CN113471431B - NaMn 0.5 Ni 0.5 B x O 2 Material, preparation thereof and application thereof in sodium-ion battery - Google Patents

NaMn 0.5 Ni 0.5 B x O 2 Material, preparation thereof and application thereof in sodium-ion battery Download PDF

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CN113471431B
CN113471431B CN202010980091.5A CN202010980091A CN113471431B CN 113471431 B CN113471431 B CN 113471431B CN 202010980091 A CN202010980091 A CN 202010980091A CN 113471431 B CN113471431 B CN 113471431B
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CN113471431A (en
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冯伊铭
韦伟峰
黄群
岳有缘
唐辰
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Central South University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of positive electrode materials of sodium-ion batteries, and particularly relates to NaMn 0.5 Ni 0.5 B x O 2 A material having a P2 and O3 phase composite phase and having a two-dimensional lamellar morphology; wherein x is more than 0 and less than or equal to 0.1. In addition, the invention also provides a method for successfully preparing the material and an application method of the material in a sodium-ion battery. The B-doped P2/O3 composite phase structure layered sodium ion battery anode material prepared by the method has higher specific capacity and excellent cycling stability.

Description

NaMn 0.5 Ni 0.5 B x O 2 Material, preparation thereof and application thereof in sodium-ion battery
Technical Field
The invention relates to a preparation method of a sodium ion secondary battery material, in particular to a preparation method of a B-doped P2/O3 composite phase layered sodium ion battery positive electrode material.
Background
With the increasing demand of the rapid development of the human economic society for energy, the problem of environmental pollution caused by the combustion of the traditional fossil energy is also paid more and more attention by people, so that the development of clean energy has important significance for realizing green sustainable development. At present, clean energy sources such as wind energy, solar energy, tidal energy and the like which can be used belong to intermittent energy sources, and the clean energy sources can be effectively used only by storing electric energy generated by a large-scale energy storage device and inputting the electric energy into a power grid with stable power. Therefore, advanced large-scale energy storage equipment is crucial to the development and use of clean energy, and the sodium ion battery has excellent performance, abundant raw material data and low priceThe lithium ion secondary battery has the advantages of being most potential to be applied to the field of large-scale energy storage. The positive electrode material is used as an important component of the sodium ion battery, and the performance and the price of the positive electrode material have important influence on the sodium ion battery, so that the development of the positive electrode material of the sodium ion battery with high performance and low cost is very important for the industrial application of the sodium ion battery. The layered transition metal oxide serving as an important sodium ion battery anode material has the advantages of excellent performance, low price and simple preparation method, and has good commercial application prospect. The layered sodium electric anode material consists of an oxygen ion close-packed framework and transition metal ions and sodium ions which are embedded in the framework and are alternately arranged, and can be divided into types of P2, O2, P3, O3 and the like according to the classification rule proposed by Demals et al, wherein P and O respectively represent Na + Occupying rhomboid and octahedral positions, the numbers 2 and 3 represent the number of transition metal layers of different O arrangements in one unit cell. P2 and O3 are two structures which are most common in layered sodium anode materials, and the content of sodium is relatively low in a P2 phase structure, and Na is + The diffusion energy barrier is relatively low, and the rate performance is good; and the O3 phase structure has higher sodium content and higher specific capacity. In order to take the advantages of the layered sodium electric anode materials with different structures into consideration, the synthesis of the layered anode with the P2/O3 composite structure is an effective way for obtaining the high-performance layered sodium electric anode material. At present, researchers have prepared Na by means of lithium doping, sodium content reduction and the like 0.5 [Li x (Fe 0.5 Mn 0.5 ) 1-x ]O 2 、Na 0.67 Mn 0.55 Ni 0.25 Ti 0.2-x Li x O 2 、Na 0.66 Li 0.18 Mn 0.71 Ni 0.21 Co 0.08 O 2+δ 、Na 0.78 Ni 0.2 Fe 0.38 Mn 0.42 O 2 、Na 0.9 Ni 0.45 Mn 0.55 O 2 And P2/O3 composite structure cathode materials are adopted. However, these methods also have some disadvantages, for example, lithium as an inactive element only plays a supporting role in the sodium ion layered cathode material and cannot participate in the electrochemical reaction, and the introduction of lithium improves the preparation of sodium ion batteryThen, the process is carried out; the reduction in sodium content necessarily sacrifices the reversible theoretical capacity of the material itself being produced, limiting its practical application.
