CN114678520B - Positive electrode material for sodium ion battery and preparation method thereof - Google Patents

Positive electrode material for sodium ion battery and preparation method thereof Download PDF

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CN114678520B
CN114678520B CN202210235717.9A CN202210235717A CN114678520B CN 114678520 B CN114678520 B CN 114678520B CN 202210235717 A CN202210235717 A CN 202210235717A CN 114678520 B CN114678520 B CN 114678520B
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王钦超
吕洁
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Yangzhou 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Inorganic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a positive electrode material for a sodium ion battery, which is P3 type oxide; the composition of the oxide is Na 0.66 Mn 0.6 Ni 0.4‑x Mg x O 2 ，0.1≤x<0.4; na of the P3 Structure of the invention 0.66 Mn 0.6 Ni 0.4‑x Mg x O 2 (0.1≤x<0.4 Has better charge-discharge performance and can be used for charging and discharging at the voltage range of 1.5-4.4V (vs. Na) + Na) and current density of 10-50 mA/g, has large reversible capacity and smaller capacity attenuation, the charge-discharge capacity is 100-180 mAh/g respectively, and the capacity of 70-80% can be maintained after 100 circles of circulation, thus having good reversibility.

Description

Positive electrode material for sodium ion battery and preparation method thereof
Technical Field
The invention relates to a positive electrode material for a sodium ion battery, and also relates to a preparation method of the positive electrode material for the sodium ion battery, belonging to the technical field of electrochemistry. Relates to the technical field of electrochemistry.
Background
In recent years, sodium ion batteries are rapidly developed and gradually applied to the fields of large-scale energy storage and the like. Compared with a lithium ion battery, the sodium ion battery has the advantages of abundant sodium resources, low price and the like, can solve the problems of insufficient lithium resources, high price of the lithium ion battery and the like, and can be applied to the large-scale energy storage field with low mass energy density requirements but low price. Although much research is currently being done on sodium-ion batteries, commercialization of sodium-ion batteries is still difficult to achieve due to the lack of suitable cathode materials. Searching for electrode materials that are inexpensive, have high energy density, and are suitable for mass production is a key to solving commercialization of sodium ion batteries. The positive electrode material of the sodium ion battery in the prior art mainly comprises O3 and P2 type layered oxide, tunnel oxide, polyanion compound and organic positive electrode material, wherein the positive electrode material has low general mass specific capacity (about 100 mAh/g), multiphase change exists in the charging and discharging process, and the cycle stability and the multiplying power performance can not meet the commercialization requirement.
Disclosure of Invention
The invention aims to: aiming at the problems in the prior art, the invention provides a positive electrode material for a sodium ion battery with higher charge-discharge capacity and good cycle performance, and also provides a preparation method of the positive electrode material.
The technical scheme is as follows: the positive electrode material for the sodium ion battery is a P3 type oxide; the composition of the oxide is Na 0.66 Mn 0.6 Ni 0.4-x Mg x O 2 ，0.1≤x<0.4。
Na of the invention 0.66 Mn 0.6 Ni 0.4-x Mg x O 2 The crystal structure of the positive electrode material is determined by X-ray diffraction (XRD), and the XRD result shows that the material is a single phase, belongs to a trigonal system, has a space group of R3m and is a layered material with a P3 structure. The morphology is determined by a Scanning Electron Microscope (SEM), and the spherical particle size is 2-10 mu m.
The preparation method of the positive electrode material for the sodium ion battery comprises the following steps:
(1) Preparation of Mn 0.6 Ni 0.4-x (CO 3 ) 1-x Precursor: mnSO is carried out 4 ·H 2 O and NiSO 4 ·6H 2 O is prepared into solution A; na is mixed with 2 CO 3 And polyacrylamide to prepare a solution B; mixing and stirring the solution A and the solution B; standing for precipitation, and cleaning to obtain Mn 0.6 Ni 0.4-x (CO 3 ) 1-x A precursor;
(2) Mn is added to 0.6 Ni 0.4-x (CO 3 ) 1-x Precursor, na 2 CO 3 And Mg (CH) 3 COO) 2 ·4H 2 Mixing the O evenly, and calcining to obtain the P3 type positive electrode material Na for the sodium ion battery 0.66 Mn 0.6 Ni 0.4-x Mg x O 2 。
Preferably, in step (1), the MnSO 4 ·H 2 O and NiSO 4 ·6H 2 The mol ratio of O is 2-6: 1, a step of; na (Na) 2 CO 3 And the mass ratio of the polyacrylamide is 1:1-2.
