CN113845158B - Preparation method of porous spherical-structure sodium nickel manganese oxide cathode material - Google Patents

Preparation method of porous spherical-structure sodium nickel manganese oxide cathode material Download PDF

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CN113845158B
CN113845158B CN202111427422.3A CN202111427422A CN113845158B CN 113845158 B CN113845158 B CN 113845158B CN 202111427422 A CN202111427422 A CN 202111427422A CN 113845158 B CN113845158 B CN 113845158B
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nickel
manganese
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carbonate
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CN113845158A (en
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童汇
季勇
喻万景
郭学益
丁治英
田庆华
何海梅
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Central South University
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    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • 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 preparation method of a porous spherical structure sodium nickel manganese oxide anode material, which comprises the following steps: (1) adding a nickel-manganese metal salt solution, a carbonate precipitator solution and a complexing agent solution into a reaction kettle filled with a base solution to carry out coprecipitation reaction to obtain a nickel-manganese binary carbonate precursor with a solid structure and different internal and external crystallinities; (2) calcining the nickel-manganese binary carbonate precursor with the solid structure, and decomposing the nickel-manganese binary carbonate with the solid structure to obtain a nickel-manganese binary oxide precursor with a layered structure; (3) and uniformly mixing the nickel-manganese binary oxide precursor with the layered structure with sodium salt, and calcining to obtain the porous spherical nickel-sodium manganate anode material. The sodium nickel manganese oxide anode material prepared by the invention is of a porous spherical structure, has excellent rate performance and cycling stability under high rate, and has higher energy density.

Description

Preparation method of porous spherical-structure sodium nickel manganese oxide cathode material
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a preparation method of a sodium cathode material.
Background
Lithium Ion Batteries (LIBs) have advantages of high energy density, long cycle life, high safety, etc., as compared to conventional batteries, and have been widely used in small portable electronic devices. However, in large-scale energy storage applications such as fixed energy storage systems with low power density requirements, since large-scale energy storage devices consume much lithium element, the low content of lithium in the earth's crust (0.0017%), high cost and uneven distribution become factors that limit the development of lithium batteries. It is therefore necessary to find another low cost alternative. Because of abundant sodium resource, easy acquisition and low cost, the development of Sodium Ion Battery (SIB) has been increasingly advancedThe more attention is paid. Wherein, the layered sodium transition metal oxide cathode material NaxMO2(M = Fe, Mn, Ni, Co, Cr and combinations thereof), has gained wide attention due to its high energy density, simple structure and easy synthesis, and has very high application potential.
P2-Na0.67Mn0.67Ni0.33O2The sodium-containing lithium ion battery is a classic sodium-containing battery anode material, and is popular among a large number of researchers for storing energy due to the fact that the sodium-containing lithium ion battery anode material is large in specific capacity, high in working voltage and capable of stably existing in air. In the research on the P2 phase nickel-manganese-based cathode material, the defects of complex phase change, easy structure collapse, limited energy density and the like inherent in the layered transition metal material in the charging and discharging process limit the further development of the layered transition metal material. In order to improve the electrochemical performance of the positive electrode material of the P2 phase nickel manganese-based sodium ion battery, the main methods adopted by the current research are methods of doping substitution, controlling the micro morphology, coating oxides, manufacturing mixed phases and the like, so as to improve the performance of the material from different angles. Research shows that the reasonably designed structure can enable sodium ions to be rapidly de-intercalated in the structure, and meanwhile, structural stress in the charge and discharge process is relieved, so that the electrochemical performance of the material is improved.
CN109599553A discloses a hollow spherical sodium nickel manganese material and a preparation method thereof, and hollow spherical Na is prepared0.5Ni0.25Mn0.75O2The anode material improves the cycling stability of the material. However, in a voltage window of 1.5-3.0V and under the current multiplying power of 2C, the specific capacity of the material is only 56.28% under the multiplying power of 0.1C, the large-multiplying-power discharge capacity is low, the working voltage of the material is low, and the energy density is low. In addition, the hollow sphere structure can reduce the energy density of the material, which is not suitable for commercial production.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the background technology and provide a preparation method of a porous spherical structure sodium nickel manganese oxide cathode material with excellent rate performance. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a porous spherical structure sodium nickel manganese oxide cathode material comprises the following steps:
(1) adding a nickel-manganese metal salt solution, a carbonate precipitator solution and a complexing agent solution into a reaction kettle filled with a base solution to carry out coprecipitation reaction to obtain a nickel-manganese binary carbonate precursor with a solid structure and different internal and external crystallinities;
(2) calcining the solid-structure nickel-manganese binary carbonate precursor obtained in the step (1), and decomposing the solid-structure nickel-manganese binary carbonate to obtain a layered-structure nickel-manganese binary oxide precursor;
(3) and (3) uniformly mixing the nickel-manganese binary oxide precursor with the layered structure obtained in the step (2) with sodium salt (the amount of the sodium salt is determined according to the molecular formula of the anode material), and calcining to obtain the porous spherical nickel-manganese oxide anode material.