Disclosure of Invention
In order to solve the technical problem of insufficient electrochemical performance of the positive electrode active material of the sodium-ion battery, the first purpose of the invention is to provide NaMn 0.5 Ni 0.5 B x O 2 The material aims to provide a novel material which has two-dimensional morphology and a P2/O3 composite crystalline phase structure and has excellent electrochemical performance in a sodium-ion battery.
The second purpose of the invention is to provide the NaMn 0.5 Ni 0.5 B x O 2 A method for preparing the material.
The third purpose of the invention is to provide the NaMn 0.5 Ni 0.5 B x O 2 An application method of the material in a sodium ion battery.
The fourth purpose of the invention is to provide a catalyst containing the NaMn 0.5 Ni 0.5 B x O 2 A sodium ion battery positive electrode made of the material.
The fifth purpose of the invention is to provide a catalyst containing the NaMn 0.5 Ni 0.5 B x O 2 Sodium ion battery of material.
NaMn 0.5 Ni 0.5 B x O 2 The material has a P2 and O3 phase composite phase and has two-dimensional lamellar morphology; wherein x is more than 0 and less than or equal to 0.1.
The invention provides brand new NaMn which has both P2 and O3 phases and has two-dimensional layered morphology 0.5 Ni 0.5 B x O 2 A material. Researches find that the material with the crystal phase structure and the shape has excellent electrochemical performance when used as a positive active material of a sodium-ion battery.
The research of the invention finds that the P2 and O3 phase composite phase and the two-dimensional morphological structure characteristics of the material and the control of the chemical formula are the key points for endowing the material with the performance in the aspect of sodium ion batteries. The research further finds that the control of the ratio of x in the material is helpful for further regulating and controlling the crystalline phase structure and morphology of the material, and is helpful for further improving the performance of the material in the aspect of sodium ion batteries.
Preferably, x is 0.01-0.05; further preferably 0.01 to 0.03; more preferably 0.01 to 0.02. The research of the invention finds that under the preferable x, the electrochemical performance of the material in the aspect of the sodium-ion battery is further improved.
The invention also discloses the NaMn 0.5 Ni 0.5 B x O 2 The preparation method of the material comprises the steps of mixing materials containing a sodium source, a manganese source, a nickel source and a boron source according to the chemical combination ratio to obtain a mixture; and (3) carrying out heat treatment on the mixture at 800-900 ℃ in an oxygen-containing atmosphere to obtain the composite material.
The invention provides a brand new means and idea for constructing a material forming a P2 and O3 phase composite phase in one step by inducing partial conversion of an O3 phase into a P2 phase through doping with boron with special content. The preparation method provided by the invention not only can successfully construct the P2 and O3 composite phase, but also is beneficial to obtaining the lamellar morphology. Research also finds that the layered morphology constructed by the preparation method and the cooperativity of the P2 and O3 composite phase can remarkably improve the electrochemical performance of the composite phase used as the positive active material of the sodium-ion battery.
Preferably, the sodium source is sodium oxide or a salt or hydroxide capable of being converted to sodium oxide; preferably at least one of sodium carbonate, sodium nitrate, sodium bicarbonate, sodium acetate and sodium hydroxide; preferably at least one of sodium carbonate and sodium nitrate.
Preferably, the manganese source is an oxide of manganese or a salt or hydroxide that can be converted to an oxide of manganese; preferred are manganese acetate, manganese nitrate, manganese carbonate, (Mn) 0.5 Ni 0.5 )CO 3 、(Mn 0.5 Ni 0.5 )(OH) 2 At least one of; more preferably (Mn) 0.5 Ni 0.5 )CO 3 、(Mn 0.5 Ni 0.5 )(OH) 2 At least one of (1).
Preferably, the nickel source is an oxide of nickel or oxygen that can be converted to nickelSalts or hydroxides of the compounds; preferably nickel acetate, nickel nitrate, nickel carbonate, (Mn) 0.5 Ni 0.5 )CO 3 、(Mn 0.5 Ni 0.5 )(OH) 2 At least one of (a); more preferably (Mn) 0.5 Ni 0.5 )CO 3 、(Mn 0.5 Ni 0.5 )(OH) 2 At least one of (1).
In the present invention, the manganese source and the nickel source are preferably composed of (Mn) 0.5 Ni 0.5 )CO 3 、(Mn 0.5 Ni 0.5 )(OH) 2 Provided is a method. It was found that (Mn) 0.5 Ni 0.5 )CO 3 、(Mn 0.5 Ni 0.5 )(OH) 2 The precursor is used as a nickel source and a manganese source, which is beneficial to further preparing the composite phase and the material with the layered morphology and further improving the electrochemical performance of the prepared material in the sodium-ion battery.
