CN115448385A - Four-phase mixed sodium-ion battery layered oxide positive electrode material and preparation method thereof - Google Patents
Four-phase mixed sodium-ion battery layered oxide positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrode materials, and discloses a four-phase mixed sodium-ion battery layered oxide positive electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: mixing and grinding a Ni source, a Co source, a Mn source, a Li source and a Na source according to a set proportion; calcining the ground mixed material for the first time; grinding the calcined product after the primary calcination is finished, pressing the calcined product into a sheet shape, then carrying out secondary calcination, wherein the calcination temperature is 700-900 ℃, the calcination time is 11-16h, cooling the calcined product from 400-600 ℃ to 200-300 ℃, and then cooling and quenching the calcined product in argon or dry air; after quenching is finished, grinding the flaky product into powder to obtain the product; the problems that the prior Na-P2 phase sodium ion battery layered oxide positive electrode material is low in first cycle coulomb efficiency, and multiple phase changes occur in the charging and discharging process can be solved.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a four-phase mixed sodium-ion battery layered oxide positive electrode material and a preparation method thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Because sodium resources are abundant and similar to the working principle of lithium ion batteries, the application of sodium ion batteries in the field of energy storage is widely concerned by academia and industry in recent years. The transition metal layered oxide cathode material is one of the most promising sodium ion battery cathode materials for commercial application at present due to high theoretical capacity. However, the layered oxide cathode material undergoes multiple phase changes during charging and discharging processes and Na + The large radius results in slow kinetics, which significantly affects the cycle performance and rate performance of the layered oxide positive electrode material of the sodium-ion battery. The currently widely reported layered oxide cathode material of the sodium-ion battery mainly consists of Na-P2 and Na-O3 phase layered oxide cathode materials (P and O respectively represent sodium ions occupying triangular prism and octahedral sites, and 2 and 3 represent the minimum structural unit of a transition metal layer). Wherein the Na-P2 phase is derived from unblocked Na + The ion channel has higher structural stability and rate capability, but the initial Na content of the synthesized Na-P2 phase positive electrode material is lower, and sodium ion vacancies are easily formed, so that the problems of low first sodium removal capacity and low first circulating coulombic efficiency are caused. Meanwhile, the 'Jahn-Taller' effect of the transition metal octahedron structure in the sodium removal/insertion process can cause the significant volume change of the cathode material in the charge and discharge process.
At present, researchers modify Na-P2 phase layered oxide cathode materials by various methods, reduce sodium ion vacancy ordering, increase sodium content and relieve volume changes caused by sodium removal/insertion. The construction of two-phase composite structures is one of the effective methods to solve these problems. On one hand, the first circulation coulombic efficiency of the Na-P2 phase positive electrode material is effectively improved through a high-sodium-content phase (Na-P3 or Na-O3); on the other hand, the volume change of the layered oxide anode caused by sodium removal/insertion is effectively relieved by the different volume change rates of the two phases, and the structural stability and the cycle performance of the anode material are improved. However, the cycle performance of the two-phase composite sodium-ion battery layered oxide positive electrode material still needs to be further improved, and after 50 cycles, the capacity fading is obvious.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a layered oxide positive electrode material of a four-phase mixed sodium-ion battery and a preparation method thereof. The anode material is a layered oxide anode material composed of four-phase solid solutions of Na-P2, na-O3, na-O1 and Li-O3, and can solve the problems of low first-cycle coulomb efficiency, multiple phase changes in the charging and discharging process and the like of the prior layered oxide anode material of the Na-P2 phase sodium-ion battery.