In the above preparation method, preferably, the specific process of the coprecipitation reaction in step (1) is as follows: dropwise adding a nickel-manganese metal salt solution, a carbonate precipitator solution and a complexing agent solution into the base solution, controlling reaction conditions to carry out coprecipitation reaction, and after complete reaction, aging, filtering, washing and drying to obtain the nickel-manganese binary carbonate precursor with a solid structure.
In the preparation method, preferably, the nickel-manganese binary oxide precursor is of an onion-like spherical structure, and the single-layer thickness is 0.01-1 μm; the nickel sodium manganate anode material with the porous spherical structure is porous and spherical, and the particle size is 5-30 mu m; the chemical formula of the porous spherical structure sodium nickel manganese oxide anode material is NaxNiyMn1-yO2(ii) a Wherein: x is more than or equal to 0.44<1，0≤y≤0.5。
In the above preparation method, preferably, the manganese salt in the nickel-manganese metal salt solution includes one or more of manganese sulfate, manganese formate, manganese acetate or manganese nitrate, more preferably manganese sulfate, and the nickel salt is one or more of nickel sulfate, nickel formate, nickel acetate or nickel nitrate, more preferably nickel sulfate; the concentration of metal ions in the nickel-manganese metal salt solution is 0.5-5 mol/L; the sodium salt comprises one or more of sodium carbonate, sodium hydroxide, sodium acetate, sodium nitrate, sodium formate and sodium iodide, and sodium carbonate is more preferable.
In the above preparation method, preferably, the carbonate in the carbonate precipitant solution includes one or more of sodium carbonate, sodium bicarbonate, ammonium bicarbonate or ammonium carbonate; the concentration of the carbonate precipitant solution is 1-5 mol/L. More preferably, sodium carbonate.
In the above preparation method, preferably, the concentration of the complexing agent solution is 0.5 to 2 mol/L; the complexing agent solution contains ammonia water and ammonium bicarbonate, and the molar ratio of the ammonium bicarbonate to the ammonia water is (0.1-1): 1. the invention directly adjusts the components and the proportion of the complexing agent to control the crystal growth, does not need to adjust the concentration of the complexing agent in the experimental process, and is more controllable. In the present invention, too high or too low a molar ratio of ammonium bicarbonate to ammonia is detrimental to the growth of the precursor. The proportion is too high, the precursor grows too fast, so that the material structure is evacuated, mechanical pulverization can occur in the circulation process, and the tap density is too low; the proportion is too low, the crystallinity inside and outside the precursor is consistent, holes cannot be generated in the material in the sintering process, a porous spherical structure cannot be obtained, and the rate capability cannot be improved.
In the above preparation method, preferably, the concentration of the base solution is 0.1 to 0.5 mol/L; the base solution contains ammonia water and ammonium bicarbonate, and the molar ratio of the ammonium bicarbonate to the ammonia water is (0.1-1): 1.
in the above preparation method, preferably, during the coprecipitation reaction, the molar ratio of the nickel-manganese metal salt solution, the carbonate precipitant solution, and the complexing agent solution is controlled to be 1: 1: (0.1-0.5).
In the above preparation method, preferably, during the coprecipitation reaction, the pH value of the reaction system is controlled to be 7-9 (more preferably 8-8.5), the stirring speed is 500-1200rpm, the temperature is 40-60 ℃, and the reaction time is 5-30 h. Sufficient reaction time is given for precipitation so as to enable particles to grow excellent morphology, and the morphology of the precursor directly influences the electrochemical performance of the material.
In the above preparation method, preferably, in the step (2), the temperature is raised from room temperature to 300-700 ℃ at a temperature raising rate of 1-5 ℃/min during calcination, and the calcination is carried out for 3-10 h. The calcination step of the invention can lead the carbonate precursor to be decomposed into the onion-like oxide, thereby facilitating the generation of a porous layered structure in the subsequent sintering process. The excessive sintering temperature can cause the crystal growth to be too large, thereby causing the transmission distance of internal sodium ions to be increased, the multiplying power performance to be reduced, and causing the material to be pulverized in the circulating process due to the excessively large sphere; the low sintering temperature can reduce the crystallinity of the material, and the problems of unobvious layered structure and generation of impurity phase can occur. Too long sintering time can also cause the problem of too large crystal growth; too short a sintering time may result in fewer voids and insufficient crystallinity of the material, thereby reducing the cycle rate performance of the material.
