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CN116588984B - Sodium-rich P2 phase layered oxide and preparation method thereof, sodium ion battery positive electrode material and battery - Google Patents

Sodium-rich P2 phase layered oxide and preparation method thereof, sodium ion battery positive electrode material and battery Download PDF

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CN116588984B
CN116588984B CN202310369831.5A CN202310369831A CN116588984B CN 116588984 B CN116588984 B CN 116588984B CN 202310369831 A CN202310369831 A CN 202310369831A CN 116588984 B CN116588984 B CN 116588984B
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CN116588984A (en
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杨树斌
王梓铭
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Beihang University
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    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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Abstract

The invention discloses a sodium-rich P2 phase layered oxide and a preparation method thereof, a sodium ion battery positive electrode material and a battery, wherein the chemical formula of the sodium-rich P2 phase layered oxide is represented by Na xAyO2, wherein Na represents a sodium element, A is selected from nickel and manganese elements, x >1, y=1, or the chemical formula of the sodium-rich P2 phase layered oxide is represented by Na xAyMzO2, wherein Na represents a sodium element, A is selected from nickel and manganese elements, M represents a doping element, and M is selected from at least one metal element different from sodium, nickel and manganese in a third period to a fifth period of the periodic table of elements, x >1,0.8 is less than or equal to y <1,0< z is less than or equal to 0.2, and y+z=1. The invention provides another technical route which is different from the prior art by pre-sodium treatment or adding sodium supplement agent, namely, the sodium-rich P2 phase layered oxide is adopted as the positive electrode material of the sodium ion battery.

Description

Sodium-rich P2 phase layered oxide, preparation method thereof, sodium ion battery positive electrode material and battery
Technical Field
The invention belongs to the field of sodium ion batteries, and particularly relates to a sodium-rich P2 layered oxide, a preparation method thereof, and a positive electrode material used as a sodium ion battery and a battery.
Background
In recent years, sodium ion batteries have been rapidly developed, which are expected to be alternative products to lithium ion batteries in many fields by virtue of low cost and high safety. To meet the demands of practical applications, sodium ion batteries require electrode materials with higher specific capacities to achieve higher energy densities. At present, hard carbon is one of the most likely sodium ion battery anode materials for industrial application due to high capacity and high stability. However, since the hard carbon negative electrode has many defects and a large specific surface area, the formation of the SEI film and more side reactions are accompanied in the first sodium intercalation process, thereby causing serious irreversible loss of sodium ions. For a sodium full cell system, all of the sodium ions used for deintercalation come from the positive electrode material, and any unacceptable loss of sodium ions results in a decrease in the energy density of the full cell, thus making many promising sodium-deficient positive electrode materials difficult to use. For example, the P2 phase positive electrode material has a wider triangular Na ion transport channel and a lower migration energy barrier, is favorable for transporting Na ions, has a Na ion transport rate obviously higher than that of the O3 phase positive electrode material, and has faster dynamics. But the P2 phase is a sodium-deficient positive electrode material, and irreversible sodium ion loss leads to obvious effect of reducing the energy density of the battery.
Zhao et al (science 2020,370, 708-711) accurately distinguished the structural competition relationship between the P2 phase and the O3 phase by introducing a cationic potential, and according to its proposed theory, as the Na content increases, the average Na ion potential increases and the electrostatic repulsive shielding between TMO 2 plates increases, facilitating the formation of the O3 phase structure. They use the cation potential to realize charge compensation by reducing Li and increasing Mn content, and designed a P2 phase positive electrode material Na 5/6Li5/18Mn13/18O2 with high sodium content, which is also the P2 phase layered oxide positive electrode material with highest Na content reported at present. According to this theory, the Na content in the P2 phase layered oxide hardly breaks through its reported theoretical value (na=5/6).
At present, researchers mainly solve irreversible sodium loss in the first sodium embedding process by adding a sodium supplementing agent or pre-sodifying a negative electrode material. For example, cui et al (ACSnano 2011,5 (8), 6487-6493.) first assembled a negative electrode material into half cells and then charged and discharged to form an SEI film on the surface of the negative electrode, and then disassembled the cells and taken out of the negative electrode material to assemble a full cell. Although the method can realize negative sodium supplementation, the process is complex and is not suitable for industrial production, zhang et al (Energy & Environmental Science2016,9 (10), 2978-3006) use Na 3 P as a sodium supplementing agent to compensate irreversible sodium loss, and the Energy density of the assembled full battery is obviously improved. However, na 3 P has poor air stability, and its decomposition products may undergo side reactions with the positive electrode material or electrolyte, resulting in reduced stability of the battery;
although irreversible sodium loss can be compensated to some extent by pre-sodium modification or addition of sodium supplements, the pre-sodium modification process is complicated, and part of the sodium supplements have poor air stability and decomposition may generate harmful products, which results in the above scheme not being suitable for industrial production. Therefore, it is necessary to develop a novel sodium-rich layered oxide cathode material so as to avoid pre-sodiumization of the anode material or addition of a sodium supplement agent in the production process of sodium ion batteries.
Disclosure of Invention
Aiming at the technical problem that the formation of SEI film and more side reactions cause serious irreversible loss of sodium ions in the process of embedding sodium in the first charging of a sodium ion battery, the invention provides a sodium ion positive electrode material, namely a sodium-rich P2 phase layered oxide. Or, in order to solve the technical problem that the sodium ion battery has serious irreversible loss, a technical route which is different from the prior art by pre-sodium treatment or adding sodium supplement agent is provided, namely, the sodium-rich P2 phase layered oxide is adopted as the positive electrode material of the sodium ion battery.
The first aspect of the present invention provides a sodium-rich P2-phase layered oxide having a chemical formula represented by Na xAyO2, wherein Na represents a sodium element, a is selected from nickel (Ni) and manganese (Mn) elements, x >1, y=1.
In some embodiments, the above-described sodium-rich layered oxide has a chemical formula of Na xNiαMnβO2, y=α+β,0< α.ltoreq.0.4, 0< β.ltoreq.0.7, preferably 0.1.ltoreq.α.ltoreq.0.4, 0.1.ltoreq.β.ltoreq.0.7, more preferably 0.2.ltoreq.α.ltoreq. 0.33,0.6.ltoreq.β.ltoreq.0.7, still more preferably 0.23.ltoreq.α.ltoreq. 0.33,0.67.ltoreq.β.ltoreq.0.7.
In some embodiments, the XRD diffraction pattern of the sodium-rich P2 phase layered oxide comprises (002) (004) (100) (102) (103) (104) crystal plane diffraction peaks, and the sodium-rich P2 phase layered oxide is a single phase of the P2 phase.
In some embodiments 1<x +.1.5; preferably, the method comprises the steps of, x is more than or equal to 1.1 and less than or equal to 1.34.
The second aspect of the invention provides a preparation method of the sodium-rich P2 phase layered oxide, which comprises the steps of weighing sodium salt, nickel oxide and manganese oxide in corresponding molar ratios according to the stoichiometric ratio of sodium, nickel and manganese elements as x to alpha to beta, mixing the sodium salt, the nickel oxide and the manganese oxide to obtain mixed powder, pressing the mixed powder after the mixing treatment to obtain pressed and molded blocks, and sintering the blocks.
In some embodiments, the sodium salt is at least one selected from sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium citrate, sodium nitrate, and sodium hydroxide.
In some embodiments, the above mixing treatment is performed by ball milling, preferably, the ball mass ratio is (5-20): 1, the dispersing agent is one or more of ethanol, acetone, N-methylpyrrolidone (NMP), isopropyl alcohol (IPA) or water, and the ball milling time is 3-24 hours.
In some embodiments, the pressing step more specifically includes loading the mixed powder into a mold, and pressing the mixed powder to form the mixed powder, wherein the pressing pressure is preferably 5 to 30Mpa;
In some embodiments, the sintering temperature in the above sintering step is between 500 and 1100 ℃, preferably between 800 and 1000 ℃, more preferably between 850 and 950 ℃, still more preferably between 880 and 930 ℃.
