CN116605918A - High-entropy doped O3 phase layered oxide, preparation method thereof, sodium ion battery positive electrode material and battery - Google Patents

High-entropy doped O3 phase layered oxide, preparation method thereof, sodium ion battery positive electrode material and battery Download PDF

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CN116605918A
CN116605918A CN202310270071.2A CN202310270071A CN116605918A CN 116605918 A CN116605918 A CN 116605918A CN 202310270071 A CN202310270071 A CN 202310270071A CN 116605918 A CN116605918 A CN 116605918A
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杨树斌
陈浩
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Beihang University
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    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract

The invention discloses a high-entropy doped O3 phase layered oxide, a preparation method thereof, a sodium ion battery anode material and a battery, wherein the chemical formula of the high-entropy doped O3 phase layered oxide is expressed as Na x A y M z O 2 Wherein Na represents sodium element, and A is selected from three elements of iron, nickel and manganese; m represents a doping element, wherein M is selected from more than five metal elements different from sodium and A in the third to fifth periods of the periodic table, x is more than or equal to 0.9 and less than or equal to 1,0.8 and less than or equal to y is more than or equal to 1, z is more than or equal to 0 and less than or equal to 0.2, and y+z=1; the high entropy doped O3 phase lamellar oxygen is obtained by doping more than five metal elements (high entropy doping) in the Fe-Ni-Mn-based layered oxide lattice at low contentThe compound has excellent environmental stability and water resistance, and when the compound is used as a positive electrode material of a sodium ion battery, the cycle capacity and the multiplying power performance are optimized.

Description

High-entropy doped O3 phase layered oxide, preparation method thereof, sodium ion battery positive electrode material and battery
Technical Field
The invention belongs to the field of new materials and sodium ion batteries, and particularly relates to a high-entropy doped O3 phase layered oxide, a preparation method thereof, a sodium ion battery anode material and a battery.
Background
Sodium Ion Batteries (SIBs) are considered to be the most promising large-scale energy storage system for replacing Lithium Ion Batteries (LIBs), with major advantages in terms of sodium-rich natural resources, excellent safety performance, and chemistry similar to commercial Lithium Ion Batteries (LIBs).
In long-term sodium-ion battery studies, a large number of electrode materials have been proposed and used as cathode materials (e.g., transition metal oxides, prussian blue, and polyanion-based materials, etc.), which exhibit excellent electrochemical properties when paired with metallic sodium. However, for practical applications, problems such as non-ideal initial coulombic efficiency of sodium batteries, insufficient recyclable sodium content, and poor industrial preparation feasibility of the cathode materials still prevent the sodium ion batteries from moving to commercial applications. Among various types of positive electrode materials, layered structure transition metal oxide Na x TMO 2 (TM is transition metal) due to its high reversible capacity, energy density up to 500Wh kg -1 And good cycle stability, and the like. The O3 phase manganese-based layered structure oxide has Ni 2+/3+/4+ Is an inherent advantage of the high operating potential of (c) and the high capacity of Mn. More importantly, the higher sodium content of this class of compounds, compared to sodium deficient P2 compounds, provides more recyclable sodium and high initial coulombic efficiency, which plays a significant role in practical sodium ion full cell systems. First, mn 3+ The Jahn-Teller effect and multiple phase changes during the sodium removal/intercalation process, such as from O3 to O '3, P'3 and P3 "phases, have an adverse effect on the circulation performance. To eliminate these obstacles, elemental doping/substitution has proven to be an effective method to mitigate this adverse effect and ultimately improve electrochemical performance. For example, oh et al report O3-Na [ Li ] 0.05 (Ni 0.25 Fe 0.25 Mn 0.5 ) 0.95 ]O 2 Synthesized by a coprecipitation method, the O3 phase has high reversible capacity and good cycle life. Meanwhile, previous studies have shown that Ni and Co are common elements in sodium-rich cathode materialsCan provide considerable capacity, and is beneficial to the formation of lamellar oxides; li, fe, co, cu, ti, zn, zr, sb and Mg are common doping elements in the cathode material. Wherein, the synergistic effect of Ti and Cu can obviously improve the environment and structural stability of the anode; fe can improve the cycling stability of the cathode material. Secondly, the problem of poor stability of the O3 phase in air also increases the synthesis difficulty, and even makes the material impossible to realize practical application. In order to solve the air stability problem, P2-Na reported by the Obrova group of problems 2/3 Ni 1/6 Cu 1/6 Mn 2/3 O 2 The positive electrode improves the air stability of the positive electrode through Cu doping. Therefore, the O3 phase positive electrode material needs to achieve a reasonable balance between stability and electrochemical performance.
The electrochemical performance or physical performance of the O3-phase sodium-ion battery anode material can be improved by doping a single element, but the improvement is limited to a single aspect, and the simultaneous improvement of the electrochemical performance and the air/environment stability cannot be achieved. This requires an entropy stabilization strategy that uses the synergistic effect of multiple elements to enhance the electrochemical and physical properties of the positive electrode material. In addition, the synthesis process using the coprecipitation synthesis method is relatively complex, and the cost of synthesizing the cathode material is high, so that a simple and efficient synthesis method needs to be explored.
Disclosure of Invention
Aiming at the technical problem that the air/environment stability of the sodium ion battery O3 phase layered oxide positive electrode material is poor, the invention provides a technical scheme that more than five metal elements are doped in an iron-nickel-manganese base layered oxide lattice in a low content (high entropy doping).