Preferably, in step (1), the solution a and the solution B are mixed in a volume ratio of 1:1 to 2.
Preferably, in the step (1), the temperature is 40-50 ℃ and the stirring time is 5-10h.
Preferably, in step (2), the Mn 0.6 Ni 0.4-x (CO 3 ) 1-x Precursor, na 2 CO 3 And Mg (CH) 3 COO) 2 ·4H 2 O molar ratio is 1:0.66:x, 0.1.ltoreq.x<0.4。
Preferably, in the step (2), the calcination temperature is 700-750 ℃ and the calcination time is 20-36 hours.
The positive electrode material synthesized by the method is a single phase of a trigonal system, the space group is R3m, the positive electrode material is a P3 structure material, and the positive electrode material has characteristic peaks of P3 structures at 15.77 degrees, 20.50 degrees, 31.97 degrees, 36.24 degrees and 37.44 degrees according to XRD test of a Cu target, and the characteristic peaks respectively represent (003), (006), (111), (012) and (114) crystal faces. In the P3 structure, metals Mn, ni and Mg respectively form octahedron in O, while Na and O form hexagonal prism, distributed in NaO 2 A layer. Because of the specificity of the P3 structure, a great amount of oxygen can be utilized for oxidation-reduction reaction to provide charge compensation, and the charge compensation device is particularly characterized in that in constant current charge and discharge, an oxidation-reduction reaction platform of oxygen exists above 4.2V voltage, namely in the charge and discharge process: due to the P3 structure of the invention, when the charging is higher than 4.2V, the oxidation-reduction reaction of oxygen starts to occur, ni 2+ /Ni 4+ And O 2- /O - The oxidation-reduction reaction is carried out simultaneously, so that the transition metal oxidation-reduction reaction and the anion valence change are realized, and the charge compensation anode material is provided, and meanwhile, a lot of oxygen elements are generated in the oxidation-reduction reaction of oxygen, so that more charge compensation can be provided, and the anode material has high charge-discharge capacity. Meanwhile, in the charging process, the material is converted from P3 to O3, in the discharging process, the material is converted from O3 to P3, and is completely converted into P3 without O3 structure, thereby realizing that the structure is completedIt is speculated that the ratio of nickel to manganese in the oxide promotes complete reversibility of the material structure.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: (1) Na of the P3 Structure of the invention 0.66 Mn 0.6 Ni 0.4-x Mg x O 2 (0.1≤x<0.4 Has better charge-discharge performance and can be used for charging and discharging at the voltage range of 1.5-4.4V (vs. Na) + Na) and current density of 10-50 mA/g, has large reversible capacity and smaller capacity attenuation, the charge-discharge capacity is 100-180 mAh/g respectively, and the capacity of 70-80% can be maintained after 100 circles of circulation, thus having good reversibility; (2) The invention prepares the anode material by coprecipitation and solid phase synthesis method, and Mn with microsphere shape can be prepared by the coprecipitation method 0.6 Ni 0.4-x (CO 3 ) 1-x The precursor, and the carbonate precursor can be synthesized into the layered oxide with the P3 structure by using a solid phase synthesis method.
Drawings
FIG. 1 is Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 And Na (Na) 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 Is an XRD pattern of X-ray with a wavelength of
FIG. 2 is (a) Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 、(b)Na 0.66 Mn 0.6 Ni 0.2 Mg 0.2 O 2 And (c) Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 SEM images of (a);
FIG. 3 is Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 The electrodes are in a first charge-discharge curve and a second charge-discharge curve with the current density of 0.1C;
FIG. 4 is Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 Charge and discharge capacity curves after cycling for 20 cycles at current densities of 0.1C, 0.2C, 0.5C, 1C and 2C, respectively.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
MnSO is carried out 4 ·H 2 O、NiSO 4 ·6H 2 O is in stoichiometric ratio (molar ratio) 2:1 preparing a solution A with the concentration of transition metal ions of 0.5mol/L, and Na 2 CO 3 And polyacrylamide (Na) 2 CO 3 And polyacrylamide in the system as a spheronizing agent) according to a mass ratio of 1:1, mixing, adding into water, and preparing into solution B with the concentration of the balling agent of 0.5 mol/L; according to the volume ratio of 1:1 mixing the solution A and the solution B, slowly adding the mixture into a stirrer by a peristaltic pump, stirring for 12 hours at 50 ℃, standing for precipitation, and repeatedly cleaning to obtain Mn 0.6 Ni 0.3 (CO 3 ) 0.9 Precipitating the precursor; stoichiometric ratio 1:0.66:0.1 Mn 0.6 Ni 0.3 (CO 3 ) 0.9 、Na 2 CO 3 And Mg (CH) 3 COO) 2 ·4H 2 O is mixed, ground after mixing, and calcined for 36 hours at 700 ℃ after full mixing, thus obtaining Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 And (3) powder.