In a third aspect, the present invention provides a sodium-rich P2-phase layered oxide, the chemical formula of the sodium-rich P2-phase layered oxide being represented by Na xAyMzO2, wherein Na represents a sodium element, a is selected from nickel (Ni) and manganese (Mn) elements, M represents a doping element, M is selected from at least one metal element other than sodium (Na), nickel (Ni) and manganese (Mn) in the third to fifth periods of the periodic table, x >1,0.8 < y <1,0< z < 0.2, y+z=1.
In some embodiments, the doping element is selected from iron (Fe), cobalt (Co), copper (Cu), titanium (Ti), magnesium (Mg), zinc (Zn), calcium (Ca), vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tin (Sn), antimony (Sb), aluminum (Al) elements.
In some embodiments, the above-described sodium-rich layered oxide has a chemical formula of Na xNiαMnβMzO2, y=α+β,0< α.ltoreq.0.4, 0< β.ltoreq.0.7, preferably 0.1.ltoreq.α.ltoreq.0.4, 0.1.ltoreq.β.ltoreq.0.7, more preferably 0.2.ltoreq.α.ltoreq. 0.34,0.6.ltoreq.β.ltoreq.0.7, still more preferably 0.23.ltoreq.α.ltoreq. 0.33,0.67.ltoreq.β.0.7.
In some embodiments, the XRD diffraction pattern of the sodium-rich P2 phase layered oxide comprises (002) (004) (100) (102) (103) (104) crystal plane diffraction peaks, and the sodium-rich P2 phase layered oxide is a P2 phase single phase.
In some embodiments 1<x +.1.5; preferably, the method comprises the steps of, x is more than or equal to 1.1 and less than or equal to 1.34.
In some embodiments, M is selected from five or more metal elements in the third to fifth periods of the periodic table.
In some embodiments, the chemical formula of the sodium-rich P2 phase layered oxide is shown above as Nax(NiαMnβ)(M1aM2bM3cM4dM5eM6f)O2,y＝α+β,z＝a+b+c+d+e+f,0＜z≤0.2,0.1≤α≤0.4,0.1≤β≤0.7,0＜a≤0.05,0＜b≤0.05,0＜c≤0.05,0＜d≤0.05,0＜e≤0.05,0≤f≤0.05;, wherein M1, M2, M3, M4, M5, M6 represent different of the doping elements.
In some embodiments 0<a.ltoreq.0.04, 0.ltoreq.b.ltoreq.0.04, 0.ltoreq.c.ltoreq.0.04, 0.ltoreq.d.ltoreq.0.04, 0.ltoreq.e.ltoreq. 0.04,0.ltoreq.f.ltoreq.0.04, more preferably, 0<a.ltoreq.0.03, 0.ltoreq.b.ltoreq.0.03, 0.ltoreq.c.ltoreq.0.03, 0.ltoreq.d.ltoreq.0.03, 0.ltoreq.e.ltoreq. 0.03,0.ltoreq.f.ltoreq.0.03. In a preferred embodiment 0<a.ltoreq.0.02, 0.ltoreq.0.02, 0.ltoreq.c.ltoreq.0.02, 0.ltoreq.d.ltoreq.0.02, 0.ltoreq.e.ltoreq. 0.02,0.ltoreq.f.ltoreq.0.02. In another preferred embodiment, at least 4 values of a to f are less than or equal to 0.02 and greater than 0. The doping element content is also one of factors influencing the performance of the doped layered oxide serving as the positive electrode material of the sodium ion battery, and the higher the doping content is, the better the doping content is, and the lower doping amount is beneficial to the improvement of the electrochemical performance of the doped layered oxide serving as the positive electrode material of the sodium ion battery.
In some embodiments, the doping element includes at least 1 to 3 metal elements selected from the fifth period, and at least 2 to 4 metal elements selected from the third period and/or the fourth period.
In some embodiments, the metal element of the fifth period is selected from zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tin (Sn), and antimony (Sb), the metal element of the third period is selected from magnesium (Mg), and aluminum (Al), and the metal element of the fourth period is selected from calcium (Ca), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), copper (Cu), and zinc (Zn).
According to the fourth aspect of the invention, the preparation method of the sodium-rich P2 phase layered oxide comprises the steps of weighing sodium salt, nickel oxide, manganese oxide and doped element oxide in corresponding molar ratios according to the stoichiometric ratio of sodium, nickel, manganese and doped elements of x to alpha to beta to z, and carrying out mixing treatment to obtain mixed powder. And (3) pressing the mixed powder after the mixing treatment to obtain a pressed block, and sintering the block.
In some embodiments, the sodium salt is at least one selected from sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium citrate, sodium nitrate, and sodium hydroxide.
In some embodiments, the above mixing treatment adopts a ball milling method for mixing, preferably, in the ball milling method for mixing, the ball mass ratio is (5-20) 1, the dispersing agent adopts one or more of ethanol, acetone, NMP, IPA or water, and the ball milling time is 3-24 hours;
In some embodiments, the pressing step more specifically includes loading the mixed powder into a mold, and pressing the mixed powder to form the mixed powder, wherein the pressing pressure is preferably 5 to 30Mpa;
In some embodiments, in the above sintering step, the sintering temperature is between 500 and 1100 ℃ and the sintering time is between 1 and 24 hours, preferably between 800 and 1000 ℃, more preferably between 850 and 950 ℃.
According to the fifth aspect of the invention, the preparation method of the sodium-rich P2 phase layered oxide comprises the steps of weighing sodium salt, nickel oxide, manganese oxide and doped element oxide with corresponding molar ratios according to the stoichiometric ratio of x to beta to z, and mixing to obtain mixed powder, wherein x is more than 1,0< alpha is less than or equal to 0.4,0< beta is less than or equal to 0.7, alpha+beta+z=1, 0< z is less than or equal to 0.2, and the doped element is at least one of iron (Fe), cobalt (Co), copper (Cu), titanium (Ti), magnesium (Mg), zinc (Zn), calcium (Ca), vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tin (Sn), antimony (Sb) and aluminum (Al).
Pressing the mixed powder after the mixing treatment to obtain a pressed block;
And sintering the block.
In some embodiments, the sodium salt is selected from at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium citrate, sodium nitrate, sodium hydroxide.
In some embodiments 1<x +.1.5; preferably, the method comprises the steps of, x is more than or equal to 1.1 and less than or equal to 1.34.
In some embodiments, 0.1. Ltoreq.α.ltoreq.0.4, 0.1. Ltoreq.β.ltoreq.0.7, preferably 0.2. Ltoreq.α.ltoreq. 0.33,0.6. Ltoreq.β.ltoreq.0.7, more preferably 0.23. Ltoreq.α.ltoreq. 0.33,0.67. Ltoreq.β.ltoreq.0.7.
In some embodiments, the sintering temperature of the sintering process is preferably between 800 ℃ and 1000 ℃, more preferably between 850 ℃ and 950 ℃.
In some embodiments, the doping element is selected from five or more of iron (Fe), cobalt (Co), copper (Cu), titanium (Ti), magnesium (Mg), zinc (Zn), calcium (Ca), vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tin (Sn), antimony (Sb), aluminum (Al).
In some embodiments, the XRD diffraction pattern of the sodium-rich P2 phase layered oxide comprises (002) (004) (100) (102) (103) (104) crystal plane diffraction peaks, and the sodium-rich P2 phase layered oxide is a single phase of the P2 phase.
The sixth aspect of the invention provides a positive electrode material of a sodium ion battery, which comprises the sodium-rich P2 phase layered oxide or the sodium-rich P2 phase layered oxide obtained by the preparation method.
The seventh aspect of the invention provides an electrode sheet comprising the sodium ion battery anode material.
An eighth aspect of the present invention provides a sodium ion battery, comprising the above-described sodium ion battery positive electrode material, or the above-described electrode sheet.
The ninth aspect of the invention provides an electric device comprising the sodium ion battery. The electric device can be an electric automobile, an electric motorcycle, an electric bicycle, an energy storage system, an electronic appliance and the like.