In order to realize the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a layered oxide positive electrode material of a four-phase mixed sodium-ion battery, which comprises the following steps:
mixing and grinding a Ni source, a Co source, a Mn source, a Li source and a Na source according to a set proportion;
calcining the ground mixed material for the first time at the temperature of 400-600 ℃ for 1-5h;
grinding the calcined product after the primary calcination is finished, pressing the calcined product into sheets, and then carrying out secondary calcination, wherein the calcination temperature is 700-900 ℃, the calcination time is 11-16h, the temperature rise process is firstly carried out to 400-600 ℃, the temperature rise rate is 3-5 ℃/min, the calcination time is kept for 1-2h, then the temperature rise process is carried out to 800-900 ℃ from 400-600 ℃, the temperature rise rate is 3-5 ℃/min, and the heat preservation time is 10-15h;
the cooling process is as follows: cooling from 800-900 deg.C to 400-600 deg.C at a rate of 3-5 deg.C/mim, maintaining for 1-2h, cooling from 400-600 deg.C to 200-300 deg.C, and quenching in argon or dry air;
after quenching is finished, grinding the flaky product into powder to obtain the product;
the Ni source is acetate, oxide, carbonate or hydroxide of Ni;
the Co source is acetate, oxide, carbonate or hydroxide of Co;
the Mn source is Mn acetate, oxide, carbonate or hydroxide;
the Li source is Li carbonate or hydroxide;
the Na source is carbonate or hydroxide of Na.
In a second aspect, the invention provides a four-phase mixed sodium-ion battery layered oxide positive electrode material prepared by the preparation method.
The beneficial effects achieved by one or more of the embodiments of the invention are as follows:
1. the preparation method is a solid-phase roasting method, adopts oxides, carbonates or acetates of Ni, co and Mn or carbonates or hydroxides of Li and Na and the like as precursor raw materials, has low cost, does not generate waste water and harmful gas in the roasting process, and is simple and environment-friendly.
2. The four-phase mixed layered oxide cathode material is prepared by Li doping and Ar or air cooling quenching. The Na-O3 phase, the Na-O1 phase and the Li-O3 phase in the multi-phase mixed structure can compensate the problem of insufficient sodium content in the Na-P2 phase, and the first cycle coulombic efficiency of the positive electrode is obviously improved; meanwhile, the multiphase mixed structure can relieve the volume expansion caused by phase change in the Na-P2 phase charging and discharging process, and the structural stability and the cycle performance of the anode material are improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 is an XRD pattern of a layered oxide positive electrode material of a four-phase mixed sodium-ion battery obtained in example 1 of the present invention;
FIG. 2 is an SEM image of a layered oxide cathode material of a four-phase mixed sodium-ion battery obtained in example 1 of the present invention;
FIG. 3 is a HAADF-STEM diagram of a layered oxide positive electrode material of a four-phase hybrid sodium-ion battery obtained in example 1 of the present invention;
fig. 4 is a charge-discharge curve of the layered oxide positive electrode material of the four-phase hybrid sodium-ion battery obtained in example 1 of the present invention;
FIG. 5 is a graph of rate performance of a layered oxide positive electrode material of a four-phase hybrid sodium-ion battery obtained in example 1 of the present invention and a comparative sample of example 1;
FIG. 6 is a cycle performance curve of the layered oxide positive electrode material of the four-phase mixed sodium-ion battery obtained in example 1 of the present invention and the comparative sample of example 1 in the charge and discharge at 1C rate;
FIG. 7 is an in-situ XRD pattern of the layered oxide positive electrode material of the four-phase mixed sodium-ion battery obtained in example 1 of the present invention;
fig. 8 is an in-situ XRD pattern of a comparative sample of the layered oxide cathode material of the four-phase hybrid sodium-ion battery obtained in example 1 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the invention provides a preparation method of a layered oxide positive electrode material of a four-phase mixed sodium-ion battery, which comprises the following steps:
mixing and grinding a Ni source, a Co source, a Mn source, a Li source and a Na source according to a set proportion;
carrying out primary calcination on the ground mixed material, wherein the primary calcination temperature is 400-600 ℃, and the calcination time is 1-5h;
grinding the calcined product after the primary calcination is finished, pressing the calcined product into sheets, and then carrying out secondary calcination, wherein the calcination temperature is 700-900 ℃, the calcination time is 11-16h, the temperature rise process is firstly carried out to 400-600 ℃, the temperature rise rate is 3-5 ℃/min, the calcination time is kept for 1-2h, then the temperature rise process is carried out to 800-900 ℃ from 400-600 ℃, the temperature rise rate is 3-5 ℃/min, and the heat preservation time is 10-15h;
the temperature reduction process comprises the following steps: cooling from 800-900 deg.C to 400-600 deg.C at a rate of 3-5 deg.C/mim, maintaining for 1-2h, cooling from 400-600 deg.C to 200-300 deg.C, and quenching in argon or dry air;
after quenching is finished, grinding the flaky product into powder to obtain the product;
the Ni source is acetate, oxide, carbonate or hydroxide of Ni;
the Co source is acetate, oxide, carbonate or hydroxide of Co;
the Mn source is Mn acetate, oxide, carbonate or hydroxide;
the Li source is Li carbonate or hydroxide;
the Na source is carbonate or hydroxide of Na.