As shown in FIG. 1, XRD characterization showed that the synthesized Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 Is a single phase, belongs to a trigonal system, and has a space group of R3m. FIG. 2 (a) SEM image shows that Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 The spherical particles are assembled by irregular nano particles with the size of 20-50nm, and the spherical size is 2-10 mu m. 70% of the sample, 20% conductive carbon black was dispersed into a 10% PVDF NMP solution. Uniformly coating the aluminum foil, drying the aluminum foil in a vacuum oven for 12 hours, and punching the aluminum foil into a round electrode plate with the diameter of 14 mm. The round electrode plate is used as a working electrode, sodium foil is used as a counter electrode, glass fiber is used as a diaphragm, and the 2032 button cell is assembled. The electrolyte is 1M NaClO 4 Ec+dec+5% fec (volume ratio of EC to DEC 1:1), the cells were assembled in a glove box filled with argon. The charge and discharge test of the battery is carried out on a Xinwei battery test system。Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 At 1.5-4.4V (vs.Na + In the electrochemical window of/Na), the reversible capacity of charge and discharge is 70-110 mAh/g, and the capacity can still be kept at 70% after 100 circles of circulation.
Example 2
MnSO is carried out 4 ·H 2 O、NiSO 4 ·6H 2 O is in stoichiometric ratio 3:1 preparing a solution A with the concentration of transition metal ions of 0.5mol/L, and Na 2 CO 3 And polyacrylamide (Na) 2 CO 3 And polyacrylamide in the system as a spheronizing agent) according to a mass ratio of 1:1, mixing, adding into water, and preparing into solution B with the concentration of the granulating agent of 0.5 mol/L; according to the volume ratio of 1:1 mixing the solution A and the solution B, slowly adding the mixture into a stirrer by a peristaltic pump, stirring for 12 hours at 50 ℃, standing for precipitation, and repeatedly cleaning to obtain Mn 0.6 Ni 0.2 (CO 3 ) 0.8 Precipitating the precursor; stoichiometric ratio 1:0.66:0.2 Mn 0.6 Ni 0.2 (CO 3 ) 0.8 、Na 2 CO 3 And Mg (CH) 3 COO) 2 ·4H 2 O is mixed, ground after mixing, and calcined for 36 hours at 700 ℃ after full mixing, thus obtaining Na 0.66 Mn 0.6 Ni 0.2 Mg 0.2 O 2 And (3) powder.
XRD characterization showed that the synthesized Na 0.66 Mn 0.6 Ni 0.2 Mg 0.2 O 2 Is a single phase, belongs to a trigonal system, and has a space group of R3m. The SEM image of FIG. 2 (b) shows that Na 0.66 Mn 0.6 Ni 0.2 Mg 0.2 O 2 The spherical particles are assembled by irregular nano particles with the size of 20-50nm, and the spherical size is 2-10 mu m. 70% of the sample, 20% conductive carbon black was dispersed into a 10% PVDF NMP solution. Uniformly coating the aluminum foil, drying the aluminum foil in a vacuum oven for 12 hours, and punching the aluminum foil into a round electrode plate with the diameter of 14 mm. The active material-carrying electrode sheet is used as a working electrode, and sodium foil is used as a counter electrode to form the button cell. The electrolyte is 1M NaClO 4 Ec+de+5% fec (volume ratio of EC to DEC 1:1), the cell was assembled in an argon filled glove boxIs carried out. The charge and discharge test of the battery was performed on a new battery test system. Na (Na) 0.66 Mn 0.6 Ni 0.2 Mg 0.2 O 2 The electrodes of the samples exhibited good electrochemical performance. In the charge and discharge of 1.5-4.4V (vs. Na + in/Na), the reversible charge-discharge capacity is respectively 60-120 mAh/g, and the capacity is still kept 70% after 100 circles of circulation.