The first aspect of the invention provides a high entropy doped O3 phase layered oxide having a chemical formula represented by Na x A y M z O 2 Wherein Na represents sodium element, and A is selected from three elements of iron (Fe), nickel (Ni) and manganese (Mn); m represents a doping element, wherein M is selected from at least five metal elements different from A in the third to fifth periods of the periodic table, x is more than or equal to 0.9 and less than or equal to 1,0.8, y is more than or equal to 1, z is more than or equal to 0 and less than or equal to 0.2, and y+z=1.
In some embodiments, the doping element M is selected from five or more elements of cobalt (Co), copper (Cu), titanium (Ti), magnesium (Mg), zinc (Zn), calcium (Ca), vanadium (Ti), chromium (Cr), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tin (Sn), antimony (Sb), and aluminum (Al).
In some embodiments, the doping element M includes: at least 1 to 3 kinds of metal elements selected from the fifth period, and at least 2 to 4 kinds of 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), antimony (Sb); the metal element in the third period is selected from magnesium (Mg) and aluminum (Al); the metal element in the fourth period is selected from calcium (Ca), titanium (Ti), vanadium (V), chromium (Cr), cobalt (Co), copper (Cu), and zinc (Zn).
In some embodiments, the subscript value of each doping element in the chemical formula of the high entropy doped O3 phase layered oxide is less than or equal to 0.05.
In some embodiments, the above-described high entropy doped O3 phase layered oxide has a chemical formula represented by Na x (Mn α Fe β Niγ)(M 1a M 2b M 3c M 4d M 5e M 6f )O 2 Y=α+β+γ, z=a+b+c+d+e+f, where M 1 、M 2 、M 3 、M 4 、M 5 、M 6 Respectively representing different metal elements; alpha is more than or equal to 0.1 and less than or equal to 0.5, beta is more than or equal to 0.1 and less than or equal to 0.4, gamma is more than or equal to 0.1 and less than or equal to 0.3, a is more than or equal to 0 and less than or equal to 0.05, b is more than or equal to 0 and less than or equal to 0.05, c is more than or equal to 0 and less than or equal to 0.05, d is more than or equal to 0 and less than or equal to 0.05, e is more than or equal to 0 and less than or equal to 0.05, and f is more than or equal to 0 and less than or equal to 0.05. Preferably, a is more than 0 and less than or equal to 0.04,0, b is more than or equal to 0.04,0, c is more than or equal to 0.04,0, d is more than or equal to 0.04,0, e is more than or equal to 0.04,0, and f is more than or equal to 0.04; more preferably, 0 < a.ltoreq. 0.03,0 < b.ltoreq. 0.03,0 < c.ltoreq. 0.03,0 < d.ltoreq. 0.03,0 < e.ltoreq. 0.03,0.ltoreq.f.ltoreq.0.03; still more preferably, 0 < a.ltoreq. 0.02,0 < b.ltoreq. 0.02,0 < c.ltoreq. 0.02,0 < d.ltoreq. 0.02,0 < e.ltoreq. 0.02,0.ltoreq.f.ltoreq.0.02.
In some embodiments, the doping element M includes: at least two of titanium (Ti), vanadium (V), chromium (Cr), copper (Cu), zinc (Zn), magnesium (Mg); and/or at least one element selected from tin (Sn), antimony (Sb), niobium (Nb), molybdenum (Mo), and zirconium (Zr).
In some embodiments, the XRD diffraction pattern of the above-described high entropy doped O3 phase layered oxide includes strong diffraction peaks (003) and (104), weak diffraction peaks (006), (101), (012) relative to the Jiang Yanshe peaks.
The second aspect of the present invention provides a method for preparing the above high entropy doped O3 phase layered oxide, comprising the steps of:
weighing sodium salt and oxide of A in corresponding molar ratio according to the chemical formula of the high-entropy doped O3 phase layered oxide, and carrying out mixing treatment on the oxide powder of the doped element M to obtain mixed powder; pressing the mixed powder to obtain a pressed block; and sintering the block.
In some implementations, the sintering process includes: and the heating temperature of the heating and heat-preserving section is 500-600 ℃, and the heat-preserving time is 1-12 hours.
In some embodiments, the sintering process includes at least two heating and heat-preserving sections, wherein the heating temperature of the first heating and heat-preserving section is 500 to 600 ℃, the heat-preserving time is 1 to 12 hours, and the heating temperature of the second heating and heat-preserving section is 700 to 1100 ℃.
In some embodiments, the sodium salt is selected from sodium carbonate (Na 2 CO 3 ) Sodium bicarbonate (NaHCO) 3 ) Sodium acetate (CH) 3 COONa), sodium oxalate (Na 2 C 2 O 4 ) Sodium citrate (C) 6 H 5 Na 3 O 7 ) Sodium nitrate (NaNO) 3 ) One or more of sodium hydroxide (NaOH).
In some implementations, the mixing treatment includes ball milling, wherein the ball milling comprises the following components in mass ratio (5-20): 1, dispersing agent adopts one or more of ethanol, acetone, N-methyl pyrrolidone (NMP), isopropyl alcohol (IPA) or water, the ball milling speed is 300-600 r/min, and the ball milling time is 3-24 h.
In some implementations, in the above-described pressing process, the steps more specifically include loading the mixed powder into a mold, and press-molding; preferably, the pressure of the pressurization is 5 to 30Mpa.
In some implementations, the sintering process is performed at a sintering temperature of 500 to 1100 ℃, at a heating rate of 3 to 20 ℃/min, and for a sintering time of 1 to 36 hours.
The third aspect of the present invention provides a positive electrode material for a sodium ion battery, comprising: a high entropy doped O3 phase layered oxide as described above; or the high entropy doped O3 phase layered oxide obtained by the preparation method.