Compared with the prior art, the invention provides a novel sodium-supplementing technical scheme of the sodium ion battery, namely, the sodium-rich P2 phase layered oxide is adopted as a positive electrode material of the sodium ion battery, so that the irreversible sodium loss can be compensated by utilizing the redundant sodium content in the sodium-rich P2 phase layered oxide in the first charge and discharge process, and the primary sodium supplementing is realized. The technical route of the invention avoids the complicated production process of pre-sodium treatment, and the problems of increased internal resistance of the positive electrode, increased porosity of the positive electrode and side reaction caused by adding the sodium supplementing agent.
The sodium-rich P2 phase layered oxide provided by the invention is used as a sodium ion battery anode material, and the existing sodium ion battery production equipment is still adopted, so that no extra process steps are added, the sodium ion battery can be quickly imported into the sodium ion battery production process, and industrial production and application are easy to realize.
The invention also has the creativeness of overcoming the technical prejudice that the theoretical limit of x=0.83 (or 5/6) is difficult to break through by theoretical calculation of Na xAyO2 or Na xAyMzO2 in the field and the layered oxide of the P2 phase, successfully preparing the layered oxide of the P2 phase rich in sodium (1<x is less than or equal to 1.5) by a high-temperature solid-phase sintering method, breaking through the theoretical limit of sodium content in the layered oxide of the P2 phase and obtaining the layered oxide of the P2 phase rich in sodium, which is not reported yet, belongs to a novel compound.
The invention also solves the technical problems that the P2 phase layered oxide belongs to a sodium-deficient positive electrode material in the prior art, the sodium content is low, serious irreversible loss of sodium ions exists when the layered oxide is applied to a battery, the first coulombic efficiency is low, and the energy density of the whole battery is low, and provides the non-reported sodium-rich P2 phase layered oxide (Na xAyO2 or Na xAyMzO2, x > 1).
Drawings
FIG. 1 is an XRD spectrum of Na 1.33Ni0.33Mn0.67O2, a layered oxide of the sodium-rich P2 phase in example 2 of the present invention.
FIG. 2 is an SEM photograph of a Na 1.33Ni0.33Mn0.67O2 -rich P2-phase layered oxide according to example 2 of the present invention.
FIG. 3 is an XRD spectrum of Na 1.33Ni0.26Mn0.67(Zn0.03Al0.02Fe0.02)O2 of the sodium-rich P2 phase layered oxide of example 3 of the present invention.
Fig. 4 is an XRD spectrum of the sodium-rich P2 phase layered oxide Na1.33Ni0.26Mn0.67(Zn0.02Nb0.01Al0.01Fe0.01Cu0.02)O2 in example 4 of the present invention.
Fig. 5 is an SEM photograph of the P2-phase high-entropy doped sodium-rich P2-phase layered oxide Na1.33Ni0.26Mn0.67(Zn0.02Nb0.01Al0.01Fe0.01Cu0.02)O2 and distribution diagrams of each element Na, ni, mn, zn, nb, al, fe and Cu therein in example 4 of the present invention.
Fig. 6 is a first-turn charge-discharge curve at a rate of 0.1C of the sodium-rich P2 phase layered oxide Na 1.33Ni0.33Mn0.67O2 as a positive electrode material of a sodium-ion battery in example 5 of the present invention.
FIG. 7 is a sodium-rich P2 phase layered oxide according to example 5 of the present invention
Na 1.33Ni0.26Mn0.67(Zn0.03Al0.02Fe0.02)O2 as positive electrode material of sodium ion battery at a rate of 0.1C.
FIG. 8 is a sodium-rich P2 phase layered oxide according to example 5 of the present invention
Na1.33Ni0.26Mn0.67(Zn0.02Nb0.01Al0.01Fe0.01Cu0.02)O2 First-turn charge-discharge curve at 0.1C as a positive electrode material of sodium ion battery.
Fig. 9 is a cycle performance test result of the sodium-rich P2 phase layered oxide of example 5 of the present invention as a positive electrode material of a sodium ion battery at a rate of 1C.
Fig. 10 is a graph showing the results of the rate performance test of the sodium-rich P2 phase layered oxide as a positive electrode material for sodium ion batteries in example 5 of the present invention.
Fig. 11 is a first-turn charge curve of the Na 0.6Ni0.33Mn0.67O2 positive electrode material in comparative example 1 of the present invention.
Fig. 12 is a comparison of the cycling performance of Na 0.6Ni0.33Mn0.67O2 and Na-rich Na 1.33Ni0.33Mn0.67O2 cathode materials in comparative example 1 of the present invention.
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
The preparation method of the positive plate of the sodium ion battery comprises the steps of 1) mixing and grinding a positive plate material of the sodium ion battery (sodium-rich P2-phase layered oxide in the invention), a conductive agent (Super P) and a binder (PVDF) according to a mass ratio of 7:2:1 for 10min, adding a proper amount of N-methylpyrrolidone (NMP) and grinding for 20min, preparing mixed slurry, and 2) coating the obtained mixed slurry on an aluminum foil wafer with a diameter of 12mm, wherein the loading amount is 1.5mg/cm 2, and drying the coated electrode plate in a vacuum oven at 80 ℃ for 12h.
The same method is adopted, and the sodium-rich P2 phase layered oxide is replaced by the P2 phase layered oxide (specific types are provided in specific examples), so that the positive plate of the comparison sample is obtained.
The assembling method of the sodium ion battery comprises the steps of taking a metal sodium sheet as a negative electrode, taking the positive electrode sheet obtained by the preparation as a positive electrode, preparing a CR2032 button battery in an argon glove box, wherein a glass fiber diaphragm is adopted as the diaphragm, naClO 4 solution with the concentration of 1M is adopted as the electrolyte, and the solvent is Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with the volume ratio of 1:1, and contains fluoroethylene carbonate (FEC) with the volume ratio of 2%.
The charge and discharge performance test of the sodium ion battery is carried out on a Land BT2000 battery test system, the test temperature is room temperature, the test voltage range is 2.0-4.3V, and the multiplying power range is 0.1-5C.
Example 1
The embodiment provides a sodium-rich P2 phase layered oxide and a preparation method thereof, namely a sodium ion battery anode material and a preparation method thereof, wherein the sodium-rich P2 phase layered oxide is represented by a chemical formula as Na xAyO2, wherein A is two elements of Mn and Ni, y=1, and the chemical formula can also be represented by Na xNiαMnβO2, x >1,0.8 is less than or equal to y <1, y=alpha+beta, 0<z is less than or equal to 0.2, and y+z=1.
The structure of the P2 phase can be determined by X-ray diffraction (XRD) test of the characteristic peaks corresponding to crystal planes in the spectrogram, and the XRD diffraction pattern of the layered oxide of the P2 phase comprises (002) (004) (100) (102) (103) (104) characteristic peaks of crystal planes.
The preparation method of the sodium-rich P2 phase layered oxide comprises the following steps:
S01, weighing sodium salt, nickel oxide and manganese oxide with corresponding molar ratios according to the molar ratio of the sodium element, the nickel element and the manganese element being x to alpha to beta, and carrying out mixing treatment to obtain mixed powder, wherein x is more than 1,0< alpha is less than or equal to 0.4,0< beta is less than or equal to 0.7, and alpha+beta=1;
S02, pressing the mixed powder after the mixing treatment to obtain a pressed block;
And S03, sintering the block.
In one embodiment of the present invention, in one embodiment, 1<x is less than or equal to 1.5; more preferably, 1.1.ltoreq.x.ltoreq.1.34 or 1.1.ltoreq.x.ltoreq.4/3.
In one embodiment of the present invention, in one embodiment, alpha is more than or equal to 0.1 and less than or equal to 0.4,0.1 beta is more than or equal to 0.7; preferably, alpha is more than or equal to 0.2 and less than or equal to 0.33,0.6 and beta is more preferably, alpha is more preferably more than or equal to 0.23 and less than or equal to 0.33,0.67 and beta is more preferably less than or equal to 0.7.
The present embodiment also provides a sodium-rich P2 phase layered oxide doped with a metal element, the chemical formula of which is represented as Na xAyMzO2, wherein Na represents a sodium element, a is selected from nickel (Ni) and manganese (Mn) elements, M represents a doping element, the M is selected from at least one metal element other than sodium, nickel and manganese in the third to fifth periods of the periodic table, the M is selected from iron (Fe), cobalt (Co), copper (Cu), titanium (Ti), magnesium (Mg), zinc (Zn), calcium (Ca), vanadium (V), chromium (Cr), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tin (Sn), antimony (Sb), aluminum (Al) elements, and the sodium-rich P2 phase layered oxide doped with a metal element may be represented as Na xNiαMnβMzO2, x1, y=α+β,0< α.4,0< β+0.7, α+z=0.0.2.