In the preparation method, preferably, in the step (3), the calcination includes pre-calcination and re-calcination, wherein the pre-calcination is performed by heating from room temperature to 300-600 ℃ at a heating rate of 1-10 ℃/min for 4-10 h; the re-calcination is to heat up to 800-950 ℃ at the heating rate of 1-10 ℃/min, and the calcination is carried out for 6-15 h. More preferably, the temperature is raised to 500 ℃ at the temperature raising rate of 5 ℃/min and is kept for presintering for 5h, and then the temperature is raised to 900 ℃ at the temperature raising rate of 5 ℃/min and is calcined for 12 h.
According to the invention, by controlling the components of the complexing agent, a nickel-manganese binary carbonate precursor with multiple crystallinity is prepared by adopting a simple coprecipitation method, and after calcination, a certain amount of sodium salt is mixed and ground, and then pre-calcination and re-calcination are carried out, so that the porous spherical sodium-ion battery sodium nickel-manganese anode material is successfully synthesized. In particular, the ammonia water and ammonium bicarbonate bi-component complexing agent solution adopted by the invention can cause the hydrolysis reaction of ammonium bicarbonate in the system, can accelerate the coordination complex reaction in a coprecipitation system, leads the growth speed of crystal grains to be gradually higher than the nucleation speed, leads the internal and external crystallinity of the nickel-manganese binary carbonate precursor to be different, during the pre-calcination process, because of the different crystallinity, the sphere shrinks to form a multilayer structure (if the growth rate and the nucleation rate are not controlled, the material can not obtain a porous structure by sintering), then proper sodium salt is mixed, in the sintering process, sodium ions can diffuse like the inside to destroy the layered structure and generate holes, so that the whole anode material has a porous spherical structure, the porous structure can better expose an electrochemical active interface, the diffusion distance of the sodium ions is shortened, and the effect of improving the material performance is achieved. In addition, the anode material provided by the invention has uniform particles, and overcomes the defects of poor rate capability and low high-rate cycle stability of the sodium nickel manganese oxide anode material.
Compared with the prior art, the invention has the advantages that:
1. in the prior art, most of the nickel sodium manganate anode material is irregular polygon or hollow sphere, so that the rate capability of the material is poor, and the tap density of the material is low due to the irregular shape. The porous spherical structure sodium nickel manganese oxide anode material prepared by the invention can ensure that more gaps are formed in the material in the polycrystalline precursor sintering process, and the porous structure can enable electrolyte to more fully infiltrate the interior of the material, so that the electrochemical reaction is more rapid. In addition, the porous structure can shorten the transmission distance of internal sodium ions and improve the rate capability of the material. And compared with a hollow structure, the porous structure has higher mechanical strength and higher energy density besides higher tap density, can ensure that the material does not have the phenomena of pulverization and the like in the circulating process, is less prone to collapse in the structure in the charging and discharging process, and has better circulating stability.
2. The sodium nickel manganese oxide cathode material prepared by the invention is of a porous spherical structure, has excellent rate capability, for example, has a specific capacity of 65.6mAh/g under a high current density of 25C (1C =160 mA/g), is 77.5% under a current density of 1C, circulates for 300 circles under a current density of 10C and a voltage range of 2-4.15V, has a capacity retention rate of 86.4%, and has excellent rate capability and cycle stability under high rate.
3. The voltage window of the sodium nickel manganese oxide anode material is 2-4.15V, and Ni ions are utilized for charging and discharging, so that the sodium nickel manganese oxide anode material has higher working voltage and higher energy density.
4. The preparation method has the advantages of low synthesis cost, easily available raw materials, simple synthesis method, easy operation, short synthesis period, safe and effective battery and suitability for large-scale production.
5. The invention adopts a commercial coprecipitation method to prepare the precursor, and the preparation process is more continuous and has more commercial prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an SEM image of a nickel manganese binary oxide precursor having a layered structure prepared in example 1.
Fig. 2 is an SEM image of the porous spherical structure sodium nickel manganese oxide cathode material prepared in example 1.
Fig. 3 is an SEM image of a cross section of the porous spherical structure sodium nickel manganese oxide cathode material prepared in example 1.
Fig. 4 is an X-ray diffraction pattern of the porous spherical structure sodium nickel manganese oxide cathode material prepared in example 1.
Fig. 5 is a first charge-discharge curve diagram of a button cell assembled by the porous spherical structure sodium nickel manganese oxide cathode material prepared in example 1 at a discharge rate of 0.1C.
Fig. 6 is a cycling curve at 10C discharge rate for a button cell assembled with the porous spherical structure sodium nickel manganese oxide positive electrode material prepared in example 1.
Fig. 7 is a graph of button cells assembled with the sodium nickel manganese oxide positive electrode material of the sodium ion battery with a porous spherical structure prepared in example 1 under different multiplying power.