A fourth aspect of the present invention provides a sodium ion battery, which is characterized by comprising the above-mentioned sodium ion battery cathode material.
The fifth aspect of the invention is an electric device, comprising the sodium ion battery. The power utilization device comprises an automobile, an electric vehicle, an energy storage power station, an electronic appliance and the like.
Compared with the prior art, the invention provides the novel high-entropy doped O3 phase layered oxide and the preparation method thereof, and compared with the traditional coprecipitation method, the preparation method (high-temperature solid phase sintering method) has the advantages of simple process, easy industrial production and amplified production, and reduced cost of products; the prepared high-entropy doped O3 phase layered oxide has excellent environmental stability and water resistance, and when being used as a positive electrode material of a sodium ion battery, the high-entropy doped O3 phase layered oxide has optimized cycle capacity and rate capability.
Drawings
FIG. 1 is an XRD spectrum of a high entropy doped O3 phase layered oxide and a comparative sample in example 2 of the present invention.
Fig. 2 is an SEM photograph and an elemental distribution diagram of the high entropy doped O3 phase layered oxide in example 2 of the present invention.
FIG. 3 is a graph showing the results of electrochemical performance test of the high entropy doped O3 phase layered oxide and the comparative sample as the positive electrode material of sodium ion battery in example 2 of the present invention; wherein (a) is a cycle performance test at a rate of 0.1C, (b) is a cycle performance test at a rate of 0.1 to 10C, (C) is a cycle performance test at a rate of 1C, and (d) is a cycle performance test at a rate of 5C.
FIG. 4 is a structural characterization and electrochemical performance test results after immersing in water of the high entropy doped O3 phase layered oxide and comparative sample as the positive electrode material of sodium ion battery in example 2 of the present invention; wherein (a) is XRD diffraction result of the HE-doping O3 phase in the soaking water for 12h and standing in the air for 7 days, and (b) is electrochemical performance of the doped O3 phase after soaking water for 12 h.
FIG. 5 is a high entropy doped O3 phase layered oxide Na according to example 3 of the present invention 1 Mn 0.4 Fe 0.3 Ni 0.2 Ti 0.02 Cu 0.02 Sn 0.02 Sb 0.02 Zn 0.02 O 2 Comparison sample Na with different doping element contents 1 Mn 0.4 Fe 0.3 Ni 0.1 Ti 0.04 Cu 0.04 Sn 0.04 Sb 0.04 Zn 0.04 O 2 As the structural characterization and electrochemical performance test result of the positive electrode material of the sodium ion battery; wherein (a) is XRD diffraction result of HE-dopping O3 phase with different doping content; the HE-dopping O3 electrochemical performance tests with different doping contents mainly comprise (b) a 0.1C small-rate test, (C) a 5C long-cycle test and (d) a 0.1C-10C rate performance test.
FIG. 6 shows the structural characterization and electrochemical performance test results of the high entropy doped O3 phase layered oxide of different Mn content in example 4 of the present invention; wherein (a) is XRD diffraction results of HE-doping O3 phases with different Mn contents, and (b) is an electrochemical performance test result of HE-doping O3 phases with different Mn contents.
FIG. 7 is a structural characterization and electrochemical performance test results of the six-element high entropy doped O3 phase layered oxide and its comparative sample of example 5 of the present invention; wherein (a) is XRD diffraction result and (b) is electrochemical performance test result.
FIG. 8 is a structural characterization and electrochemical performance test results of a 500 ℃ heat preservation sintering and comparison sample of the high entropy doped O3 phase layered oxide of example 6 of the present invention; wherein (a) is XRD diffraction result and (b) is electrochemical performance test result.
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 sodium ion battery positive plate disclosed by the invention comprises the following steps of: 1) Mixing and grinding a sodium ion battery anode material (high entropy doped O3 phase layered oxide in the invention) with 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), grinding for 20min, and preparing to obtain mixed slurry; 2) Coating the obtained mixed slurry on an aluminum foil wafer with the diameter of 12mm, wherein the loading capacity is 1.4mg/cm 2 And pre-drying the coated electrode slice at 40 ℃ for 0.5 to 5 hours, and then drying the electrode slice in a vacuum oven at 80 ℃ for 24 hours.
The same method is adopted, and the high-entropy doped O3 phase layered oxide is replaced by other layered oxides (specific types are provided in specific examples), so that the positive plate of the comparison sample is obtained.
The method for assembling the sodium ion battery comprises the following steps: the metal sodium sheet is used as a negative electrode, the prepared positive electrode sheet is used as a positive electrode, a CR2032 button cell is prepared in an argon glove box, a glass fiber diaphragm is adopted as a diaphragm, and NaClO with the concentration of 1M is adopted as electrolyte 4 Solution, solvent volume ratio 1:1 and dimethyl carbonate (DMC) and contains 2% by volume of fluoroethylene carbonate (FEC).
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 2.0-4.2V, and the multiplying power range is 0.1-10C.
Example 1
The embodiment provides a high-entropy doped O3 phase layered oxide Na x A y M z O 2 A is selected from three elements of iron (Fe), nickel (Ni) and manganese (Mn), M represents a doping element, and M is selected from more than five metal elements different from sodium (Na), iron (Fe), nickel (Ni) and manganese (Mn) in the third to fifth periods of the periodic table; in the embodiment, the M element is selected from more than five elements of 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), wherein x is more than or equal to 0.9 and less than or equal to 1,0.8, y is more than or equal to 1, z is more than or equal to 0 and less than or equal to 0.2, and y+z=1.