The flaking increases the contact between the particles, facilitating the diffusion of ions and obtaining the desired structure.
In the secondary calcining process, the reactions in different temperature sections are different, the sintering at 400-600 ℃ is mainly that the oxides react to generate a primary product, and because the solid-phase ion transmission is slower, the reaction degree needs to be increased at a higher temperature of 800-900 ℃, so that the uniformity of the material is improved.
In the cooling process, cooling at different temperature sections and different cooling speeds have important effects on defect formation and structural rearrangement of the anode material in atomic scale, the heat preservation at 400-600 ℃ is favorable for forming a basic layered structure, and the subsequent rapid cooling is favorable for retaining the defect structure.
In some embodiments, the molar ratio of the Ni source, the Co source, the Mn source, the Li source, and the Na source is 0-0.2:0.1:0.3-0.5:0.1-0.4:0.7-0.8.
Preferably, the molar ratio of the Ni source, the Co source, the Mn source, the Li source and the Na source is 0.1-0.2:0.1:0.3-0.5:0.1-0.4:0.7 to 0.8, and the Ni source content is not 0.
In some embodiments, the pressed sheet structure has a thickness of 0.5-2mm.
In some embodiments, the pressure at which the sheet is pressed is 10 to 30MPa.
In some embodiments, the Ni source, the Co source, the Mn source, the Li source and the Na source are added into an agate mortar or a ball milling pot according to a set proportion and mixed and ground for 1-5h.
In some embodiments, the temperature rise process of the secondary calcination is to rise to 450-550 ℃ at the rate of 3-5 ℃/min, keep for 1-2h, then rise to 850-900 ℃ from 450-550 ℃, at the rate of 3-5 ℃/min, and keep for 10-15h.
Preferably, the temperature reduction process of the secondary calcination comprises the following steps: cooling from 850-900 deg.C to 450-550 deg.C at a rate of 3-5 deg.C/mim, maintaining for 1-2h, cooling from 450-550 deg.C to 200-300 deg.C, and quenching in argon or dry air.
Further preferably, the quenching is performed by cooling with argon gas or dry air in a glove box or a dry room for a battery.
In a second aspect, the invention provides a layered oxide positive electrode material of a four-phase mixed sodium-ion battery, which is prepared by the preparation method.
In some embodiments, the layered oxide positive electrode material of the four-phase mixed sodium-ion battery consists of a four-phase solid solution of Na-P2, na-O3, na-O1, and Li-O3 phases, na 0.7 Li x Ni 0.3-x/2 Mn 0.6-x/2 Co 0.1 O 2 ，x=0.1-0.3。
In order to better explain the invention, the following further illustrate the main content of the invention in connection with specific examples, but the content of the invention is not limited to the following examples.
Example 1
Weighing 2mmol of nickel acetate tetrahydrate, 5mmol of manganese acetate tetrahydrate, 1mmol of cobalt acetate tetrahydrate, 7.35mmol of sodium hydroxide and 2.1mmol of lithium hydroxide, pouring into a clean agate mortar, and fully grinding for 1h until the materials are fully and uniformly mixed. To prevent Li and Na loss, both LiOH and NaOH required 5% excess during the addition. And (3) putting the ground mixed materials into a crucible, and then placing the crucible into a muffle furnace for heat treatment, wherein the reaction temperature is 500 ℃, the calcination time is 5h, and the heating rate from room temperature to 500 ℃ is 3 ℃/min.
And naturally cooling the sample to room temperature, taking the sample out of the muffle furnace, grinding the sample into powder in a mortar, and pressing the powder into a wafer at the pressure of 15MPa.
The wafer was again placed in the crucible and calcined in a muffle furnace at 900 ℃ for 15h. The temperature rise process is that the temperature is raised from room temperature to 500 ℃ at the speed of 3 ℃/min, then the temperature is raised from 500 ℃ to 900 ℃ and is kept for 15h, and the temperature rise speed is 5 ℃/min.