In one embodiment 1<x.ltoreq.1.5, preferably, x is more than or equal to 1.1 and less than or equal to 1.34 or x is 1.1.ltoreq.x or 1.1 x is less than or equal to.
In one embodiment of the present invention, in one embodiment, alpha is more than or equal to 0.1 and less than or equal to 0.4,0.1 beta is more than or equal to 0.7; preferably, alpha is more than or equal to 0.2 and less than or equal to 0.33,0.6 and beta is more preferably, alpha is more preferably more than or equal to 0.23 and less than or equal to 0.33,0.67 and beta is more preferably less than or equal to 0.7.
The embodiment also provides a preferable P2-phase sodium-rich layered oxide with high entropy doping, wherein the doping element (M) includes five or more metal elements.
More preferably, the doping element (M) in the high-entropy doped sodium-rich P2-phase layered oxide comprises at least 1 to 3 metal elements selected from a fifth period and at least 2 to 4 metal elements selected from a third period and/or a fourth period, the high-entropy doped P2-phase layered oxide in an entropy stable state is obtained through the staggered matching of the sizes of metal atoms in different periods, namely the structural stability of the high-entropy doped P2-phase layered oxide can be improved through the staggered matching of the metal atoms in different periods, and in a preferred embodiment, the metal elements in the fifth period are selected from zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tin (Sn) and antimony (Sb), the metal elements in the third period are selected from magnesium (Mg) and aluminum (Al), and the metal elements in the fourth period are selected from calcium (Ca), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), cobalt (Co), copper (Cu) and zinc (Zn);
in a specific embodiment, the doping element (M) comprises at least two of titanium (Ti), vanadium (V), chromium (Cr), copper (Cu), zinc (Zn), magnesium (Mg), and/or at least one of tin (Sn), antimony (Sb), niobium (Nb), molybdenum (Mo), zirconium (Zr).
The preparation method of the sodium-rich P2 phase layered oxide doped with metal elements or the high-entropy doped sodium-rich P2 phase layered oxide comprises the following steps:
S11, weighing sodium salt, nickel oxide, manganese oxide and doped element oxide with corresponding molar ratios according to the stoichiometric ratio of x to alpha to beta to z, and mixing to obtain mixed powder, wherein x is more than 1,0< alpha is less than or equal to 0.4,0< beta is less than or equal to 0.7, alpha+beta+z=1, and 0< z is less than or equal to 0.2.
S12, pressing the mixed powder after the mixing treatment to obtain a pressed block;
And S13, sintering the block.
In one embodiment 1<x.ltoreq.1.5, preferably, x is more than or equal to 1.1 and less than or equal to 1.34 or x is 1.1.ltoreq.x or 1.1 x is less than or equal to.
In one embodiment of the present invention, in one embodiment, alpha is more than or equal to 0.1 and less than or equal to 0.4,0.1 beta is more than or equal to 0.7; preferably, alpha is more than or equal to 0.2 and less than or equal to 0.33,0.6 and beta is more preferably, alpha is more preferably more than or equal to 0.23 and less than or equal to 0.33,0.67 and beta is more preferably less than or equal to 0.7.
In the step S10 or S11, the sodium source in the raw material is selected from one or more of sodium carbonate (Na 2CO3), sodium bicarbonate (NaHCO 3), sodium acetate (CH 3 COONa), sodium oxalate (Na 2C2O4), sodium citrate (C 6H5Na3O7), sodium nitrate (NaNO 3) and sodium hydroxide (NaOH), the raw material nickel oxide comprises NiO and Ni 2O3, and the manganese oxide comprises MnO, mnO 2、Mn2O3、Mn3O4、Mn2O5 and the like.
The purpose of the mixing treatment in steps S01 and S11 is to mix the raw materials sufficiently and uniformly, and methods that can achieve the purpose of uniform mixing by using different mechanical devices, such as mechanical stirring and dispersing, may be used. In a specific embodiment, the mixing treatment is performed by ball milling, more specifically, wet ball milling is preferred, and solvents that may be added during wet ball milling include, but are not limited to, ethanol, water, N-methylpyrrolidone (NMP), isopropyl alcohol (IPA), etc. the liquids may be used without ball milling, and may also be changed according to different conditions. The wet ball milling time is selected from 3 to 24 hours, the ball milling speed is 300 to 600r/min, more preferably, the ball milling time is 5 to 20 hours, and the rotating speed is about 300 to 400r/min.
In the pressing treatment in steps S02, S12, a cold pressing treatment is preferably employed, and the pressurizing pressure is 5 to 30Mpa, preferably 5 to 10Mpa.
The sintering treatment in the steps S03 and S13 is carried out, the sintering temperature is 500-1100 ℃, the heating rate is 3-20 ℃ per minute, and the sintering time is 1-24 hours. Preferably between 800 and 1000 ℃, more preferably between 850 and 950 ℃.
Example 2
The present embodiment provides a specific sodium-rich P2 phase layered oxide Na 1.33Ni0.33Mn0.67O2 (also denoted as Na 4/3Ni1/3Mn2/3O2) and its preparation method comprising the steps of:
(1) According to the molar ratio of the sodium, nickel and manganese elements being x to alpha to beta, wherein x=1.33, alpha=0.33 and beta=0.67, weighing Na 2CO3, nickel oxide and manganese oxide with corresponding molar ratios, mixing to obtain mixed powder, specifically, respectively weighing Na 2CO3, niO and MnO 2 powder according to the molar ratio of 0.665 to 0.33 to 0.67 in experiments, placing the powder in an agate tank, adding agate balls according to the mass ratio of 10 to 1 of the balls, adding a proper amount of ethanol as a grinding aid, and finally ball milling the ball milling tank on a ball mill for 4 hours. And after ball milling is finished, the ball milling tank is placed into a 80 ℃ blast oven to be dried for 10 hours, and mixed powder is obtained.
(2) And (3) pressing the mixed powder after the mixing treatment to obtain a pressed block, specifically, loading the dried mixed powder into a die, and tabletting under the pressure of 10MPa to obtain a round block with the diameter of 14 mm.
(3) And sintering the block, namely placing the pressed round block into an alumina crucible, placing the crucible into a muffle furnace, sintering for 12 hours in an air atmosphere at 910 ℃, cooling along with the furnace, grinding and sieving the sintered block to obtain a target product.
When the obtained target product is subjected to X-ray diffraction (XRD), as shown in fig. 1, characteristic peaks (or diffraction peaks) of the P2 phase of the target product appear at 15.8 degrees, 32.1 degrees, 35.8 degrees, 39.3 degrees, 43.4 degrees and 48.8 degrees, the characteristic peaks correspond to crystal planes (002) (004) (100) (102) (103) (104), which indicate that the target product only comprises the characteristic peaks of the P2 phase, and the target product Na 1.33Ni0.33Mn0.67O2 is in a P2 phase structure, wherein the (002) corresponds to the P2 phase Jiang Yanshe peak, the (004) (100) (102) (103) (104) is a weak diffraction peak, and the pure-phase sodium-rich P2 phase layered oxide Na 1.33Ni0.33Mn0.67O2 is proved to be successfully synthesized.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the target product, and it can be seen that the target product sodium-rich P2 phase layered oxide is microscopically granular, and the particle size ranges from 1 to 10 μm.