Preferably, the boron source is H 3 BO 3 At least one of borate and boric acid ester.
In the invention, the raw materials are required to be mixed according to the stoichiometric ratio of the chemical formula (the molar ratio of Na to Mn to Ni to B is (1-1.05): 0.5 to 0.5: x). Furthermore, the content of the P2 phase in the layered sodium electrode material increases with the content of the doped B, and when x is 0.01-0.05; further preferably 0.01 to 0.03; more preferably 0.01 to 0.02, the electrochemical properties of the material are more excellent.
In the present invention, the raw materials may be mixed by conventional means, for example, dry mixing or wet mixing to obtain a mixed material.
In the present invention, the heat treatment is performed in an oxygen-containing atmosphere. The oxygen-containing atmosphere is oxygen, air or a mixed gas of oxygen and protective gas; oxygen is preferred.
Preferably, the temperature in the heat treatment process is 800-850 ℃; further preferably 800 to 830 ℃. The invention can obtain the material with high crystallinity and the composite crystalline phase structure and morphology at the preferable lower temperature.
Preferably, the temperature rise rate in the heat treatment process is 5-10 ℃/min.
The present inventors have also surprisingly found that the atmosphere control during the heat treatment process is another key to influencing the composite phase structure. Preferably, the flow rate of the oxygen-containing atmosphere in the heat treatment process is 0.1-0.5L/min; more preferably 0.2 to 0.3L/min. It was found that controlling the atmosphere flow of the heat treatment in this range enables the successful construction of the composite phase material unexpectedly.
Preferably, the heat treatment time is 12 to 24 hours.
In the invention, in order to further improve the preparation of the material, the mixture is preferably pretreated at the temperature of 400-600 ℃ in advance before the heat treatment; then heat treatment is carried out at the required temperature. It was found that the two-stage heat treatment contributes to further improvement in obtaining the material.
Preferably, the atmosphere of the pretreatment process is an oxygen-containing atmosphere;
the flow rate of the pretreated oxygen-containing atmosphere is 0.1-0.5L/min; further preferably 0.2-0.3L/min;
preferably, the temperature rise rate in the pretreatment process is 1-3 ℃/min;
preferably, the pretreatment time is 4-8 hours.
The invention relates to a preferable NaMn 0.5 Ni 0.5 B x O 2 The preparation method of the material comprises the following steps:
step I: according to the proportion of Na: mn: ni: the molar ratio of the B element is (1-1.05): 0.5: 0.5: x, mixing a nickel-manganese source, a sodium source and a boron source, grinding until no obvious granular sensation exists, and then uniformly mixing the mixed powder at a stirring speed of 200-1200 r/min to obtain a mixture (mixture); the nickel manganese source is (Mn) 0.5 Ni 0.5 )CO 3 Or (Mn) 0.5 Ni 0.5 )(OH) 2 (ii) a The sodium source is sodium carbonate or sodium nitrate powder; the boron source is H 3 BO 3 Powder;
step II: and (4) heating the mixture prepared in the step I to 400-600 ℃ at a heating rate of 1-3 ℃/min in an oxygen or air atmosphere, preserving heat for 4-8 hours, heating to 800-900 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 12-24 hours, and cooling along with a furnace to obtain the required material.
The invention also provides the NaMn 0.5 Ni 0.5 B x O 2 The application of the material is to use the material as a positive active material of a sodium-ion battery.
The research finds that the electrochemical performance of the sodium-ion battery can be unexpectedly improved due to the P2/O3 composite phase structure, the layered morphology and the special control of x of the material.
The invention also provides a sodium ion battery anode comprising the NaMn 0.5 Ni 0.5 B x O 2 A material.
Preferably, the positive electrode comprises a positive electrode current collector and a positive electrode material compounded on the surface of the positive electrode current collector; the positive electrode material comprises a conductive agent, a binder and the NaMn 0.5 Ni 0.5 B x O 2 A material.
The invention also provides a sodium ion battery which contains the NaMn 0.5 Ni 0.5 B x O 2 A material; preferably, the sodium ion battery comprises the positive electrode.
Advantageous effects
1. The invention provides NaMn with a brand-new P2 and O3 composite phase and two-dimensional lamellar morphology 0.5 Ni 0.5 B x O 2 Materials, and has been found to surprisingly improve their electrochemical performance in sodium ion batteries thanks to the composite crystalline phase structure, two-dimensional morphology, and the synergistic control of the formula x.