In one embodiment, the M element in the high-entropy doped O3 phase layered oxide is selected from five or six metal elements, and the chemical formula is Na x (Mn α Fe β Niγ)(M 1a M 2b M 3c M 4d M 5e M 6f )O 2 Wherein M is 1 、M 2 、M 3 、M 4 、M 5 、M 6 Representing different doping elements, wherein alpha is more than or equal to 0.1 and less than or equal to 0.5, beta is more than or equal to 0.1 and less than or equal to 0.4, gamma is more than or equal to 0.1 and less than or equal to 0.3, a is more than or equal to 0 and less than or equal to 0.04,0, b is more than or equal to 0.04,0, c is more than or equal to 0.04,0, d is more than or equal to 0.04,0, e is more than or equal to 0.04,0 and f is more than or equal to 0.04.
In an embodiment, the doping element M 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; the high-entropy doped O3 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 O3 phase layered compound can be increased through the staggered matching of the metal atoms in different periods; in a preferred embodiment, the metal element of the fifth period is selected from zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), tin (Sn), antimony (Sb) elements; the metal element in the third period is selected from magnesium (Mg) and aluminum (Al); the metal element in the fourth period is selected from calcium (Ca), titanium (Ti), vanadium (V), chromium (Cr), cobalt (Co), copper (Cu) and zinc (Zn);
in a specific embodiment, the doping element M includes: at least two of titanium (Ti), vanadium (V), chromium (Cr), copper (Cu), zinc (Zn), magnesium (Mg); and/or at least one element selected from tin (Sn), antimony (Sb), niobium (Nb), molybdenum (Mo), and zirconium (Zr).
The preparation method of the high-entropy doped O3 phase layered oxide comprises the following steps:
s01: weighing raw materials with corresponding molar ratios according to the chemical formula of the high-entropy doped O3 phase layered oxide to obtain mixed powder, and mixing the mixed powder, wherein the raw materials comprise: sodium salt and oxide of a, oxide powder doped with element M;
s02: pressing the mixed powder after ball milling treatment to obtain pressed and molded blocks;
s03: and sintering the block.
In a specific implementation, the purpose of the above mixing treatment 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 process 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 not passed through the ball milling balls, and may also be changed according to circumstances. The time of wet ball milling is 3 to 24 hours, and the ball milling speed is 300 to 600r/min; more preferably, the ball milling time is 5 to 20 hours and the rotational speed is about 300 to 400r/min.
In particular, in the above-mentioned pressing treatment, a cold pressing treatment is preferably employed, and the pressurizing pressure is 5 to 30Mpa, preferably 5 to 10Mpa.
In a specific implementation, in the sintering treatment, the sintering temperature is 500-1100 ℃, the heating rate is 3-20 ℃/min, and the sintering time is 1-24 h.
More preferably, the sintering treatment includes at least two sections of heating and heat-preserving sections, so that the doping elements are more uniformly diffused into the crystal lattice of the layered oxide to form the high-entropy doped O3-phase layered oxide, and the high-entropy doped O3-phase layered oxide reaches an entropy stable state. The heating and heat preservation interval in the first section is preferably 500 to 600 ℃, and the heat preservation time is 1 to 12 hours; the section of heating and heat preserving section solves or relieves the problem that Na and other metal atoms Mn, fe, ni and other atoms are difficult to mix and arrange in a layered oxide structure because sodium carbonate is easy to sink in the sintering process; the second heating and heat-preserving interval is preferably 700-1100 ℃ and the heat-preserving time is 1-24 h so as to enable doping atoms to be fully diffused.
In the sintering treatment process, sodium salt in the raw materials is heated and then is subjected to solid-phase sintering reaction with metal oxide at high temperature. In one embodiment, the sodium salt is sodium carbonate (Na 2 CO 3 ) In other embodiments, the sodium carbonate in the feedstock may also be replaced with other sodium salts, such as sodium bicarbonate (NaHCO 3 ) Sodium acetate (CH) 3 COONa), sodium oxalate (Na 2 C 2 O 4 ) Sodium citrate (C) 6 H 5 Na 3 O 7 ) Sodium nitrate (NaNO) 3 ) Sodium hydroxide (NaOH), and the like. The nickel oxide in the raw material comprises NiO and Ni 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The manganese oxide includes: mnO, mnO 2 、Mn 2 O 3 、Mn 3 O 4 、Mn 2 O 5 Etc.; the manganese oxide in the raw materials comprises: mnO, mnO 2 、Mn 2 O 3 、Mn 3 O 4 、Mn 2 O 5 Etc.
In step S01, the term "corresponding molar ratio" in the present invention includes not only the stoichiometric molar ratio of each element in the chemical formula of the high-entropy doped O3-phase layered oxide, but also Na 1 Mn 0.4 Fe 0.3 Ni 0.2 Ti 0.02 Cu 0.0 2 Sn 0.02 Sb 0.02 Zn 0.02 O 2 For example, the stoichiometric molar ratio refers to the preparation of Na per mole 1 Mn 0.4 Fe 0.3 Ni 0.2 Ti 0.0 2 Cu 0.02 Sn 0.02 Sb 0.02 Zn 0.02 O 2 Wherein the molar ratio of each element is Na: mn: fe: ni: ti: cu: sn: sb: zn=1: 0.4:0.3:0.2:0.02:0.02:0.02:0.02:0.02; that is, based on the ratio of the corner mark values of the elements in the chemical formula; the method also comprises the steps of properly increasing or decreasing and adjusting the stoichiometric mole ratio of one or more raw material components, and calculating the corresponding feed mole ratio of the actual feed amount of the raw material components; more specifically, the appropriate incremental-decremental post-adjustment dosing mole ratio is 90% to 110% of the stoichiometric mole ratio; in a specific implementation, both the feed molar ratio and the stoichiometric molar ratio are used within the meaning of the "corresponding molar ratio" according to the invention. In a specific embodiment, na 2 CO 3 The actual feed molar ratio of (2) is 102 to 105% of the stoichiometric molar ratio, and the rest of the oxides of A and M are calculated according to the stoichiometric molar ratio, respectively according to the feed molar ratio and the stoichiometric molar ratio.