Fig. 8 is an SEM image of a cross-section of the nickel manganese binary oxide precursor prepared in comparative example 1.
Fig. 9 is an SEM image of the dense spherical structure sodium nickel manganese oxide cathode material prepared in comparative example 1.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a preparation method of a porous spherical structure sodium nickel manganese oxide cathode material comprises the following steps:
(1) preparing a nickel-manganese binary carbonate precursor: according to manganese sulfate: the nickel sulfate is 2: 1, weighing raw materials according to the molar ratio, and dissolving the raw materials in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution; according to ammonia water: ammonium bicarbonate is 4: 1, respectively preparing 0.5mol/L ammonia water/ammonium bicarbonate mixed complexing agent solution and 0.1mol/L ammonia water/ammonium bicarbonate base solution.
Adding a mixed metal salt solution, a 2mol/L sodium carbonate precipitant solution and a 0.5mol/L ammonia water/ammonium bicarbonate mixed complexing agent solution into the 0.1mol/L ammonia water/ammonium bicarbonate mixed base solution by a peristaltic pump by adopting a coprecipitation method, and controlling the molar ratio of the mixed metal salt, the precipitant sodium carbonate and the ammonia water/ammonium bicarbonate mixed complexing agent to be 1: 1: 0.4, reacting for 20 hours under the conditions that the pH value is 8, the stirring speed is 950 revolutions per minute and the temperature is 50 ℃, filtering after the reaction is finished, repeatedly washing, removing impurities and drying to obtain a nickel-manganese binary carbonate precursor (Mn) with a solid structure0.67Ni0.33）CO3。
(2) And (2) heating the nickel-manganese binary carbonate precursor with the solid structure in the step (1) from room temperature to 500 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-manganese binary oxide precursor with the multilayer onion-like structure, wherein the microscopic view of the nickel-manganese binary oxide precursor is shown in figure 1.
(3) Mixing and grinding 0.01mol of the nickel-manganese binary oxide precursor in the step (2) and 0.0105mol of sodium carbonate (Na is excessive by 5%), putting the mixture into a muffle furnace, heating the mixture to 500 ℃ at the heating rate of 5 ℃/min in the air atmosphere for presintering for 5h, heating the mixture to 900 ℃ at the same heating rate for calcining for 12h, and obtaining the porous spherical nickel-manganese acid sodium anode material Na0.67Mn0.67Ni0.33O2The microscopic view thereof is shown in FIGS. 2 and 3.
Fig. 1 is an SEM image of a nickel manganese binary oxide precursor of a multilayer onion-like structure prepared in example 1, the particle size is about 20 μm, and the material is in a layer-by-layer onion-like spherical shape. Fig. 2 and 3 are SEM images and sectional SEM images of the porous spherical structure sodium nickel manganese oxide positive electrode material prepared in example 1, and it can be seen from the images that the particle size is about 20 μm and the material has a porous spherical structure. FIG. 4 is an X-ray diffraction pattern of the porous spherical sodium nickel manganese oxide cathode material prepared in example 1, all peaks corresponding to standard cards, demonstrating successful Na synthesis0.67Mn0.67Ni0.33O2And (3) a positive electrode material.
Assembling the battery: weighing 0.2000g of the sodium nickel manganese oxide positive electrode material obtained in the embodiment, adding 0.0250g of conductive carbon black serving as a conductive agent and 0.0250g of PVDF (polyvinylidene fluoride) serving as a binder, uniformly mixing, coating on an aluminum foil to prepare a positive electrode plate, taking a metal sodium plate as a negative electrode in a vacuum glove box, taking a battery diaphragm as a Whatman GF/D glass fiber diaphragm, and taking 1mol/L of NaClO electrolyte as4(EC: DMC = 1: 1 (vol) +5% FEC), assembled into a CR2025 button cell.
The sodium nickel manganese oxide anode material prepared by the embodiment has a porous spherical shape, and the spherical size is relatively uniform, and is specifically represented by the spherical particle size of the material being 15-20 microns. After the material is assembled into a half-cell, electrochemical performance test is carried out within the interval of 2-4.15V, and as shown in figure 5, the first discharge specific capacity can reach 82.4 mAh/g. The prepared cathode material is subjected to rate capability test, and as shown in fig. 6, the discharge specific capacities of the prepared cathode material at 1, 2, 5, 10, 20 and 25C are respectively 84.6, 84.3, 82.7, 80, 72 and 65.6 mAh/g; as shown in FIG. 7, the first specific discharge capacity at a current rate of 10C can reach 81.4mAh/g, the specific discharge capacity after 300 cycles at 10C can reach 70.3mAh/g, and the capacity retention rate is 86.4%.