2. The invention provides a preparation method of the material, which is based on the doping of B and the control of the doping amount of B, and can obtain a P2/O3 composite phase based on a mechanism of partial induced conversion of O3 phase into P2; moreover, the electrochemical performance of the material in the sodium-ion battery can be further improved by further matching with the combined control of a heat treatment mechanism, atmosphere and atmosphere flow.
Compared with the existing doping method, in the preparation method, the layered sodium-electricity positive electrode material with the P2/O3 composite phase is obtained by doping a small amount of B element without reducing the sodium content and changing the transition metal component, the content ratio of P2 and O3 phases in the material can be regulated and controlled by controlling the doping amount of the B element, and the layered sodium-electricity positive electrode material with better crystallinity can be obtained at a lower sintering temperature. Due to the synergistic effect of the P2 phase and the O3 phase in the material, the B-doped P2/O3 composite phase layered sodium electric anode material prepared by the method has excellent electrochemical performance.
Drawings
Figure 1X-ray diffraction pattern of the example 1 positive electrode material;
FIG. 2 is a scanning electron micrograph of the positive electrode material of example 1;
FIG. 3 0.2C cycle test pattern for the positive electrode material of example 1;
FIG. 4X-ray diffraction pattern of the cathode material of example 2;
FIG. 5 0.2C cycle test plot of the positive electrode material of example 2;
FIG. 6X-ray diffraction pattern of the positive electrode material of example 3;
fig. 7 0.2C cycle test plot of example 3 positive electrode material.
Detailed Description
Example 1
NaMn 0.5 Ni 0.5 B x O 2 Preparation of (x ═ 0.01): the method comprises the following steps:
with (Mn) 0.5 Ni 0.5 )CO 3 、Na 2 CO 3 、H 3 BO 3 The powder is taken as a raw material, and the weight ratio of Na: mn: ni: the molar ratio of B is 1.05: 0.5: 0.5: 0.01, placing the raw materials in a mortar, fully grinding and crushing, uniformly stirring at the stirring speed of 450r/min, transferring the uniformly mixed powder into a tube furnace, heating to 450 ℃ at the heating rate of 1 ℃/min under the oxygen atmosphere (the oxygen flow is 0.2L/min), preserving heat for 6h, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 24h, and cooling with the furnace to obtain the B-doped P2/O3 composite phase layered sodium anode material.
And (3) electrochemical performance determination:
uniformly mixing the positive electrode material obtained by the method, acetylene black and PVDF in a mass ratio of 8:1:1 by taking NMP as a medium to prepare slurry, uniformly coating the slurry on an aluminum foil, drying the aluminum foil in vacuum at 120 ℃, cutting the aluminum foil into a positive electrode sheet with the diameter of 12mm, taking a sodium metal sheet as a negative electrode, taking glass fiber GF/D as a diaphragm and 1M NaClO 4 The solution of PC/FEC (95: 5 by volume) as an electrolyte was charged into a glove box filled with argon gas to prepare a CR2016 type coin cell, which was the cell of example 1.
The battery is subjected to charge-discharge cycle test in a blue CT2001A battery test system under the same test conditions, wherein the voltage interval is 2-4V, and the test temperature is 25 ℃.
Comparative example 1
The only difference compared to example 1 is that x is 0. Namely, the B-free doped NaMn is prepared without adding a boron source 0.5 Ni 0.5 O 2 Positive electrode material, this is comparative example 1 material. As can be seen from FIG. 1, compared with comparative example 1, the doped material of example 1 has a P2/O3 composite structure, the distorted phase O3' disappears, and the peak has a sharp shape, a high peak strength and good crystallinity. As can be seen from fig. 2, example 1 after B doping still retains its spherical morphology similar to comparative example 1, but its primary particles are lamellar.
The undoped layered positive electrode material NaMn of the comparative example was measured by the electrochemical measurement method of example 1 0.5 Ni 0.5 O 2 Electrochemical measurements were performed and labeled as comparative example 1 cells.
The electrochemical results of the battery assembled by the materials of the example 1 and the comparative example 1 are shown in fig. 3, and as can be seen from fig. 3, compared with the battery of the comparative example 1, the specific discharge capacity at 0.2 rate of the battery of the example 1 is 117mAh/g (94.1 mAh/g in the comparative example 1), the cycle retention rate after 100 cycles is 97.8%, and the cycle retention rate of the comparative example 1 is only 62.2%, so that the P2/O3 composite structure formed after B doping can effectively improve the structural stability of the layered material, and has excellent discharge capacity, cycle stability and other properties.