Example 2
The embodiment provides a specific high-entropy doped O3 phase layered oxide Na 1 Mn 0.4 Fe 0.3 Ni 0.2 Ti 0.02 Cu 0.02 Sn 0.02 Sb 0.02 Zn 0.02 O 2 And a preparation method thereof, wherein the preparation method comprises the following steps:
s11: weighing raw materials with corresponding molar ratios according to the chemical formula of the high-entropy doped O3 phase layered oxide to obtain mixed powder, and performing ball milling treatment on the mixed powder; specifically, the molar ratio is 0.525:0.4:0.15:0.2:0.02:0.02:0.02:0.01:0.02, respectively weighing Na 2 CO 3 、MnO 2 、Fe 2 O 3 、NiO、TiO 2 、CuO、SnO 2 、Sb 2 O 5 And ZnO powder is placed in a ball milling tank, and the ball material mass ratio is 10:1, adding ball milling pellets, adding a proper amount of ethanol as a dispersing agent, finally placing a ball milling tank on a ball mill for ball milling for 4 hours, and placing the ball milling tank in a blast oven at 80 ℃ for drying for 10 hours after ball milling is completed to obtain mixed powder after ball milling;
s12: cold pressing the mixed powder subjected to ball milling at a pressure of 10 MPa; specifically, the dried mixed powder is placed in a circular groove die with the diameter of 14mm, and tabletting is carried out under the pressure of 10MPa to obtain a circular block with the diameter of 14 mm;
s13: and sintering the block, namely placing the pressed round block into an alumina crucible, placing the crucible into a muffle furnace, heating the crucible to 500 ℃ from room temperature, then preserving heat for 5 hours, then heating to 900 ℃, preserving heat for 12 hours, heating at a speed of 5 ℃/min, and taking out the crucible after naturally cooling to normal temperature to obtain a target product.
Preparation of a control: the similar preparation method is adopted, and the difference is that the types and the amounts of the metal oxides in the raw materials are changed, so that a comparison sample of the non-high entropy doped O3 phase layered oxide is prepared, and the preparation method comprises the following steps: monobasic doping (hereinafter referred to as monobasic-doping) Na 1 Mn 0.4 Fe 0.3 Ni 0.2 Cu 0.1 O 2 Binary doped (hereinafter referred to as binary-doping) Na 1 Mn 0.4 Fe 0.3 Ni 0.2 Ti 0.05 Cu 0.05 O 2 Ternary doping (hereinafter referred to as ternary-doping) Na 1 Mn 0.4 Fe 0.3 Ni 0.2 Ti 0.033 Cu 0.033 Sb 0.033 O 2 。
The obtained target product and the comparative sample were subjected to X-ray diffraction (XRD) and as shown in fig. 1, it can be seen that the prepared high entropy doped (hereinafter, HE-doping is used instead), binary-doping and ternary-doping samples have diffraction peaks at 17.0 °, 33.7 °, 35.3 °, 36.6 ° and 42.2 °, which are characteristic peaks of O3 phase, respectively corresponding to crystal planes (003), (006), (101), (102) and (104). Wherein, (003) and (104) are strong diffraction peaks, and (006), (101) and (102) are relatively weak diffraction peaks. The diffraction peaks of the O3 phase (003) plane of binary-doping and HE-doping are 16.5 ° and 16.4 °, respectively, relative to the diffraction peak of the 17.0 ° of the monobasic doping O3 phase (003), which means that the interplanar spacing of binary-doping and HE-doping becomes large, that is, the introduction of a high ionic radius element causes the lattice spacing to become large. Fig. 2 is an SEM photograph and an element distribution diagram of a high entropy doped O3 phase layered oxide, and it can be seen that each element Na, mn, fe, ni, ti, cu, sn, sb, zn therein is uniformly distributed, which indicates that a homogeneous layered oxide is obtained.
The embodiment also provides the application of the obtained O3-phase layered oxide of HE-dopping as a positive electrode material of a sodium ion battery, namely the positive electrode material of the sodium ion battery and the sodium ion battery. The compacted density of the tested HE-dopping O3 phase positive electrode material was 3.38g/cm 3 。
And preparing the obtained HE-doping O3 phase layered oxide and a comparison sample into a positive plate, and assembling to obtain the sodium ion battery. Fig. 3 shows the results of electrochemical performance testing of the O3 phase layered oxide of HE-dopping of the present invention and a control as a positive electrode material for sodium ion batteries. FIG. 3a is a cycle performance test at a rate of 0.1C, showing that the HE-dopingO3 phase has an initial discharge capacity of 158mAh/g, higher than other single or multi-element doped O3 phases; FIG. 3b is a rate capability test, showing that the O3 phase of HE-dopping has significantly superior rate capability; the results of the cyclic performance tests at 1C and 5C rates respectively show that the specific discharge capacities of the O3 phase of HE-dopping at 1C and 5C rates are 113mAh/g and 83mAh/g respectively, and the cyclic stability is good, and is significantly better than that of the mono-and binary-doped O3 phase.