Example 3
The embodiment provides a Na-rich P2 phase layered oxide Na 1.33Ni0.26Mn0.67(Zn0.03Al0.02Fe0.02)O2 (the chemical formula can also be expressed as Na 4/3Ni0.26Mn2/3(Zn0.03Al0.02Fe0.02)O2) containing element doping, wherein Zn, al and Fe are doping elements, and the preparation method comprises the following steps:
(1) Powder of Na 2CO3、NiO、MnO2、ZnO、Al2O3、Fe2O3 with the corresponding molar ratio of 0.665:0.26:0.67:0.03:0.01:0.01 is weighed according to the stoichiometric ratio of Na, ni, mn, zn, al, fe elements of 1.33:0.26:0.67:0.03:0.02:0.02, placed in an agate tank, agate balls are added according to the ball mass ratio of 10:1, then a proper amount of ethanol is added as a grinding aid, and finally the ball milling tank is placed on a ball mill for ball milling for 4 hours. And after ball milling is finished, the ball milling tank is placed into a 80 ℃ blast oven to be dried for 10 hours, and mixed powder is obtained.
(2) And (3) pressing the mixed powder after the mixing treatment to obtain a pressed block, specifically, loading the dried mixed powder into a die, and tabletting under the pressure of 10MPa to obtain a round block with the diameter of 14 mm.
(3) And sintering the block, namely placing the pressed round block into an alumina crucible, placing the crucible into a muffle furnace, sintering for 12 hours in an air atmosphere at 930 ℃, cooling along with the furnace, grinding and sieving the sintered block to obtain a target product.
The obtained target product is tested by X-ray diffraction (XRD), and as shown in figure 3, the characteristic diffraction peak of the P2 phase appears on the crystal faces of (002) (004) (100) (102) (103) (104), and the pure-phase sodium-rich P2 phase layered oxide Na 1.33Ni0.26Mn0.67(Zn0.03Al0.02Fe0.02)O2 is proved to be successfully synthesized.
Example 4
The embodiment provides a preparation method of a high-entropy doped sodium-rich P2 phase layered oxide Na1.33Ni0.26Mn0.67(Zn0.02Nb0.01Al0.01Fe0.01Cu0.02)O2,, which comprises the following steps:
(1) Na2CO3、NiO、MnO2、ZnO、Nb2O5、Al2O3、Fe2O3、CuO powder with the corresponding molar ratio of 0.665:0.26:0.67:0.005:0.005:0.02 is weighed according to the stoichiometric ratio of Na, ni, mn, zn, nb, al, fe, cu elements of 1.33:0.26:0.67:0.02:0.01:0.01:0.02, placed in an agate tank, agate balls are added according to the ball mass ratio of 10:1, then a proper amount of ethanol is added as a grinding aid, and finally the ball milling tank is placed on a ball mill for ball milling for 4 hours. And after ball milling is finished, the ball milling tank is placed into a 80 ℃ blast oven to be dried for 10 hours, and mixed powder is obtained.
(2) And (3) pressing the mixed powder after the mixing treatment to obtain a pressed block, specifically, loading the dried mixed powder into a die, and tabletting under the pressure of 10MPa to obtain a round block with the diameter of 14 mm.
(3) And sintering the block, namely placing the pressed round block into an alumina crucible, placing the crucible into a muffle furnace, sintering for 12 hours in an air atmosphere at 910 ℃, cooling along with the furnace, grinding and sieving the sintered block to obtain a target product.
The obtained target product and the comparative sample were subjected to X-ray diffraction (XRD) test, and as shown in fig. 4, it can be seen that characteristic peaks of P2 phases of the target product appear at 15.8 °, 32 °, 35.7 °, 39.3 °, 43.5 °, 48.7 °, which correspond to (002) (004) (100) (102) (103) (104) crystal planes, respectively, which indicate that the target product only includes the characteristic peaks of P2 phases, and the target product Na1.33Ni0.26Mn0.67(Zn0.02Nb0.01Al0.01Fe0.01Cu0.02)O2 has a P2 phase structure, wherein (002) corresponds to the P2 phase Jiang Yanshe peak, and (004) (100) (102) (103) (104) is a weak diffraction peak, which proves that pure-phase sodium-rich P2 phase layered oxide Na1.33Ni0.26Mn0.67(Zn0.02Nb0.01Al0.01Fe0.01Cu0.02)O2 is successfully synthesized. It can be seen from fig. 5 that the prepared sample morphology is a layered block, na, ni, mn, zn, nb, al, fe and Cu elements are uniformly distributed.
Example 5
The embodiment provides an application of a sodium-rich P2 phase layered oxide as a positive electrode material of a sodium ion battery, namely, a positive electrode material of a sodium ion battery, a positive electrode plate and a sodium ion battery.
In this example, the sodium-rich P2-phase layered oxides obtained in examples 2 to 4 above were used as positive electrode materials for sodium ion batteries, respectively, to prepare positive electrode sheets, and button sodium ion batteries were assembled to test their electrochemical properties, and the results are shown in fig. 6 to 10.
Wherein, fig. 6 to 8 show the first charge-discharge curves of the sodium-rich P2 phase layered oxides Na1.33Ni0.33Mn0.67O2、Na1.33Ni0.26Mn0.67(Zn0.03Al0.02Fe0.02)O2 and Na1.33Ni0.26Mn0.67(Zn0.02Nb0.01Al0.01Fe0.01Cu0.02)O2 as the positive electrode materials of the sodium ion batteries in examples 2 to 4 at a rate of 0.1C, and it can be seen that their first charge specific capacities are respectively 310mah·g -1、291mAh·g-1、284mAh·g-1 and the discharge specific capacities are respectively 148mah·g -1、128mAh·g-1、125mAh·g-1, which indicates that the sodium ions from the positive electrode to the negative electrode are far more than the sodium ions from the negative electrode to the positive electrode during charging, and the excessive sodium ions can be used for one-time sodium supplementation of the negative electrode materials.
Fig. 9 also shows a comparison of the cycle performance test of the three sodium-rich P2-phase layered oxides as a positive electrode material of a sodium ion battery under the 1C multiplying power, and it can be seen that after 100 cycles, the discharge specific capacities of the three sodium-rich P2-phase layered oxides are 72.6mah·g -1、81.9mAh·g-1、91.1mAh·g-1 respectively, wherein the high-entropy doped sodium-rich P2-phase layered oxides maintain the highest discharge specific capacity, and in particular, the high-entropy doped sodium-rich P2-phase layered oxides also show the best cycle stability, and the capacity is hardly attenuated after 100 cycles.
By comparing the test results (fig. 10) under different multiplying powers (0.1C-5C), it can be further seen that the high entropy doped sodium-rich P2 layered oxide of the present invention can be used as a positive electrode material of a sodium ion battery, the initial capacity of the positive electrode material can reach 125mAhg -1 under the charge-discharge multiplying power of 0.1C, the capacity of the positive electrode material under 0.2C is about 114mAhg -1, when the charge-discharge multiplying power is increased to 5C, the positive electrode material still remains less than 60mAhg -1, and particularly, when the charge-discharge multiplying power is restored to 0.5C, the high entropy doped layered oxide of the present invention can completely restore to the capacity of 110mAhg -1 under 0.5C, and the capacity of the positive electrode material of Na 1.33Ni0.33Mn0.67O2 positive electrode material is only 100mAhg -1,Na1.33Ni0.26Mn0.67(Zn0.03Al0.02Fe0.02)O2, which is less than 90mAhg -1. The capacity can be restored, and the repeated intercalation and deintercalation of sodium ions does not destroy the structure of the high-entropy doped layered oxide, namely, the high-entropy doping can produce the beneficial technical effect of improving the structural stability of the layered oxide material.
The high-entropy doped layered oxide provided by the invention has excellent multiplying power performance as a positive electrode material of a sodium ion battery, and is also related to the fact that the conductivity of the material can be improved by introducing high-entropy doping into the layered oxide, and the introduced multi-element generates chemical disorder and distortion to locally disturb site energy, so that the distribution of site energy is generated. When this distribution is wide enough that the energies of adjacent sites overlap, ion hopping between them will be facilitated. If such a network of sites with similar energy is permeated, macroscopic ion diffusion will be enhanced by disorder. An increase in conductivity is exhibited in terms of material properties. This can be calculated by the first sexual principle and experiments prove that introducing chemical disorder into the inorganic solid electrolyte by high entropy doping can increase the ionic conductivity by several orders of magnitude, thereby reducing the overall cell resistance to improve performance.