Example 2
NaMn 0.5 Ni 0.5 B x O 2 Preparation of (x ═ 0.03): the method comprises the following steps:
with (Mn) 0.5 Ni 0.5 )CO 3 、Na 2 CO 3 、H 3 BO 3 The powder is taken as a raw material, and the weight ratio of Na: mn: ni: the molar ratio of B is 1.05: 0.5: 0.5: 0.03 proportioning, placing the raw materials in a mortar for full grinding and crushing, uniformly stirring at the stirring speed of 700r/min, transferring the uniformly mixed powder into a tube furnace, heating to 500 ℃ at the heating rate of 2 ℃/min in the oxygen atmosphere (the oxygen flow is 0.2L/min), preserving the heat for 4h, heating to 800 ℃ at the heating rate of 8 ℃/min, preserving the heat for 24h, and cooling along with the furnace to obtain the B-doped P2/O3 composite phase layered sodium anode material. As shown in FIG. 4, the material prepared by the stoichiometric doping has a P2/O3 composite phase structure, and has better crystallinity.
Comparative example 2
Compared with example 2, the difference is only that x is 0, and NaMn under the conditions of example 2 is prepared 0.5 Ni 0.5 O 2 Material (different preparation method from comparative example 1, and different internal Structure)
The electrochemical performance of the materials of example 2 and comparative example 2 is determined by the electrochemical method of example 1, and the result is shown in fig. 5, as can be seen from fig. 5, the first-cycle specific discharge capacity of the battery of example 2 is 107mAh/g (88.4 mAh/g in comparative example 2) at 0.2 rate, the cycle retention rate after 100 cycles is 92.0%, and the cycle retention rate of comparative example 1 is only 85.0%, that is, the P2/O3 composite phase structure of the B-doped structure can effectively improve the discharge capacity and the structural stability of comparative example 2, and improve the electrochemical performance.
Example 3
NaMn 0.5 Ni 0.5 B x O 2 Preparation of (x ═ 0.05): the method comprises the following steps:
with (Mn) 0.5 Ni 0.5 )CO 3 、Na 2 CO 3 、H 3 BO 3 The powder is taken as a raw material, and the weight ratio of Na: mn: ni: the molar ratio of B is 1.05: 0.5: 0.5: 0.05 ingredient, placing the raw materials into a mortar for full grinding and crushing, then uniformly stirring the raw materials at the stirring speed of 600r/min, and uniformly mixing the raw materialsThe powder is transferred into a muffle furnace and heated to 400 ℃ at the heating rate of 1 ℃/min in the oxygen atmosphere (the oxygen flow is 0.2L/min), the temperature is kept for 8h, then heated to 850 ℃ at the heating rate of 5 ℃/min, the temperature is kept for 12h, and the B-doped P2/O3 composite structure layered sodium-electricity anode material can be obtained after furnace cooling.
Comparative example 3
Comparative example 3 (comparative example 3) was prepared, differing only in that the oxygen flow rate at the time of heat treatment was changed to 0.8L/min. As can be seen from fig. 6, the setting of the atmosphere flow rate at the heat treatment was too high compared to example 3, and the final phase formation was unfavorable because of the extremely large amount of sodium-deficient P2 phase, the extremely small amount of O3 phase, and the high content of NiO impurity.
The cathode materials obtained in example 3 and comparative example 3 were subjected to electrochemical measurements using the electrochemical method of example 1. As a result, as shown in fig. 7, it can be seen from fig. 7 that the first cycle specific discharge capacity of the battery of example 3 is similar to that of the battery of comparative example 3 at a 0.2C rate, and the capacity is not improved, but the cycle retention rate after 100 cycles is 83.3% (71.8% in comparative example 3).
Example 4:
the only difference compared to example 1 is that the oxygen flow rate was 0.3L/min. As a result, it was found to have a P2/O3 composite phase similar to that of the example, and to have a lamellar morphology. The electrochemical properties of the material of this case were measured by the method of example 1. The results were: the first-circle specific discharge capacity of the battery under the multiplying power of 0.2C is 116.6mAh/g, and the cycle retention rate after 100-circle circulation is 95.9%.

Claims (26)

1. NaMn 0.5 Ni 0.5 B x O 2 A material characterized by: the composite material has P2 and O3 phase composite phases and has two-dimensional lamellar morphology; wherein x is more than 0 and less than or equal to 0.1.