The temperature reduction process is that the temperature is reduced from 900 ℃ to 500 ℃ at the speed of 5 ℃/mim, the temperature is preserved for 1h in a muffle furnace at the temperature of 500 ℃, and then the steel is cooled to 300 ℃, and then the steel is rapidly transferred to a glove box for argon cooling quenching.
And grinding the finally obtained wafer into powder in a mortar or a ball mill to obtain the four-phase mixed layered oxide sodium-ion battery positive electrode material.
In order to comparatively study the charge and discharge capacity, rate capability and cycle performance of the layered oxide cathode material by Li doping and Ar gas cooling quenching, the present example also prepared a layered oxide cathode material without Li doping and gas cooling quenching as a comparative sample. The preparation process comprises the following steps: weighing 3mmol of nickel acetate tetrahydrate, 6mmol of manganese acetate tetrahydrate, 1mmol of cobalt acetate tetrahydrate and 7.035mmol of sodium hydroxide, pouring into a clean agate mortar, and fully grinding for 1h until the materials are fully and uniformly mixed. To prevent Na loss, naOH was added in 5% excess.
And (3) putting the ground mixed material into a crucible, and then placing the crucible into a muffle furnace for heat treatment, wherein the reaction temperature is 500 ℃, the calcination time is 5h, and the heating rate from room temperature to 500 ℃ is 3 ℃/min.
And naturally cooling the sample to room temperature, taking the sample out of the muffle furnace, grinding the sample into powder in a mortar, and pressing the powder into a wafer at the pressure of 15MPa.
The wafer was again placed in the crucible and calcined in a muffle furnace at 900 ℃ for 15h. The temperature rise process is that the temperature is raised from the room temperature to 500 ℃ at the rate of 3 ℃/min, and then the temperature is raised from 500 ℃ to 900 ℃ and is kept for 15h, and the temperature rise rate is 5 ℃/min.
The temperature reduction process is that the temperature is reduced from 900 ℃ to 500 ℃, the speed is 5 ℃/mim, the temperature is preserved for 1h in a muffle furnace at 500 ℃, and then the temperature is cooled to 300 ℃, and then the temperature is transferred to a glove box or a drying room for batteries to realize argon or dry air cooling quenching.
And grinding the finally obtained wafer into powder in a mortar or a ball mill to obtain the four-phase mixed sodium-ion battery layered oxide cathode material.
As shown by the XRD pattern and the structure refinement result of FIG. 1, the layered oxide positive electrode material obtained in example 1 of the present invention is composed of four phases of Na-P2, na-O3, na-O1 and Li-O3. The results of the structure refinement indicated that the Na-P2, na-O3, na-O1 and Li-O3 contents were approximately 47.3%, 5.3%, 18.1% and 29.3%.
The SEM image of fig. 2 shows that the prepared four-phase mixed layered oxide positive electrode material is thick plate-like microparticles.
The HAADF-STEM diagram of FIG. 3 also shows that the layered oxide positive electrode material obtained in example 1 is composed of four phases of Na-P2, na-O3, na-O1 and Li-O3.
FIG. 4 is a charge-discharge curve showing that the specific discharge capacity of the positive electrode material of the four-phase mixed layered oxide obtained in example 1 is as high as 181.1 mAh g -1 The first-cycle coulombic efficiency is 91.2%, which shows that the preparation method can prepare the layered oxide cathode material with high specific capacity and first-cycle coulombic efficiency.
The battery rate performance graph of fig. 5 shows that the four-phase mixed layered oxide cathode material prepared by the present invention has a rate performance significantly superior to that of the comparative sample.
As shown in fig. 6, after the four-phase mixed layered oxide positive electrode material prepared in example 1 of the present invention is subjected to 200 cycles of charge and discharge at a rate of 1C, the capacity retention rate is 83.5%, which is higher than 75.3% of the comparative sample. Meanwhile, the specific capacity of the four-phase mixed layered oxide cathode material prepared in the embodiment 1 of the invention in the circulating process is far higher than that of a comparative sample.