To verify the stability of the O3 phase of HE-doping of the present invention, the O3 phase of HE-doping of the present invention was immersed in water and exposed to air for 12h, respectively, and then the sample was dried (vacuum 80 ℃ for 12 h) and subjected to XRD test, and the test results are shown in fig. 4a, it can be seen that the XRD patterns of the immersed water and the sample after air exposure were not different from those of the initial sample, indicating that the structure was not changed, and the O3 phase of HE-doping was relatively stable in both air and aqueous environments, and had environmental stability and water resistance. To further verify the electrochemical performance of the HE-doping O3 phase of the soaking water, the HE-doping O3 phase after soaking water was tested to assemble a battery and the cycle performance at 0.1C rate was tested. The results in FIG. 4b show that the HE-doping O3 phase is capable of maintaining a high capacity of 153mAh/g (mono-doping 130mAh/g, binary-doping 128 mAh/g) despite the soaking water for 12h, with a capacity retention of 75.2% after 100 cycles, far superior to the mono-doping (49.6%) and binary-doping (44.8%) O3 phases.
In other embodiments, the starting material Na is reduced 2 CO 3 The content of (2) can obtain a high-entropy doped O3 phase layered oxide with low sodium content; in one embodiment, the molar ratio is 0.45:0.4:0.15:0.2:0.02:0.02:0.02:0.01:0.02, respectively weighing Na 2 CO 3 、MnO 2 、Fe 2 O 3 、NiO、TiO 2 、CuO、SnO 2 、Sb 2 O 5 And ZnO powder, and the rest conditions are unchanged, thus obtaining the high entropy doped O3 phase layered oxide Na 0.9 Mn 0.4 Fe 0.3 Ni 0.2 Ti 0.02 Cu 0.02 Sn 0.02 Sb 0.02 Zn 0.02 O 2 。
Example 3
In this example, another high-entropy doped O3 phase layered oxide Na with different doping element contents was prepared by changing the ratio of metal oxides in the raw materials by a preparation method similar to that of example 2 1 Mn 0.4 Fe 0.3 Ni 0.1 Ti 0.04 Cu 0.04 Sn 0.04 Sb 0.04 Zn 0.04 O 2 And it was used as a positive electrode material of a sodium ion battery, the battery was assembled and tested for electrochemical performance, and the test results are shown in fig. 5.
The results of the electrochemical performance test of the high-entropy doped O3 phase layered oxide as the positive electrode material of sodium ion battery by the two different doping element contents in examples 2 and 3 are compared, and the results are shown in fig. 5. As shown in XRD diffraction pattern of FIG. 5a, high doping amount of pure phase Na of O3 can be obtained by high temperature solid phase sintering 1 Mn 0.4 Fe 0.3 Ni 0.1 Ti 0.04 Cu 0.04 Sn 0.04 Sb 0.0 4 Zn 0.04 O 2 . As can be seen from FIGS. 5b-d, the high entropy doped O3 phase layered oxide Na of example 2 1 Mn 0.4 Fe 0.3 Ni 0.2 Ti 0.0 2 Cu 0.02 Sn 0.02 Sb 0.02 Zn 0.02 O 2 Although the doping element content of (C) is lower than that of Na in example 3 1 Mn 0.4 Fe 0.3 Ni 0.1 Ti 0.04 Cu 0.04 Sn 0.04 Sb 0.04 Zn 0.04 O 2 However, from the aspect of specific capacity, cycle performance and rate performance, the high-entropy doped O3 phase layered oxide of example 2 is superior to that of example 3, and it is seen that the doping element content is also one of the factors affecting the performance of the high-entropy doped O3 phase layered oxide as a positive electrode material of a sodium ion battery, and the doping content is not higher, better, but rather the lower doping amount is beneficial to the improvement of the electrochemical performance of the high-entropy doped O3 phase layered oxide as a positive electrode material of a sodium ion battery. Therefore, the high entropy doped O3 phase layered oxide is represented by a chemical formula, na x (Mn αF e β Ni γ )(M 1a M 2b M 3c M 4d M 5e M 6f )O 2 Wherein, alpha is more than or equal to 0.1 and less than or equal to 0.5, beta is more than or equal to 0.1 and less than or equal to 0.4, gamma is more than or equal to 0.1 and less than or equal to 0.3, preferably, a is more than or equal to 0 and less than or equal to 0.03,0, b is more than or equal to 0.03,0, c is more than or equal to 0.03,0, d is more than or equal to 0.03,0, e is more than or equal to 0.03,0 and f is more than or equal to 0.03. More preferably, 0 < a.ltoreq. 0.02,0 < b.ltoreq. 0.02,0 < c.ltoreq. 0.02,0 < d.ltoreq. 0.02,0 < e.ltoreq. 0.02,0.ltoreq.f.ltoreq.0.02.
Example 4
In this example, another high-entropy doped O3 phase layered oxide Na with different Mn element contents was prepared by changing the ratio of metal oxides in the raw materials by a preparation method similar to that of example 2 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.02 Ti 0.02 Sn 0.02 Sb 0.0 2 Zn 0.02 O 2 And used as a positive electrode material of a sodium ion battery, and the specific results are shown in fig. 6 below.
As shown in FIG. 6a, the appearance of the (003) and (104) planes in the XRD diffraction pattern demonstrates Na 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.0 2 Ti 0.02 Sn 0.02 Sb 0.02 Zn 0.02 O 2 Is O3 phase. In addition, the electrochemical data results of FIG. 6b show that at 1C rate, high manganese positive electrode Na 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.02 Ti 0.02 Sn 0.02 Sb 0.02 Zn 0.02 O 2 Has a specific discharge capacity of 112mAh/g and a capacity thereofThe volume retention rate is 77.7 percent, and the product has certain circulation stability.
