lithium manganate shown in figure 3, the product particles prepared by the method are far smaller than the conventional product, and the crystal form characteristics are obvious.
Fig. 4-5 are electrochemical performance tests performed by using the product prepared in the example as a positive electrode active material, and it can be seen from the figures that the capacity of the product prepared by the present invention can reach more than 110mAh/g, and the capacity can be maintained more than 99% after 200 cycles of charge and discharge, which further illustrates that the product prepared by the present method effectively solves the problem of capacity reduction caused by dissolution of lithium manganate during the charge and discharge processes.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.