Example 3
MnSO is carried out 4 ·H 2 O、NiSO 4 ·6H 2 O is in stoichiometric ratio 6:1 preparing a solution A with the concentration of transition metal ions of 0.5mol/L, and Na 2 CO 3 And polyacrylamide (Na) 2 CO 3 And polyacrylamide in the system as a spheronizing agent) according to a mass ratio of 1:1, mixing, adding into water, and preparing into solution B with the concentration of the granulating agent of 0.5 mol/L; according to the volume ratio of 1:1 mixing the solution A and the solution B, slowly adding the mixture into a stirrer by a peristaltic pump, stirring for 12 hours at 50 ℃, standing for precipitation, and repeatedly cleaning to obtain Mn 0.6 Ni 0.1 (CO 3 ) 0.7 Precipitating the precursor; stoichiometric ratio 1:0.66:0.3 Mn 0.6 Ni 0.1 (CO 3 ) 0.7 、Na 2 CO 3 And Mg (CH) 3 COO) 2 ·4H 2 O is mixed, ground after mixing, and calcined for 36 hours at 700 ℃ after full mixing, thus obtaining Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 And (3) powder.
XRD characterization showed that the synthesized Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 Is a single phase, belongs to a trigonal system, and has a space group of R3m. The SEM image of FIG. 2 (a) shows that Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 The spherical particles are assembled by irregular nano particles with the size of 20-50nm, and the spherical size is 2-10 mu m. 70% of the sample, 20% conductive carbon black was dispersed into a 10% PVDF NMP solution. Uniformly coating the aluminum foil, drying the aluminum foil in a vacuum oven for 12 hours, and punching the aluminum foil into a round electrode plate with the diameter of 14 mm. The round electrode plate is used as a working electrode, and sodium foil is used as a counter electrode to form the button cell. The electrolyte is 1M NaClO 4 Ec+dec+5% fec (volume ratio of EC to DEC 1:1), cell assembly was performed in an argon filled glove box. The charge and discharge test of the battery was performed on a new battery test system. Na (Na) 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 Good electrochemical properties are exhibited. As shown in FIG. 3, the voltage at the time of charge and discharge is 1.5 to 4.4V (vs.Na + Na), na (Na) 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 The first charge capacity is 225mAh/g, and the first discharge capacity is 125mAh/g. FIG. 4 shows Na at different current densities 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 After 20 circles of circulation, the charge-discharge reversible capacity is respectively 60-150 mAh/g, and the capacity is still 80% after 100 circles of circulation.
Example 1 Synthesis of P3-Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 The ratio of Mn in the transition metal is 0.6, and the ratio of Ni and Mg is 3:1, the oxidation-reduction reaction of oxygen can be promoted. EXAMPLE 2 Synthesis of P3-Na 0.66 Mn 0.6 Ni 0.2 Mg 0.2 O 2 The positive electrode material has a Mn to Ni to Mg ratio of 3:1:1 and belongs to the P3 positive electrode material, and the positive electrode material has a charge/discharge voltage of 1.5-4.4V (vs. Na + in/Na), the reversible charge-discharge capacity is respectively 60-120 mAh/g, and the capacity is still kept 70% after 100 circles of circulation. During the charge and discharge processes, ni and O both participate in the oxidation-reduction reaction, and charge compensation is provided together, so that the electrode material has high charge and discharge capacity. For synthesizing Na of P3 structure 0.66 Mn 0.6 Ni 0.4-x Mg x O 2 The Mg content must be controlled to 0.1 x<In the range of 0.4. When the content of Mg is less than 0.1, the synthesized Na 0.66 Mn 0.6 Ni 0.4-x Mg x O 2 Belonging to the P2 structure (P63/mmc unit cell). When Na is 0.66 Mn 0.6 Mg 0.4 O 2 In this case, it is difficult to synthesize a pure P3 phase, which contains a large amount of MgO impurity.
Examples 1 to 3 synthetic P3-Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 ，P3-Na 0.66 Mn 0.6 Ni 0.2 Mg 0.2 O 2 And P3-Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 The proportion of Ni and Mg in the positive electrode material of the sodium ion battery is different. During charge and discharge, ni 2 + /Ni 3+ 、Ni 3+ /Ni 4+ With O 2- /O - The redox reaction provides a different amount of charge compensation. In general, P3-Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 Middle Ni 2+ /Ni 3+ 、Ni 3+ /Ni 4+ The reaction provides a relatively large charge, and shows a relatively long charge-discharge slope below 4.3V. And P3-Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 In Ni 2+ /Ni 3+ 、Ni 3+ /Ni 4+ The charge provided by the reaction is minimal, while the valence of oxygen (O 2- /O - Reaction) provides the most charge. Overall, with increasing Mg content, P3-Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 Maximum reversible capacity of (2), next P3-Na 0.66 Mn 0.6 Ni 0.2 Mg 0.2 O 2 And P3-Na 0.66 Mn 0.6 Ni 0.3 Mg 0.1 O 2 Is minimized. That is, as the Mg content increases, the charge provided by Ni decreases and the charge compensation provided by the redox reaction of oxygen increases. At Na (Na) 0.66 Mn 0.6 Ni 0.4-x Mg x O 2 In the positive electrode material, as the content of Mg is increased gradually, the Na-O-Mg configuration is increased gradually, and more O connected with Na and Mg has lone pair electrons, so that more O participates in oxidation-reduction reaction to provide capacity. Thus P3-Na 0.66 Mn 0.6 Ni 0.1 Mg 0.3 O 2 The reversible capacity of the catalyst is maximum, and the cycle stability and the rate capability are most excellent; while the Ni content is increased, ni 2+ /Ni 4+ The charge provided by oxidation-reduction reaction is increased, which is beneficial to promoting the valence change of transition metal to provide capacity, ni 2+ /Ni 4+ And O 2- /O - The redox reactions proceed simultaneously.