Comparing the electrochemical performance test results of the O3 phase high entropy doped layered oxide prepared in this example with those of example 2, it can be seen that the content of Mn element is increased and the capacity is reduced by increasing the content of Mn element under the same doping element, and Na in the chemical formula of the high entropy doped O3 phase layered oxide x (Mn α Fe β Niγ)(M 1a M 2b M 3c M 4d M 5e M 6f )O 2 More preferably, 0.1.ltoreq.α.ltoreq.0.4, 0.1.ltoreq.β.ltoreq. 0.3,0.1.ltoreq.γ.ltoreq.0.2, 0 < a.ltoreq. 0.02,0 < b.ltoreq. 0.02,0 < c.ltoreq. 0.02,0 < d.ltoreq. 0.02,0 < e.ltoreq. 0.02,0.ltoreq.f.ltoreq.0.02.
Example 5
This example was conducted by a production method similar to that of example 2, changing the ratio of the metal oxide in the raw material and increasing ZrO 2 Preparing another high-entropy doped O3 phase layered oxide Na with six doping elements 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.02 Ti 0.02 Mg 0.02 Zn 0.02 Sb 0.01 Zr 0.01 O 2 . The comparison sample is unitary Cu doped Na 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.1 O 2 And binary Cu, mg doped Na 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.05 Mg 0.05 O 2 . The results of the implementation are shown in FIG. 7.
As shown in FIG. 7a, the appearance of the (003) and (104) planes in the XRD diffraction pattern demonstrates Na 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.0 2 Ti 0.02 Mg 0.02 Zn 0.02 Sb 0.01 Zr 0.01 O 2 、Na 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.1 O 2 And Na (Na) 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.05 Mg 0.05 O 2 All are O3 phases. In addition, the electrochemical data results of FIG. 6b show that at 1C magnification, six-membered doped cathode material Na 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.02 Ti 0.02 Mg 0.02 Zn 0.02 Sb 0.01 Zr 0.01 O 2 Has a specific discharge capacity of 121mAh/g, which is far higher than Na 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.1 O 2 (112 mAh/g) and Na 1 Mn 0.5 Fe 0.3 Ni 0.1 Cu 0.05 Mg 0.05 O 2 (108 mAh/g) and which has a relatively high capacity retention of 70%. Six-membered high entropy doping is shown to be also beneficial to the improvement of electrochemical performance.
Example 6
In this example, a high entropy doped layered oxide Na was prepared by changing the heat retention time during sintering by a method similar to that of example 2, namely, removing the heat retention time of 500-600℃for 6-12 hours, and comparing it with the heat retention time and method of example 2 1 Mn 0.4 Fe 0.3 Ni 0.2 Cu 0.02 Ti 0.02 Sn 0.02 Zn 0.02 Sb 0.02 O 2 . The results of the implementation are shown in FIG. 8.
As shown in FIG. 8a, the HE-doping sample subjected to heat preservation and sintering at 500 ℃ is an O3 phase, and the HE-doping sample not subjected to heat preservation at 500 ℃ is a P2/O3 composite phase, which shows that the heat preservation time is favorable for sintering to form a pure O3 phase, mainly because sodium carbonate is easy to sink in the sintering process, and the heat preservation and sintering at 500-600 ℃ can be used for relieving the phenomenon, so that the problem of mixed arrangement of Na, mn, fe, ni and other atoms in the layered oxide structure is favorable to be solved or relieved. The 500 ℃ heat-preserving sintered HE-doping O3 phase has an initial specific discharge capacity of 122mAh/g, while the non-heat-preserving sintered HE-doping P2/O3 phase has an initial specific discharge capacity of 58mAh/g. Although the non-insulated sintered HE-doping P2/O3 phase has better cycling stability, the specific discharge capacity of the HE-doping O3 phase is about twice that of the non-insulated sintered HE-doping P2/O3 phase.
Therefore, in the sintering treatment of the high-entropy doped O3 phase layered oxide of the present invention, it is preferable to include a heating and heat-preserving section having a heating temperature of 500 to 600 ℃ and a heat-preserving time of 1 to 12 hours. In a specific embodiment, the heating and heat preserving section comprises at least two sections, wherein the heating temperature of the first heating and heat preserving section is between 500 ℃ and 600 ℃, the heat preserving time is between 1 and 12 hours, the heating temperature of the second heating and heat preserving section is between 700 ℃ and 1100 ℃, and the heat preserving time is preferably between 1 and 24 hours. In another specific embodiment, the method can further comprise more than three heating and heat-preserving sections, and the temperature and time of the heating and heat-preserving sections are adjusted, so that the heating and heat-preserving time is shortened on the premise of ensuring that various doping elements are fully diffused, and the preparation energy consumption is reduced. The specific process adjustments in these sintering processes can be accomplished through a limited number of process optimization experiments, all of which are within the scope of the present invention.
The XRD diffraction pattern of the high-entropy doped O3-phase layered oxide includes strong diffraction peaks (003) and (104) with respect to weak diffraction peaks (006), (101) and (012). Jiang Yanshe peaks (003) and (104), in some embodiments, the diffraction intensity (104) is stronger than (003), in other embodiments, the diffraction intensity (003) is stronger than (104); similarly, the intensity of each weak diffraction peak (006), (101), (012) is relative to the intensity of the strong diffraction peak (003) and (104), and the diffraction intensity of each (006), (101), (012) may be different in different embodiments.