Example 2:
a preparation method of a porous spherical structure sodium nickel manganese oxide cathode material comprises the following steps:
(1) preparing a nickel-manganese binary carbonate precursor: according to manganese sulfate: nickel sulfate is 1: 1, weighing raw materials according to the molar ratio, and dissolving the raw materials in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution; according to ammonia water: ammonium bicarbonate is 4: 1, respectively preparing 0.5mol/L ammonia water/ammonium bicarbonate mixed complexing agent solution and 0.1mol/L ammonia water/ammonium bicarbonate base solution.
Adding a mixed metal salt solution, a 2mol/L sodium carbonate precipitant solution and a 0.5mol/L ammonia water/ammonium bicarbonate mixed complexing agent solution into the 0.1mol/L ammonia water/ammonium bicarbonate mixed base solution by a peristaltic pump by adopting a coprecipitation method, and controlling the molar ratio of the mixed metal salt, the precipitant sodium carbonate and the ammonia water/ammonium bicarbonate mixed complexing agent to be 1: 1: 0.4, reacting for 20 hours under the conditions that the pH value is 8, the stirring speed is 950 revolutions per minute and the temperature is 50 ℃, filtering after the reaction is finished, repeatedly washing, removing impurities and drying to obtain a nickel-manganese binary carbonate precursor (Mn) with a solid structure0.5Ni0.5)CO3。
(2) And (2) heating the nickel-manganese binary carbonate precursor with the solid structure in the step (1) from room temperature to 450 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-manganese binary oxide precursor with the multilayer onion-like structure.
(3) Mixing and grinding 0.01mol of the nickel-manganese binary oxide precursor in the step (2) and 0.0105mol of sodium carbonate (Na is excessive by 5%), putting the mixture into a muffle furnace, heating the mixture to 450 ℃ at the heating rate of 5 ℃/min in the air atmosphere for presintering for 5h, heating the mixture to 900 ℃ at the same heating rate for calcining for 12h, and obtaining the nickel-manganese positive electrode material Na with the porous spherical structure0.67Mn0.5Ni0.5O2。
Assembling the battery: the same as in example 1.
The sodium nickel manganese oxide anode material prepared by the embodiment has a porous spherical shape, and the spherical size is relatively uniform, and is specifically represented by the spherical particle size of the material being 10-20 μm. After the material is assembled into a half battery, electrochemical performance test is carried out within the range of 2-4.15V, and the first discharge specific capacity can reach 81.2 mAh/g. The prepared anode material is subjected to rate capability test, and the discharge specific capacities of the anode material at 1, 2, 5, 10, 20 and 25 ℃ are respectively 84.2, 75.4, 72.7, 69, 60.1 and 53.6 mAh/g; the first discharge specific capacity can reach 69.6mAh/g under the current multiplying power of 10C, the discharge specific capacity can reach 50.3mAh/g after 300 cycles under 10C, and the capacity retention rate is 72.2%.
Example 3:
a preparation method of a porous spherical structure sodium nickel manganese oxide cathode material comprises the following steps:
(1) preparing a nickel-manganese binary carbonate precursor: according to manganese sulfate: the nickel sulfate is 2: 1, weighing raw materials according to the molar ratio, and dissolving the raw materials in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution; respectively preparing ammonia water: ammonium bicarbonate is 1: 1, respectively preparing 0.5mol/L ammonia water/ammonium bicarbonate mixed complexing agent solution and 0.1mol/L ammonia water/ammonium bicarbonate base solution.
Adding a mixed metal salt solution, a 2mol/L sodium carbonate precipitant solution and a 0.5mol/L ammonia water complexing agent solution into the 0.1mol/L ammonia water base solution by a peristaltic pump by adopting a coprecipitation method, and controlling the molar ratio of the mixed metal salt, the precipitant sodium carbonate and the ammonia water/ammonium bicarbonate mixed complexing agent to be 1: 1: 0.4, reacting for 20 hours under the conditions that the pH value is 8, the stirring speed is 950 revolutions per minute and the temperature is 50 ℃, filtering after the reaction is finished, repeatedly washing, removing impurities and drying to obtain a nickel-manganese binary carbonate precursor (Mn) with a solid structure0.67Ni0.33)CO3。
(2) And (2) heating the nickel-manganese binary carbonate precursor with the solid structure in the step (1) from room temperature to 550 ℃ at the heating rate of 5 ℃/min, and calcining for 6h to obtain the nickel-manganese binary oxide precursor with the multilayer onion-like structure.