2. NaMn as claimed in claim 1 0.5 Ni 0.5 B x O 2 A material characterized by: and x is 0.01-0.05.
3. As in claimNaMn as described in claim 1 0.5 Ni 0.5 B x O 2 A material characterized by: and x is 0.01-0.03.
4. NaMn as claimed in any one of claims 1 to 3 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: according to the proportion of Na: mn: ni: the molar ratio of the B element is (1-1.05): 0.5: 0.5: x, mixing materials containing a sodium source, a manganese source, a nickel source and a boron source to obtain a mixture; and (3) carrying out heat treatment on the mixture at 800-900 ℃ in an oxygen-containing atmosphere to obtain the composite material.
5. NaMn as claimed in claim 4 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the sodium source is sodium oxide or a salt or hydroxide that can be converted to sodium oxide.
6. NaMn as claimed in claim 5 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the sodium source is at least one of sodium carbonate, sodium nitrate, sodium bicarbonate, sodium acetate and sodium hydroxide.
7. NaMn as claimed in claim 4 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the manganese source is manganese oxide or salt or hydroxide which can be converted into manganese oxide.
8. NaMn as claimed in claim 7 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the manganese source is manganese acetate, manganese nitrate, manganese carbonate, (Mn) 0.5 Ni 0.5 )CO 3 、(Mn 0.5 Ni 0.5 ) (OH) 2 At least one of (1).
9. NaMn as claimed in claim 4 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the nickel source is nickel oxide or a salt or hydroxide that can be converted to nickel oxide.
10. NaMn as claimed in claim 9 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the nickel source is nickel acetate, nickel nitrate, nickel carbonate, (Mn) 0.5 Ni 0.5 )CO 3 、(Mn 0.5 Ni 0.5 ) (OH) 2 At least one of (1).
11. NaMn as claimed in claim 4 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the boron source is H 3 BO 3 At least one of borate and boric acid ester.
12. NaMn as claimed in claim 4 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the temperature of the heat treatment process is 800-850 ℃.
13. NaMn as claimed in claim 4 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the heating rate in the heat treatment process is 5-10 ℃/min.
14. NaMn as claimed in claim 4 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the heat treatment time is 12-24 hours.
15. NaMn as claimed in claim 4 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the flow rate of the oxygen-containing atmosphere in the heat treatment process is 0.1-0.5L/min.
16. NaMn as claimed in claim 4 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the oxygen-containing atmosphere is oxygen, air or a mixed gas of oxygen and protective gas.
17. NaMn as claimed in any of claims 4 to 16 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: before heat treatment, the mixture is pretreated at the temperature of 400-600 ℃.
18. NaMn of claim 17 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the atmosphere of the pretreatment process is an oxygen-containing atmosphere.
19. NaMn as claimed in claim 18 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the flow rate of the pretreated oxygen-containing atmosphere is 0.1-0.5L/min.
20. The NaMn of claim 17 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the temperature rise rate in the pretreatment process is 1-3 ℃/min.
21. The NaMn of claim 17 0.5 Ni 0.5 B x O 2 The preparation method of the material is characterized by comprising the following steps: the pretreatment time is 4-8 hours.
22. NaMn as claimed in any one of claims 1 to 3 0.5 Ni 0.5 B x O 2 Material, or NaMn obtained by the preparation method of any one of claims 4-21 0.5 Ni 0.5 B x O 2 Use of a material characterized by being used as a positive active material for a sodium-ion battery.
23. A positive electrode for sodium ion battery, comprising the positive electrode composition according to any one of claims 1 to 3NaMn of (2) 0.5 Ni 0.5 B x O 2 Material, or NaMn prepared by the preparation method of any one of claims 4-21 0.5 Ni 0.5 B x O 2 A material.
24. The positive electrode of the sodium-ion battery of claim 23, comprising a positive electrode current collector and a positive electrode material compounded on the surface thereof; the positive electrode material comprises a conductive agent, a binder and the NaMn 0.5 Ni 0.5 B x O 2 A material.
25. A sodium ion battery comprising NaMn as defined in any one of claims 1 to 3 0.5 Ni 0.5 B x O 2 Material, or NaMn obtained by the preparation method of any one of claims 4-21 0.5 Ni 0.5 B x O 2 A material.
26. The sodium-ion battery of claim 25, wherein the sodium-ion battery comprises the positive electrode of claim 23 or 24.
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