As the positive electrode material of the sodium ion battery, a sodium-rich P2 phase layered oxide with x being more than or equal to 1.1 is preferable to provide sufficient sodium ions to realize the effect of sodium supplementation, more preferably with x being more than or equal to 1.1 and less than or equal to 1.5, still more preferably with x being more than or equal to 1.1 and less than or equal to 1.34, and still more preferably, a sodium-rich P2 phase layered oxide with high entropy doping is selected.
Example 6
By changing the ratio of Na 2CO3、NiO、MnO2 in the raw materials and the oxide powder doped with the elements, the applicant also sinters and synthesizes other sodium-rich P2 phase layered oxides with element doping by using a preparation method similar to that of example 3, as shown in the following table:
Example 7
By changing the ratio of Na 2CO3、NiO、MnO2 in the raw materials and the oxide powder of the doping element, the applicant also sinters and synthesizes other high entropy doped sodium-rich P2 phase layered oxides by using a preparation method similar to that of example 4, as shown in the following table:
Comparative example 1
The comparative example provides an electrochemical performance test of the existing P2 phase layered oxide Na 0.6Ni0.33Mn0.67O2 serving as a positive electrode material of a sodium ion battery, and the P2 phase layered oxide Na 0.6Ni0.33Mn0.67O2 is also prepared by adopting a high-temperature solid-phase synthesis method.
Fig. 11 shows a first-turn charge-discharge curve of Na 0.6Ni0.33Mn0.67O2 positive electrode material, and it can be seen that the first-turn charge specific capacity is 186mah·g -1, the discharge specific capacities are 144mah·g -1, respectively, and the first-turn charge specific capacity is significantly lower than that of sodium-rich Na 1.33Ni0.33Mn0.67O2 positive electrode material (310 mah·g -1), which indicates that the sodium-rich P2-phase layered oxide of the present invention can provide excessive sodium ions in the first charge process. Fig. 12 shows a comparison of the cycling performance of Na 0.6Ni0.33Mn0.67O2 and Na 1.33Ni0.33Mn0.67O2 -rich positive electrode materials, and shows that the cycling stability of Na 1.33Ni0.33Mn0.67O2 -rich positive electrode materials is superior to Na 0.6Ni0.33Mn0.67O2, which is attributable to the fact that Na 1.33Ni0.33Mn0.67O2 -rich positive electrode materials can provide redundant sodium ions, and the sodium ion loss during the charge and discharge process is equivalent to having a sodium supplementing effect, thereby realizing the improvement of the cycling performance of the battery.
Comparative example 2
To illustrate the effect of sintering temperature on the product in the high temperature solid phase sintering process, this comparative example provides products at different sintering temperatures, similar to example 2, except that the sintering temperature was changed during the preparation process, and the phase of the resulting product was analyzed, with the results shown in the following table:
reaction conditions Chemical formula Phase analysis
880°C,12h Na1.33Ni0.33Mn0.67O2 P2/O'3 phase
930°C,12h Na1.33Ni0.33Mn0.67O2 P2/O3 diphase
950°C,12h Na1.33Ni0.33Mn0.67O2 O3 phase
The invention discovers that the phase state of the sodium-rich layered oxide is related to temperature, and as the temperature increases, the phase state is firstly P2/O'3 phase, then P2 phase, P2/O3 double phase and finally O3 phase. It can be seen that there is a suitable sintering temperature interval T (T 1 to T 2) for the preparation of the sodium-rich P2 phase layered oxide, and that P2/O'3 phases are formed when the sintering temperature is lower than the sintering temperature interval temperature T 1, and that P2/O3 phases are gradually converted from pure P2 phase to P2/O3 bi-phase and then to O3 phase when the sintering temperature is higher than the sintering temperature interval temperature T 2. In this embodiment, the sintering temperature interval T is between 880 ℃ and 930 ℃ (880 ℃ < T <930 ℃). It can be seen that the pure phase sodium-rich P2 phase layered oxide appears in a narrower temperature range.
Comparative example 3
Similar to example 3, except that the sintering temperature was changed during the preparation, the phase of the obtained product was analyzed, and the results are shown in the following table:
Similar to comparative example 2, there is also an adapted sintering temperature interval T (T 1 to T 2) and similar law for the pure sodium-rich P2 phase layered oxide with doping elements present, when the sintering temperature is lower than T 2, a P2/O'3 phase is formed, and when the sintering temperature is increased, a pure P2 phase gradually forms a P2/O3 biphasic transition into an O3 phase. In this embodiment, the sintering temperature interval T is between 900 ℃ and 950 ℃,900 ℃ < T <950 ℃.
Comparative example 4
Similar to example 4, except that the sintering temperature was changed during the preparation, the phase of the obtained product was analyzed, and the results are shown in the following table:
Similar to comparative example 2, there is also an adapted sintering temperature interval T (T 1 to T 2) and similar law for pure P2 phase sodium-rich layered oxides with high entropy doping, when the sintering temperature is lower than T 2, a P2/O'3 phase is formed, and when the sintering temperature is increased, a pure P2 phase gradually forms a P2/O3 biphasic transition to an O3 phase. In this embodiment, the sintering temperature interval T is between 880 ℃ and 930 ℃,880 ℃ < T <930 ℃.
It can be seen that the sintering temperature in the high temperature solid phase sintering process has an influence on the synthesis of the sodium-rich P2 phase layered oxide, and the preferred sintering temperature of the sodium-rich P2 phase layered oxide of the present invention is in the range of 880 ℃ to 950 ℃. It should be noted that, as a result of the synthesis of a new compound, which is generally a multi-factor result, the preferred synthesis conditions for the compounds with different elemental compositions may vary, and in other embodiments, the preferred sintering temperature of the sodium-rich P2 phase layered oxide of the present invention is in the range of 800 ℃ to 1000 ℃, more preferably 850 ℃ to 950 ℃, and other sintering conditions can be obtained by adjusting the elemental composition and sintering time and other factors through limited experimental optimization while remaining within the scope of the present invention.