(3) 0.01mol of nickel-manganese binary oxide precursor in the step (2) and 0.0 mol of nickel-manganese binary oxide precursor105mol of sodium carbonate (Na is excessive by 5 percent) is mixed and ground, then the mixture is put into a muffle furnace, the temperature is raised from room temperature to 550 ℃ for pre-burning for 6h at the temperature raising rate of 5 ℃/min in the air atmosphere, and the temperature is raised to 900 ℃ at the same temperature raising rate for calcining for 12h, so that the sodium nickel manganese oxide anode material Na with a porous spherical structure is obtained0.67Mn0.67Ni0.33O2。
Assembling the battery: the same as in example 1.
The sodium nickel manganese oxide anode material prepared by the embodiment has a porous spherical shape, and the spherical size is relatively uniform, and is specifically represented by the spherical particle size of the material being 10-20 μm. After the material is assembled into a half battery, electrochemical performance test is carried out within the range of 2-4.15V, and the first discharge specific capacity can reach 76.2 mAh/g. The prepared anode material is subjected to rate capability test, and the discharge specific capacities of the anode material at 1, 2, 5, 10, 20 and 25 ℃ are respectively 76.2, 73.8, 70.7, 62.3, 54.6 and 50.2 mAh/g; the first discharge specific capacity can reach 63.8mAh/g under the current multiplying power of 10C, the discharge specific capacity can reach 49.3mAh/g after 300 cycles under 10C, and the capacity retention rate is 77.3%.
Example 4:
a preparation method of a porous spherical structure sodium nickel manganese oxide cathode material comprises the following steps:
(1) preparing a nickel-manganese binary carbonate precursor: according to manganese sulfate: the nickel sulfate is 2: 1, weighing raw materials according to the molar ratio, and dissolving the raw materials in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution; respectively preparing ammonia water: ammonium bicarbonate is 4: 1, respectively preparing 0.5mol/L ammonia water/ammonium bicarbonate mixed complexing agent solution and 0.1mol/L ammonia water/ammonium bicarbonate base solution.
Adding a mixed metal salt solution, a 2mol/L sodium carbonate precipitant solution and a 0.5mol/L ammonia water complexing agent solution into the 0.1mol/L ammonia water base solution by a peristaltic pump by adopting a coprecipitation method, and controlling the molar ratio of the mixed metal salt, the precipitant sodium carbonate and the ammonia water/ammonium bicarbonate mixed complexing agent to be 1: 1: 0.4, reacting for 30 hours under the conditions that the pH value is 8, the stirring speed is 950 revolutions per minute and the temperature is 50 ℃, filtering after the reaction is finished, repeatedly washing, removing impurities and drying to obtain the nickel with the solid structureManganese binary carbonate precursor (Mn)0.67Ni0.33)CO3。
(2) And (2) heating the nickel-manganese binary carbonate precursor with the solid structure in the step (1) from room temperature to 600 ℃ at the heating rate of 5 ℃/min, and calcining for 6h to obtain the nickel-manganese binary oxide precursor with the multilayer onion-like structure.
(3) Mixing and grinding 0.01mol of the nickel-manganese binary oxide precursor in the step (2) and 0.0105mol of sodium carbonate (Na is excessive by 5%), putting the mixture into a muffle furnace, heating the mixture to 600 ℃ at the heating rate of 5 ℃/min in the air atmosphere for presintering for 6h, heating the mixture to 900 ℃ at the same heating rate for calcining for 12h, and obtaining the nickel-manganese positive electrode material Na with the porous spherical structure0.67Mn0.67Ni0.33O2。
Assembling the battery: the same as in example 1.
The sodium nickel manganese oxide anode material prepared by the embodiment has a porous spherical shape, and the spherical size is relatively uniform, and is specifically represented by the spherical particle size of the material being 15-20 microns. After the material is assembled into a half battery, electrochemical performance test is carried out within the range of 2-4.15V, and the first discharge specific capacity can reach 70.2 mAh/g. The prepared anode material is subjected to rate capability test, and the discharge specific capacities of the anode material at 1, 2, 5, 10, 20 and 25 ℃ are respectively 70.2, 68.3, 65.7, 53.1, 50.2 and 47.6 mAh/g; the first discharge specific capacity can reach 54.2mAh/g under the current multiplying power of 10C, and the discharge specific capacity can reach 43.3mAh/g after 300 cycles under the current multiplying power of 10C, and the capacity retention rate is 79.9 percent.
Comparative example 1:
a preparation method of a sodium nickel manganese oxide positive electrode material with a compact spherical structure comprises the following steps:
(1) preparing a nickel-manganese binary carbonate precursor: according to manganese sulfate: the nickel sulfate is 2: 1, weighing raw materials according to the molar ratio, and dissolving the raw materials in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution; respectively preparing 0.5mol/L ammonia water complexing agent solution and 0.1mol/L ammonia water base solution.