As shown in fig. 7 and 8, in-situ XRD during charging and discharging processes of the four-phase mixed layered oxide positive electrode material prepared in example 1 and the comparative sample shows that lattice change and strain amount caused by phase change of the four-phase mixed layered oxide positive electrode material during charging and discharging processes are much smaller than those of the comparative sample. The in-situ XRD result shows that the volume change caused by the phase change in the charging and discharging process is effectively relieved by the four-phase mixing, the irreversible phase change is also avoided, and the structural stability of the positive electrode material in the charging and discharging process is improved.
Example 2
2.5mmol of nickel acetate tetrahydrate, 5.5mmol of manganese acetate tetrahydrate, 1mmol of cobalt acetate tetrahydrate, 7.7mmol of sodium hydroxide and 1.1mmol of lithium hydroxide are weighed and poured into a clean agate mortar, and the materials are fully ground for 2 hours until the materials are fully and uniformly mixed. To prevent Li and Na loss, liOH and NaOH were both added in 10% excess.
And (3) putting the ground mixed material into a crucible, and then placing the crucible into a muffle furnace for heat treatment, wherein the reaction temperature is 400 ℃, the calcination time is 5h, and the heating rate from room temperature to 400 ℃ is 3 ℃/min.
And naturally cooling the sample to room temperature, taking the sample out of the muffle furnace, grinding the sample into powder in a mortar, and pressing the powder into a wafer at the pressure of 15MPa.
The wafer was again placed in the crucible and calcined in a muffle furnace at 900 ℃ for 15h. The temperature rise process is that the temperature is firstly raised to 400 ℃ from the room temperature at the rate of 3 ℃/min, and then the temperature is raised to 900 ℃ from 400 ℃ and is kept for 15h, and the temperature rise rate is 5 ℃/min. The temperature reduction process is that the temperature is reduced from 900 ℃ to 400 ℃ at the speed of 5 ℃/mim, the temperature is preserved for 2h in a muffle furnace at the temperature of 400 ℃, and the temperature is cooled to 200 ℃, and then the battery is transferred to a drying room for a battery to be dried and air-cooled and quenched.
And grinding the finally obtained wafer into powder in a mortar to obtain the four-phase mixed sodium-ion battery layered oxide cathode material.
Example 3
2.25mmol nickel acetate tetrahydrate, 5.25mmol manganese acetate tetrahydrate, 1mmol cobalt acetate tetrahydrate, 7.56mmol sodium hydroxide and 1.62mmol lithium hydroxide are weighed and poured into a clean agate mortar, and fully ground for 5 hours until the materials are fully and uniformly mixed. To prevent Li and Na loss, both LiOH and NaOH required 8% excess during the addition.
And (3) putting the ground mixed material into a crucible, and then placing the crucible into a muffle furnace for heat treatment, wherein the reaction temperature is 600 ℃, the calcination time is 5h, and the heating rate from room temperature to 600 ℃ is 3 ℃/min.
And naturally cooling the sample to room temperature, taking the sample out of the muffle furnace, grinding the sample into powder in a mortar, and pressing the powder into a wafer at the pressure of 15MPa.
The wafer was again placed in the crucible and calcined in a muffle furnace at 900 ℃ for 15h. The temperature rise process is that the temperature is firstly raised to 600 ℃ from the room temperature at the rate of 3 ℃/min, and then the temperature is raised to 900 ℃ from 600 ℃ for 10h, and the temperature rise rate is 5 ℃/min.
The temperature reduction process is that the temperature is reduced from 900 ℃ to 600 ℃, the speed is 5 ℃/mim, the temperature is preserved for 2h in a muffle furnace at the temperature of 600 ℃, and then the temperature is cooled to 300 ℃, and then the temperature is transferred to a glove box for dry air cooling and quenching.
And grinding the finally obtained wafer into powder in a mortar to obtain the four-phase mixed sodium-ion battery layered oxide cathode material.
Example 4
2.25mmol nickel oxide, 5.25mmol manganese oxide, 1mmol cobalt oxide, 3.85mmol sodium carbonate and 0.825mmol lithium carbonate are weighed into a clean agate mortar and fully ground for 5h until the materials are fully and uniformly mixed. To prevent loss of Li and Na, both sodium carbonate and lithium carbonate were added in 10% excess.