It should be noted that, in light of the present disclosure, those skilled in the art can reasonably predict that the sodium-rich P2 phase layered oxide with x >1 can be synthesized, and that by changing experimental conditions (such as pressure sintering), the sodium-rich P2 phase layered oxide Na xAyO2 or Na xAyMzO2 with x having different values (such as x=1.01, 1.05, 1.4, 1.5 or 2) is obtained, and all the obtained sodium-rich P2 phase layered oxides with x >1 are within the technical concept of the present disclosure.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (34)

1.一种富钠P2相层状氧化物，其特征在于，所述富钠P2相层状氧化物的化学式表示为NaxNiαMnβO2，y=α+β，其中，Na代表钠元素，x＞1，y=1；所述富钠P2相层状氧化物的XRD衍射图谱包括（002）（004）（100）（102）（103）（104）晶面衍射峰。1. A sodium-rich P2 phase layered oxide, characterized in that the chemical formula of the sodium-rich P2 phase layered oxide is Na x Ni α Mn β O 2 , y = α + β , wherein Na represents the sodium element, x > 1, y = 1; the XRD diffraction pattern of the sodium-rich P2 phase layered oxide includes (002) (004) (100) (102) (103) (104) crystal plane diffraction peaks. 2.如权利要求1所述的富钠P2相层状氧化物，其特征在于，所述富钠P2相层状氧化物的化学式中0＜α≤0.4，0＜β≤0.7；2. The sodium-rich P2 phase layered oxide according to claim 1, characterized in that in the chemical formula of the sodium-rich P2 phase layered oxide, 0＜ α≤0.4 , 0＜ β≤0.7 ; 和/或，1＜x≤1.5。And/or, 1＜ x ≤1.5. 3.如权利要求2所述的富钠P2相层状氧化物，其特征在于，1.1≤x≤1.34；3. The sodium-rich P2 phase layered oxide according to claim 2, characterized in that 1.1≤ x ≤1.34; 和/或，0.1≤α≤0.4，0.1≤β≤0.7。And/or, 0.1≤ α ≤0.4, 0.1≤ β ≤0.7. 4.如权利要求3所述的富钠P2相层状氧化物，其特征在于，0.2≤α≤0.33，0.6≤β≤0.7。4. The sodium-rich P2 phase layered oxide according to claim 3, characterized in that 0.2≤ α ≤0.33, 0.6≤ β ≤0.7. 5.如权利要求3所述的富钠P2相层状氧化物，其特征在于，0.23≤α≤0.33，0.67≤β≤0.7。5. The sodium-rich P2 phase layered oxide according to claim 3, characterized in that 0.23≤ α ≤0.33, 0.67≤ β ≤0.7. 6.一种如权利要求1至5中任一项所述的富钠P2相层状氧化物的制备方法，其特征在于，步骤包括：6. A method for preparing a sodium-rich P2 phase layered oxide according to any one of claims 1 to 5, characterized in that the steps include: 按照钠、镍、锰元素的化学计量比为x: α: β，称取相应摩尔比的钠盐、镍氧化物和锰氧化物，并进行混合处理，得到混合粉末；According to the stoichiometric ratio of sodium, nickel and manganese elements being x : α : β , sodium salt, nickel oxide and manganese oxide in corresponding molar ratios are weighed and mixed to obtain a mixed powder; 将混合处理后的所述混合粉末压制处理，得到压制成型的块状物；Pressing the mixed powder after mixing to obtain a pressed block; 将所述块状物烧结处理。The block is sintered. 7.如权利要求6所述的富钠P2相层状氧化物的制备方法，其特征在于，所述钠盐选自碳酸钠、碳酸氢钠、醋酸钠、草酸钠、柠檬酸钠、硝酸钠中的至少一种。7. The method for preparing a sodium-rich P2 phase layered oxide according to claim 6, wherein the sodium salt is selected from at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium citrate, and sodium nitrate. 8.如权利要求6或7中所述的富钠P2相层状氧化物的制备方法，其特征在于，所述混合处理采用球磨法混合；8. The method for preparing the sodium-rich P2 phase layered oxide according to claim 6 or 7, characterized in that the mixing treatment is carried out by ball milling; 和/或，所述压制步骤中，步骤具体的包括，将所述混合粉末装入模具中，加压压制成型；And/or, in the pressing step, the steps specifically include: loading the mixed powder into a mold and pressing and molding it; 和/或，所述烧结步骤中，烧结温度介于500至1100℃。And/or, in the sintering step, the sintering temperature is between 500 and 1100°C. 9.如权利要求8所述的制备方法，其特征在于，所述球磨法混合中，球料质量比为(5~20)：1，分散剂采用乙醇、丙酮、N-甲基吡咯烷酮、异丙醇或水中的一种或多种，球磨时间为3至24h；9. The preparation method according to claim 8, characterized in that, in the ball milling mixing, the ball-to-material mass ratio is (5-20):1, the dispersant is one or more of ethanol, acetone, N-methylpyrrolidone, isopropanol or water, and the ball milling time is 3 to 24 hours; 和/或，所述加压的压力为5至30MPa；And/or, the pressurized pressure is 5 to 30 MPa; 和/或，所述烧结温度介于800℃至1000℃。And/or, the sintering temperature is between 800°C and 1000°C. 10.如权利要求9所述的制备方法，其特征在于，所述烧结温度介于850℃至950℃。10 . The preparation method according to claim 9 , wherein the sintering temperature is between 850° C. and 950° C. 11.如权利要求9所述的制备方法，其特征在于，所述烧结温度介于880℃至930℃。11. The preparation method according to claim 9, characterized in that the sintering temperature is between 880°C and 930°C. 12.一种富钠P2相层状氧化物，其特征在于，所述富钠P2相层状氧化物的化学式表示为NaxNiαMnβMzO2，y=α+β，其中，Na代表钠元素，M代表掺杂元素，所述M选自元素周期表第三周期至第五周期中的至少一种不同于钠、镍和锰的金属元素，x＞1，0.8≤y＜1，0＜z≤0.2，y+z=1；所述富钠P2相层状氧化物的XRD衍射图谱包括（002）（004）（100）（102）（103）（104）晶面衍射峰。12. A sodium-rich P2 phase layered oxide, characterized in that the chemical formula of the sodium-rich P2 phase layered oxide is Na x Ni α Mn β M z O 2 , y = α + β , wherein Na represents the sodium element, M represents the doping element, and the M is selected from at least one metal element other than sodium, nickel and manganese in the third to fifth periods of the periodic table, x > 1, 0.8≤ y＜ 1, 0 ＜z ≤0.2, y + z = 1; the XRD diffraction pattern of the sodium-rich P2 phase layered oxide includes (002) (004) (100) (102) (103) (104) crystal plane diffraction peaks. 13.如权利要求12所述的富钠P2相层状氧化物，其特征在于，所述掺杂元素选自铁、钴、铜、钛、镁、锌、钙、钒、铬、锆、铌、钼、钌、锡、锑、铝元素。13. The sodium-rich P2 phase layered oxide according to claim 12, characterized in that the doping element is selected from iron, cobalt, copper, titanium, magnesium, zinc, calcium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, tin, antimony, and aluminum. 14.如权利要求12所述的富钠P2相层状氧化物，其特征在于，所述富钠P2相层状氧化物的化学式中，0＜α≤0.4，0＜β≤0.7；14. The sodium-rich P2 phase layered oxide according to claim 12, characterized in that in the chemical formula of the sodium-rich P2 phase layered oxide, 0＜ α≤0.4 , 0＜ β≤0.7 ; 和/或，1＜x≤1.5。And/or, 1＜ x ≤1.5. 15.如权利要求14所述的富钠P2相层状氧化物，其特征在于，0.1≤α≤0.4，0.1≤β≤0.7；15. The sodium-rich P2-phase layered oxide according to claim 14, characterized in that 0.1≤ α ≤0.4, 0.1≤ β ≤0.7; 和/或，1.1≤x≤1.34。And/or, 1.1≤ x ≤1.34. 16.如权利要求14所述的富钠P2相层状氧化物，其特征在于，0.2≤α≤0.33，0.6≤β≤0.7。16. The sodium-rich P2 phase layered oxide according to claim 14, characterized in that 0.2≤ α ≤0.33, 0.6≤ β ≤0.7. 17.如权利要求14所述的富钠P2相层状氧化物，其特征在于，0.23≤α≤0.33，0.67≤β≤0.7。17. The sodium-rich P2-phase layered oxide according to claim 14, characterized in that 0.23≤ α ≤0.33, 0.67≤ β ≤0.7. 18.如权利要求12至17中任一项所述的富钠P2相层状氧化物，其特征在于，所述M选自元素周期表第三周期至第五周期中的五种以上不同于钠、镍和锰的金属元素。18. The sodium-rich P2 phase layered oxide according to any one of claims 12 to 17, characterized in that the M is selected from five or more metal elements other than sodium, nickel and manganese in the third to fifth periods of the periodic table. 19.如权利要求18所述的富钠P2相层状氧化物，其特征在于，所述富钠P2相层状氧化物的化学式表示Nax(NiαMnβ)(M1aM2bM3cM4dM5eM6f) O2，y=α+β，z=a+b+c+d+e+f，0.1≤α≤0.4，0.1≤β≤0.7，0＜a≤0.05，0＜b≤0.05，0＜c≤0.05，0＜d≤0.05，0＜e≤0.05，0≤f≤0.05。