Mixing a metal salt solution, a 2mol/L sodium carbonate precipitant solution and a 0.5mol/L ammonia water complexing agent solution by adopting a coprecipitation methodAdding the mixed metal salt, a precipitator sodium carbonate and a complexing agent ammonia water into the 0.1mol/L ammonia water base solution through a peristaltic pump, and controlling the molar ratio of the mixed metal salt, the precipitator sodium carbonate and the complexing agent ammonia water to be 1: 1: 0.4, reacting for 20 hours under the conditions that the pH value is 8, the stirring speed is 950 revolutions per minute and the temperature is 50 ℃, filtering after the reaction is finished, repeatedly washing, removing impurities and drying to obtain a nickel-manganese binary carbonate precursor (Mn) with a solid structure0.67Ni0.33)CO3。
(2) And (2) heating the nickel-manganese binary carbonate precursor with the solid structure in the step (1) from room temperature to 500 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-manganese binary oxide precursor with the solid structure (the section is shown in figure 8).
(3) Mixing and grinding 0.01mol of the nickel-manganese binary oxide precursor in the step (2) and 0.0105mol of sodium carbonate (Na is excessive by 5%), putting the mixture into a muffle furnace, heating the mixture to 500 ℃ at a heating rate of 5 ℃/min in the air atmosphere for presintering for 5h, heating the mixture to 900 ℃ at the same heating rate for calcining for 12h, and obtaining the nickel-manganese acid sodium anode material (shown in figure 9) Na with a compact spherical structure0.67Mn0.67Ni0.33O2。
As shown in fig. 8 and 9, the precursor prepared in this comparative example has consistent internal and external crystallinity, and after sintering with sodium mixture, a dense sphere without pores is obtained.
Assembling the battery: the same as in example 1.
The sodium nickel manganese oxide anode material prepared by the comparative example has a compact spherical shape, and the spherical size is uniform, and the specific expression is that the spherical particle size of the material is 15-20 mu m. After the material is assembled into a half battery, electrochemical performance test is carried out within the range of 2-4.15V, and the first discharge specific capacity can reach 70 mAh/g. The prepared anode material is subjected to rate capability test, and the discharge specific capacities of the anode material at 1, 2, 5, 10, 20 and 25C are respectively 70, 66.3, 62.1, 50.1, 42.2 and 39.6 mAh/g; the first discharge specific capacity is 51.3mAh/g under the current multiplying power of 10C, the discharge specific capacity is 33.2mAh/g after 300 cycles under 10C, and the capacity retention rate is 64.7%.
Comparative example 2:
a preparation method of a sodium nickel manganese oxide positive electrode material with a hollow spherical structure comprises the following steps:
(1) preparing a nickel-manganese binary carbonate precursor: according to manganese sulfate: the nickel sulfate is 2: 1, weighing raw materials according to the molar ratio, and dissolving the raw materials in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution; respectively preparing ammonia water: ammonium bicarbonate is 1: 2, respectively preparing 0.5mol/L ammonia water/ammonium bicarbonate mixed complexing agent solution and 0.1mol/L ammonia water/ammonium bicarbonate base solution.
Adding a mixed metal salt solution, a 2mol/L sodium carbonate precipitator solution and a 0.5mol/L ammonia water complexing agent solution into the 0.1mol/L ammonia water base solution by a peristaltic pump by adopting a coprecipitation method, and controlling the molar ratio of the mixed metal salt, the precipitator sodium carbonate and the complexing agent ammonia water to be 1: 1: 0.4, reacting for 20 hours under the conditions that the pH value is 8, the stirring speed is 950 revolutions per minute and the temperature is 50 ℃, filtering after the reaction is finished, repeatedly washing, removing impurities and drying to obtain a nickel-manganese binary carbonate precursor (Mn) with a solid structure0.67Ni0.33)CO3。
(2) And (2) heating the nickel-manganese binary carbonate precursor with the solid structure in the step (1) from room temperature to 500 ℃ at the heating rate of 5 ℃/min, and calcining for 5h to obtain the nickel-manganese binary oxide precursor with the core-shell structure.
(3) Mixing and grinding 0.01mol of the nickel-manganese binary oxide precursor in the step (2) and 0.0105mol of sodium carbonate (Na is excessive by 5%), putting the mixture into a muffle furnace, heating the mixture to 500 ℃ at the heating rate of 5 ℃/min in the air atmosphere for presintering for 5h, heating the mixture to 900 ℃ at the same heating rate for calcining for 12h, and obtaining the nickel-manganese positive electrode material Na with a hollow structure0.67Mn0.67Ni0.33O2。
Assembling the battery: the same as in example 1.