And (3) putting the ground mixed materials into a crucible, and then placing the crucible into a muffle furnace for heat treatment, wherein the reaction temperature is 600 ℃, the calcination time is 5h, and the temperature rising rate from room temperature to 600 ℃ is 3 ℃/min.
And naturally cooling the sample to room temperature, taking the sample out of the muffle furnace, grinding the sample into powder in a mortar, and pressing the powder into a wafer at the pressure of 15MPa.
The wafer is placed into the crucible again and calcined in a muffle furnace for 10h at 800 ℃. The temperature rise process is that the temperature is raised from room temperature to 500 ℃ at the speed of 3 ℃/min, then the temperature is raised from 500 ℃ to 800 ℃ and kept for 10h, and the temperature rise speed is 5 ℃/min.
The temperature reduction process is that the temperature is reduced from 800 ℃ to 500 ℃ at the speed of 5 ℃/mim, the temperature is preserved for 2h in a muffle furnace at 500 ℃, and then the temperature is cooled to 300 ℃, and then the product is transferred to a drying room for batteries to be cooled and quenched by argon.
And grinding the finally obtained wafer into powder in a ball mill to obtain the four-phase mixed sodium-ion battery layered oxide positive electrode material.
Example 5
2mmol of nickel hydroxide, 5mmol of manganese hydroxide, 1mmol of cobalt hydroxide, 3.85mmol of sodium carbonate and 1.1mmol of lithium carbonate are weighed and poured into a clean agate mortar, and the materials are fully ground for 5 hours until the materials are fully and uniformly mixed. To prevent loss of Li and Na, both sodium carbonate and lithium carbonate were added in 10% excess.
And (3) putting the ground mixed materials into a crucible, and then placing the crucible into a muffle furnace for heat treatment, wherein the reaction temperature is 400 ℃, the calcination time is 5h, and the heating rate from room temperature to 400 ℃ is 3 ℃/min.
And naturally cooling the sample to room temperature, taking the sample out of the muffle furnace, grinding the sample into powder in a mortar, and pressing the powder into a wafer at the pressure of 30MPa. The wafer was again placed in the crucible and calcined in a muffle furnace at 700 ℃ for 10h.
The temperature rise process is that the temperature is firstly raised from the room temperature to 400 ℃ at the speed of 3 ℃/min, then the temperature is raised from 400 ℃ to 700 ℃ and is kept for 10h, and the temperature rise speed is 5 ℃/min.
The temperature reduction process is that the temperature is reduced from 700 ℃ to 400 ℃, the speed is 5 ℃/mim, the temperature is preserved for 2h in a muffle furnace at 500 ℃, then the temperature is cooled to 200 ℃, and then the temperature is transferred to a glove box for dry air cooling and quenching.
And grinding the finally obtained wafer into powder in a mortar to obtain the four-phase mixed sodium-ion battery layered oxide cathode material.
Example 6
1mmol of nickel carbonate, 2.5mmol of manganese oxide, 1mmol of cobalt oxide, 3.85mmol of sodium carbonate and 1.1mmol of lithium carbonate are weighed and poured into a clean agate mortar, and the materials are fully ground for 3 hours until the materials are fully and uniformly mixed. To prevent loss of Li and Na, both sodium carbonate and lithium carbonate were added in 10% excess.
And (3) putting the ground mixed materials into a crucible, and then placing the crucible into a muffle furnace for heat treatment, wherein the reaction temperature is 600 ℃, the calcination time is 5h, and the heating rate from room temperature to 500 ℃ is 3 ℃/min.
And naturally cooling the sample to room temperature, taking the sample out of the muffle furnace, grinding the sample into powder in a mortar, and pressing the powder into a wafer at the pressure of 15MPa.
The wafer was again placed in the crucible and calcined in a muffle furnace at 900 ℃ for 10h.
The temperature rise process is that the temperature is raised from the room temperature to 500 ℃ at the rate of 3 ℃/min, and then the temperature is raised from 500 ℃ to 900 ℃ and kept for 10h, and the temperature rise rate is 5 ℃/min.
The temperature reduction process is that the temperature is reduced from 900 ℃ to 500 ℃ at the speed of 5 ℃/mim, the temperature is preserved for 2 hours in a muffle furnace at the temperature of 500 ℃, and then the steel plate is cooled to 300 ℃ and then transferred to a glove box for dry air cooling quenching.