19. The sodium-rich P2 phase layered oxide according to claim 18, characterized in that the chemical formula of the sodium-rich P2 phase layered oxide is represented by Nax ( NiαMnβ )(M1aM2bM3cM4dM5eM6f) O2 , y = α + β , z = a + b + c + d + e + f , 0.1≤α≤0.4, 0.1≤β≤0.7, 0 ＜ a≤0.05 , 0 ＜ b≤0.05 , 0 ＜ c≤0.05 , 0＜d≤0.05, 0 ＜ e≤0.05 , 0≤f≤0.05 . 20.如权利要求12至17、19中任一项所述的富钠P2相层状氧化物，其特征在于，所述掺杂元素中包括至少1至3种选自第五周期的金属元素；和，至少2至4种选自第三周期和/或第四周期的金属元素。20. The sodium-rich P2 phase layered oxide according to any one of claims 12 to 17 and 19, characterized in that the doping elements include at least 1 to 3 metal elements selected from the fifth period; and at least 2 to 4 metal elements selected from the third period and/or the fourth period. 21.如权利要求20所述的富钠P2相层状氧化物，其特征在于，所述第五周期的金属元素选自锆、铌、钼、钌、锡、锑元素；所述第三周期的金属元素选自镁、铝元素；所述第四周期的金属元素选自钙、钛、钒、铬、铁、钴、铜、锌元素。21. The sodium-rich P2 phase layered oxide as described in claim 20 is characterized in that the metal elements of the fifth period are selected from zirconium, niobium, molybdenum, ruthenium, tin, and antimony; the metal elements of the third period are selected from magnesium and aluminum; and the metal elements of the fourth period are selected from calcium, titanium, vanadium, chromium, iron, cobalt, copper, and zinc. 22.一种如权利要求12至21中任一项所述的富钠P2相层状氧化物的制备方法，其特征在于，步骤包括：22. A method for preparing a sodium-rich P2-phase layered oxide according to any one of claims 12 to 21, characterized in that the steps include: 按照钠、镍、锰、掺杂元素的化学计量比为x:α:β:z，称取相应摩尔比的钠盐、镍氧化物、锰氧化物和掺杂元素的氧化物，并进行混合处理，得到混合粉末；According to the stoichiometric ratio of sodium, nickel, manganese and doping element being x : α : β : z , sodium salt, nickel oxide, manganese oxide and oxide of the doping element in corresponding molar ratios are weighed and mixed to obtain a mixed powder; 将混合处理后的所述混合粉末压制处理，得到压制成型的块状物；Pressing the mixed powder after mixing to obtain a pressed block; 将所述块状物烧结处理。The block is sintered. 23.如权利要求22所述的制备方法，其特征在于，所述钠盐选自碳酸钠、碳酸氢钠、醋酸钠、草酸钠、柠檬酸钠、硝酸钠中的至少一种。23. The preparation method according to claim 22, characterized in that the sodium salt is selected from at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium citrate and sodium nitrate. 24.如权利要求22或23中所述的富钠P2相层状氧化物的制备方法，其特征在于，所述混合处理采用球磨法混合；24. The method for preparing a sodium-rich P2-phase layered oxide according to claim 22 or 23, characterized in that the mixing treatment is carried out by ball milling; 和/或，所述压制步骤中，步骤具体的包括，将所述混合粉末装入模具中，加压压制成型；And/or, in the pressing step, the steps specifically include: loading the mixed powder into a mold and pressing and molding it; 和/或，所述烧结步骤中，烧结温度介于500至1100℃，烧结时间为1至24h。And/or, in the sintering step, the sintering temperature is between 500 and 1100° C., and the sintering time is between 1 and 24 hours. 25.如权利要求24所述的制备方法，其特征在于，所述球磨法混合中，球料质量比为(5~20)：1，分散剂采用乙醇、丙酮、N-甲基吡咯烷酮、异丙醇或水中的一种或多种，球磨时间为3至24h；25. The preparation method according to claim 24, characterized in that, in the ball milling mixing, the ball-to-material mass ratio is (5-20):1, the dispersant is one or more of ethanol, acetone, N-methylpyrrolidone, isopropanol or water, and the ball milling time is 3 to 24 hours; 和/或，所述加压的压力为5至30MPa；And/or, the pressurized pressure is 5 to 30 MPa; 和/或，所述烧结温度介于800℃至1000℃。And/or, the sintering temperature is between 800°C and 1000°C. 26.如权利要求25所述的制备方法，其特征在于，所述烧结温度介于850℃至950℃。26. The preparation method according to claim 25, characterized in that the sintering temperature is between 850°C and 950°C. 27.一种富钠P2相层状氧化物的制备方法，其特征在于，步骤包括：按照钠、镍、锰、掺杂元素的化学计量比为x:α:β:z，称取相应摩尔比的钠盐、镍氧化物、锰氧化物和掺杂元素的氧化物，并进行混合处理，得到混合粉末，其中x＞1，0＜α≤0.4，0＜β≤0.7，α+β+z=1，0＜z≤0.2；所述掺杂元素选自铁、钴、铜、钛、镁、锌、钙、钒、铬、锆、铌、钼、钌、锡、锑、铝元素中的至少一种；27. A method for preparing a sodium-rich P2 phase layered oxide, characterized in that the steps include: weighing sodium salt, nickel oxide, manganese oxide and oxide of the doping element in corresponding molar ratios according to the stoichiometric ratio of sodium, nickel, manganese and doping element of x : α : β : z , and mixing them to obtain a mixed powder, wherein x >1, 0 < α≤0.4, 0< β≤0.7, α + β+z =1, 0 < z≤0.2; the doping element is selected from at least one of iron, cobalt, copper, titanium, magnesium, zinc, calcium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, tin, antimony and aluminum; 将混合处理后的所述混合粉末压制处理，得到压制成型的块状物；Pressing the mixed powder after mixing to obtain a pressed block; 将所述块状物烧结处理。The block is sintered. 28.如权利要求27所述富钠P2相层状氧化物的制备方法，其特征在于，所述钠盐选自碳酸钠、碳酸氢钠、醋酸钠、草酸钠、柠檬酸钠、硝酸钠中的至少一种。28. The method for preparing a sodium-rich P2 phase layered oxide as claimed in claim 27, characterized in that the sodium salt is selected from at least one of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium citrate and sodium nitrate. 29.如权利要求27或28所述的富钠P2相层状氧化物的制备方法，其特征在于，所述掺杂元素选自铁、钴、铜、钛、镁、锌、钙、钒、铬、锆、铌、钼、钌、锡、锑、铝元素中的五种以上；29. The method for preparing a sodium-rich P2-phase layered oxide according to claim 27 or 28, characterized in that the doping element is selected from five or more of iron, cobalt, copper, titanium, magnesium, zinc, calcium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, tin, antimony, and aluminum; 和/或，所述富钠P2相层状氧化物的XRD衍射图谱包括（002）（004）（100）（102）（103）（104）晶面衍射峰；And/or, the XRD diffraction pattern of the sodium-rich P2 phase layered oxide includes (002) (004) (100) (102) (103) (104) crystal plane diffraction peaks; 和/或，1＜x≤1.5；and/or, 1＜ x ≤1.5; 和/或，0.1≤α≤0.4，0.1≤β≤0.7；and/or, 0.1≤ α ≤0.4, 0.1≤ β ≤0.7; 和/或，所述烧结处理的烧结温度介于800℃至1000℃。And/or, the sintering temperature of the sintering process is between 800°C and 1000°C. 30.如权利要求29所述的富钠P2相层状氧化物的制备方法，其特征在于，1.1≤x≤1.34；30. The method for preparing a sodium-rich P2-phase layered oxide according to claim 29, wherein 1.1 ≤ x ≤ 1.34; 和/或，0.2≤α≤0.33，0.6≤β≤0.7；and/or, 0.2≤ α ≤0.33, 0.6≤ β ≤0.7; 和/或，所述烧结温度介于850℃至950℃。And/or, the sintering temperature is between 850°C and 950°C. 31.如权利要求30所述的富钠P2相层状氧化物的制备方法，其特征在于，0.23≤α≤0.33，0.67≤β≤0.7。31. The method for preparing a sodium-rich P2-phase layered oxide according to claim 30, wherein 0.23≤ α ≤0.33, and 0.67≤ β ≤0.7. 32.一种钠离子电池正极材料，其特征在于，包括如权利要求1至5、12至21中任一项所述的富钠P2相层状氧化物；或，如权利要求6至11、22至31中任一项所述的制备方法得到的富钠P2相层状氧化物。32. A sodium ion battery positive electrode material, characterized in that it comprises a sodium-rich P2 phase layered oxide as described in any one of claims 1 to 5 and 12 to 21; or a sodium-rich P2 phase layered oxide obtained by the preparation method as described in any one of claims 6 to 11 and 22 to 31. 33.一种钠离子电池，其特征在于，包括如权利要求32所述的钠离子电池正极材料。33. A sodium ion battery, characterized in that it comprises the sodium ion battery positive electrode material according to claim 32. 34.一种用电装置，其特征在于，包括如权利要求33所述的钠离子电池。34. An electrical device, characterized in that it comprises the sodium ion battery as claimed in claim 33.
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