Claims (7)

1. A positive electrode material for sodium ion batteries is characterized in that: the positive electrode material is P3 type oxide; the composition of the oxide is Na 0.66 Mn 0.6 Ni 0.4-x Mg x O 2 ，0.1≤x<0.4。
2. A method for preparing the positive electrode material for sodium ion battery according to claim 1, comprising the steps of:
(1) Preparation of Mn 0.6 Ni 0.4-x (CO 3 ) 1-x Precursor: mnSO is carried out 4 ·H 2 O and NiSO 4 ·6H 2 O is prepared into solution A; na is mixed with 2 CO 3 And polyacrylamide to prepare a solution B; mixing and stirring the solution A and the solution B; standing for precipitation, and cleaning to obtain Mn 0.6 Ni 0.4-x (CO 3 ) 1-x A precursor;
(2) Mn is added to 0.6 Ni 0.4-x (CO 3 ) 1-x Precursor, na 2 CO 3 And Mg (CH) 3 COO) 2 ·4H 2 Mixing the O evenly, and calcining to obtain the P3 type anode material Na 0.66 Mn 0.6 Ni 0.4-x Mg x O 2 。
3. The preparation method according to claim 2, characterized in that: in step (1), the MnSO 4 ·H 2 O and NiSO 4 ·6H 2 The mol ratio of O is 2-6: 1, a step of; na (Na) 2 CO 3 And the mass ratio of the polyacrylamide is 1:1-2.
4. The preparation method according to claim 2, characterized in that: in the step (1), the solution A and the solution B are mixed according to a volume ratio of 1:1 to 2.
5. The preparation method according to claim 2, characterized in that: in the step (1), the temperature is 40-50 ℃ and the stirring time is 5-10h in the mixing and stirring process.
6. The preparation method according to claim 2, characterized in that: in step (2), the Mn 0.6 Ni 0.4-x (CO 3 ) 1-x Precursor, na 2 CO 3 And Mg (CH) 3 COO) 2 ·4H 2 O molar ratio is 1:0.66:x, 0.1.ltoreq.x<0.4。
7. The preparation method according to claim 2, characterized in that: in the step (2), the calcination temperature is 700-750 ℃ and the calcination time is 20-36 hours.
CN202210235717.9A 2022-02-17 2022-03-10 Positive electrode material for sodium ion battery and preparation method thereof Active CN114678520B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107946581A (en) * 2017-11-29 2018-04-20 复旦大学 A kind of power-type sodium-ion battery positive material and preparation method thereof
CN111224093A (en) * 2019-10-12 2020-06-02 南方科技大学 Electrode material with manganese concentration gradient, preparation method thereof and sodium-ion battery
CN113675394A (en) * 2021-07-08 2021-11-19 南京大学深圳研究院 Potassium ion battery positive electrode material, preparation method and potassium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107946581A (en) * 2017-11-29 2018-04-20 复旦大学 A kind of power-type sodium-ion battery positive material and preparation method thereof
CN111224093A (en) * 2019-10-12 2020-06-02 南方科技大学 Electrode material with manganese concentration gradient, preparation method thereof and sodium-ion battery
CN113675394A (en) * 2021-07-08 2021-11-19 南京大学深圳研究院 Potassium ion battery positive electrode material, preparation method and potassium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
多金属共掺杂制备Na_(0.67)Mn_(0.67)Ni_(0.33-x)Co_xO_2钠离子电池正极材料及电化学性能优化机理研究;张远朋;赵方晖;张国举;杨洁;段连峰;;机械工程学报(10);全文 *

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