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 (11)

1. A high-entropy doped O3 phase layered oxide is characterized in that the chemical formula of the high-entropy doped O3 phase layered oxide is represented by Na x A y M z O 2 Wherein Na represents sodium element, and A is selected from three elements of iron, nickel and manganese; m represents a doping element, wherein M is selected from at least five metal elements different from sodium and A in the third to fifth periods of the periodic table, x is more than or equal to 0.9 and less than or equal to 1,0.8 and less than or equal to y is more than or equal to 1, z is more than or equal to 0 and less than or equal to 0.2, and y+z=1;
preferably, the M is selected from more than five elements of cobalt, copper, titanium, magnesium, zinc, calcium, vanadium, chromium, zirconium, niobium, molybdenum, ruthenium, tin, antimony and aluminum.
2. The high entropy doped O3 phase layered oxide of claim 1, wherein M comprises: at least 1 to 3 kinds of metal elements selected from the fifth period, and at least 2 to 4 kinds of metal elements selected from the third period and/or the fourth period;
preferably, the metal element of the fifth period is selected from zirconium, niobium, molybdenum, ruthenium, tin, antimony elements; the metal element in the third period is selected from magnesium and aluminum elements; the metal element in the fourth period is selected from calcium, titanium, vanadium, chromium, cobalt, copper and zinc.
3. The high entropy doped O3 phase layered oxide of claim 1, wherein the high entropy doped O3 phase layered oxide has a chemical formula represented by Na x (Mn α Fe β Niγ)(M 1a M 2b M 3c M 4d M 5e M 6f )O 2 ，y＝α+β+γ，z＝a+b+c+d+e+f，0.1≤α≤0.5，0.1≤β≤0.4，0.1≤γ≤0.3，0＜a≤0.05，0＜b≤0.05，0＜c≤0.05，0＜d≤0.05，0＜e≤0.05，0≤f≤0.05；
Preferably, a is more than 0 and less than or equal to 0.04,0, b is more than or equal to 0.04,0, c is more than or equal to 0.04,0, d is more than or equal to 0.04,0, e is more than or equal to 0.04,0, and f is more than or equal to 0.04;
more preferably, 0 < a.ltoreq. 0.03,0 < b.ltoreq. 0.03,0 < c.ltoreq. 0.03,0 < d.ltoreq. 0.03,0 < e.ltoreq. 0.03,0.ltoreq.f.ltoreq.0.03;
still more preferably, 0 < a.ltoreq. 0.02,0 < b.ltoreq. 0.02,0 < c.ltoreq. 0.02,0 < d.ltoreq. 0.02,0 < e.ltoreq. 0.02,0.ltoreq.f.ltoreq.0.02.
4. A high entropy doped O3 phase layered oxide according to any one of claims 1 to 3, wherein M comprises: at least two of titanium, vanadium, chromium, copper, zinc, magnesium;
and/or at least one element selected from tin, antimony, niobium, molybdenum, and zirconium.
5. A high entropy doped O3 phase layered oxide according to any one of claims 1 to 3, wherein the XRD diffraction pattern of the high entropy doped O3 phase layered oxide comprises strong diffraction peaks (003) and (104), weak diffraction peaks (006), (101), (012) relative to the Jiang Yanshe peaks.
6. A method for preparing the high entropy doped O3 phase layered oxide according to any one of claims 1 to 5, comprising the steps of:
the chemical formula of the high-entropy doped O3 phase layered oxide is that sodium salt, oxide of A and oxide of M with corresponding molar ratios are weighed and mixed to obtain mixed powder;
pressing the mixed powder to obtain a pressed block;
and sintering the block.
7. The method of claim 6, wherein the sintering process comprises a heating and heat-preserving section having a heating temperature of 500 ℃ to 600 ℃ and a heat-preserving time of 1 to 12 hours;
or, the sintering treatment comprises at least two sections of heating and heat-preserving sections, wherein the heating temperature of the first heating and heat-preserving section is between 500 ℃ and 600 ℃, the heat-preserving time is between 1 and 12 hours, and the heating temperature of the second heating and heat-preserving section is between 700 ℃ and 1100 ℃.
8. The method according to claim 6 or 7, wherein the sodium salt is at least one selected from the group consisting of sodium carbonate, sodium bicarbonate, sodium acetate, sodium oxalate, sodium citrate, sodium nitrate, and sodium hydroxide;
and/or the mixing treatment comprises ball milling method mixing, wherein the ball material mass ratio in the ball milling method mixing is (5-20): 1, dispersing agent adopts one or more of ethanol, acetone, N-methyl pyrrolidone, isopropanol or water, ball milling speed is 300-600 r/min, and ball milling time is 3-24 h;
and/or, in the pressing treatment, the steps more specifically include loading the mixed powder into a mold, and pressing and molding; preferably, the pressure of the pressurization is 5 to 30Mpa;
and/or, in the sintering treatment, the sintering temperature is between 500 and 1100 ℃, the heating rate is between 3 and 20 ℃/min, and the sintering time is between 1 and 36 hours.
9. A sodium ion battery positive electrode material, characterized in that the sodium ion battery positive electrode material comprises: the high entropy doped O3 phase layered oxide of any one of claims 1 to 5; or, the high entropy doped O3 phase layered oxide obtained by the production method according to any one of claims 6 to 8.
10. A sodium ion battery comprising the sodium ion battery positive electrode material of claim 9.
11. An electrical device comprising a sodium ion battery as claimed in claim 10.
CN202310270071.2A 2023-03-15 2023-03-15 High-entropy doped O3 phase layered oxide, preparation method thereof, sodium ion battery positive electrode material and battery Pending CN116605918A (en)

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