And grinding the finally obtained wafer into powder in a ball mill to obtain the four-phase mixed sodium-ion battery layered oxide cathode material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a layered oxide positive electrode material of a four-phase mixed sodium-ion battery is characterized by comprising the following steps: the method comprises the following steps:
mixing Ni source, co source, mn source, li source and Na source according to the mol ratio of 0-0.2:0.1:0.3-0.5:0.1-0.4:0.7-0.8, mixing and grinding, wherein the content of the Ni source is not 0;
carrying out primary calcination on the ground mixed material, wherein the primary calcination temperature is 400-600 ℃, and the calcination time is 1-5h;
after the primary calcination is finished, grinding the calcined product, pressing the calcined product into a sheet shape, and then carrying out secondary calcination, wherein the calcination temperature is 700-900 ℃, the calcination time is 11-16h, the temperature rise process is firstly to 400-600 ℃, the temperature rise rate is 3-5 ℃/min, the temperature is kept for 1-2h, then the temperature rise process is from 400-600 ℃ to 800-900 ℃, the temperature rise rate is 3-5 ℃/min, and the temperature is kept for 10-15h;
the temperature reduction process comprises the following steps: cooling from 800-900 deg.C to 400-600 deg.C at a rate of 3-5 deg.C/mim, maintaining for 1-2h, cooling from 400-600 deg.C to 200-300 deg.C, and quenching in argon or dry air;
after quenching is finished, grinding the flaky product into powder to obtain the product.
2. The preparation method of the layered oxide positive electrode material of the four-phase mixed sodium-ion battery according to claim 1, characterized in that: the Ni source is acetate, oxide, carbonate or hydroxide of Ni;
the Co source is acetate, oxide, carbonate or hydroxide of Co;
the Mn source is Mn acetate, oxide, carbonate or hydroxide;
the Li source is carbonate or hydroxide of Li;
the Na source is carbonate or hydroxide of Na.
3. The preparation method of the layered oxide positive electrode material of the four-phase mixed sodium-ion battery according to claim 1, characterized in that: the thickness of the pressed sheet structure is 0.5-2mm.
4. The preparation method of the layered oxide positive electrode material of the four-phase mixed sodium-ion battery according to claim 3, characterized in that: the pressure when pressing into sheets is 10-30MPa.
5. The preparation method of the layered oxide positive electrode material of the four-phase mixed sodium-ion battery according to claim 1, characterized in that: and adding the Ni source, the Co source, the Mn source, the Li source and the Na source into an agate mortar or a ball-milling tank according to a set proportion, and mixing and grinding for 1-5h.
6. The preparation method of the layered oxide positive electrode material of the four-phase mixed sodium-ion battery according to claim 1, characterized in that: the temperature rise process of the secondary calcination is that the temperature is raised to 450-550 ℃ at the rate of 3-5 ℃/min and kept for 1-2h, and then the temperature is raised from 450-550 ℃ to 850-900 ℃ at the rate of 3-5 ℃/min and kept for 10-15h.
7. The preparation method of the layered oxide positive electrode material of the four-phase mixed sodium-ion battery according to claim 6, characterized in that: the temperature reduction process of the secondary calcination comprises the following steps: cooling from 850-900 deg.C to 450-550 deg.C at a rate of 3-5 deg.C/mim, maintaining for 1-2h, cooling from 450-550 deg.C to 200-300 deg.C, and quenching in argon or dry air.
8. The preparation method of the layered oxide positive electrode material of the four-phase mixed sodium-ion battery according to claim 7, characterized in that: and cooling and quenching in a glove box or a drying room for a battery by adopting argon or dry air.
9. A four-phase mixed sodium-ion battery layered oxide positive electrode material is characterized in that: the preparation method of the layered oxide cathode material of the four-phase mixed sodium-ion battery, which is disclosed by any one of claims 1-8.
10. The layered oxide positive electrode material of the four-phase mixed sodium-ion battery according to claim 9, characterized in that: it is composed of Na-P2, na-O3, na-O1 and Li-O3 phase four-phase solid solution, na 0.7 Li x Ni 0.3-x/2 Mn 0.6-x/2 Co 0.1 O 2 ，x=0.1-0.3。
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