The spherical size of the sodium nickel manganese oxide cathode material prepared by the comparative example is uniform, and the specific expression is that the spherical particle size of the material is 18-20 mu m. After the material is assembled into a half battery, electrochemical performance test is carried out within the range of 2-4.15V, and the first discharge specific capacity can reach 72 mAh/g. The prepared anode material is subjected to rate capability test, and the discharge specific capacities of the anode material at 1, 2, 5, 10, 20 and 25C are 72, 67.3, 61.1, 49.1, 43.2 and 38.6mAh/g respectively; the first discharge specific capacity is 50.6mAh/g under the current multiplying power of 10C, the discharge specific capacity is 35.2mAh/g after 300 cycles under the current multiplying power of 10C, and the capacity retention rate is 69.6%.
Comparative example 3:
a preparation method of a porous sodium nickel manganese oxide positive electrode material with a sphere-like structure comprises the following steps:
(1) preparing a nickel-manganese binary carbonate precursor: according to manganese sulfate: the nickel sulfate is 2: 1, weighing raw materials according to the molar ratio, and dissolving the raw materials in deionized water to prepare 2mol/L mixed metal salt solution; preparing 2mol/L sodium carbonate precipitant solution; respectively preparing ammonia water: ammonium bicarbonate is 4: 1, respectively preparing 0.5mol/L ammonia water/ammonium bicarbonate mixed complexing agent solution and 0.1mol/L ammonia water/ammonium bicarbonate base solution.
Adding a mixed metal salt solution, a 2mol/L sodium carbonate precipitator solution and a 0.5mol/L ammonia water complexing agent solution into the 0.1mol/L ammonia water base solution by a peristaltic pump by adopting a coprecipitation method, and controlling the molar ratio of the mixed metal salt, the precipitator sodium carbonate and the complexing agent ammonia water to be 1: 1: 0.4, reacting for 20 hours under the conditions that the pH value is 8, the stirring speed is 950 revolutions per minute and the temperature is 50 ℃, filtering after the reaction is finished, repeatedly washing, removing impurities and drying to obtain a nickel-manganese binary carbonate precursor (Mn) with a solid structure0.67Ni0.33)CO3。
(2) And (2) heating the nickel-manganese binary carbonate precursor with the solid structure in the step (1) from room temperature to 800 ℃ at the heating rate of 5 ℃/min, and calcining for 6h to obtain the nickel-manganese binary oxide precursor with the multilayer spherical structure.
(3) Mixing and grinding 0.01mol of the nickel-manganese binary oxide precursor in the step (2) and 0.0105mol of sodium carbonate (Na is excessive by 5%), putting the mixture into a muffle furnace, heating the mixture to 500 ℃ at the heating rate of 5 ℃/min in the air atmosphere for presintering for 5h, heating the mixture to 900 ℃ at the same heating rate for calcining for 12h, and obtaining the nickel-manganese positive electrode material Na with the porous spheroidal structure0.67Mn0.67Ni0.33O2。
Assembling the battery: the same as in example 1.
The sodium nickel manganese oxide anode material prepared by the comparative example has a compact spherical shape, and the spherical size is uniform, and the specific expression is that the spherical particle size of the material is 20-22 mu m. After the material is assembled into a half battery, electrochemical performance test is carried out within the range of 2-4.15V, and the first discharge specific capacity can reach 71.2 mAh/g. The prepared anode material is subjected to rate capability test, and the discharge specific capacities of the anode material at 1, 2, 5, 10, 20 and 25C are 71.2, 66.3, 57.1, 52.1, 49.2 and 42.6mAh/g respectively; the first discharge specific capacity is 53.3mAh/g under the current multiplying power of 10C, the discharge specific capacity is 38.2mAh/g after 300 cycles under the current multiplying power of 10C, and the capacity retention rate is 71.7%.

Claims (7)

1. A preparation method of a porous spherical structure sodium nickel manganese oxide cathode material is characterized by comprising the following steps:
(1) adding a nickel-manganese metal salt solution, a carbonate precipitator solution and a complexing agent solution into a reaction kettle filled with a base solution to carry out coprecipitation reaction to obtain a nickel-manganese binary carbonate precursor with a solid structure and different internal and external crystallinities; the concentration of the complexing agent solution is 0.5-2 mol/L; the complexing agent solution contains ammonia water and ammonium bicarbonate, and the molar ratio of the ammonium bicarbonate to the ammonia water is (0.1-1): 1;
(2) calcining the solid-structure nickel-manganese binary carbonate precursor obtained in the step (1), and decomposing the solid-structure nickel-manganese binary carbonate to obtain a layered-structure nickel-manganese binary oxide precursor;
(3) uniformly mixing the nickel-manganese binary oxide precursor with the layered structure obtained in the step (2) with sodium salt, and calcining to obtain the porous spherical nickel-manganese oxide positive electrode material;
in the step (2), the temperature is raised from room temperature to 300-700 ℃ at the temperature raising rate of 1-5 ℃/min during calcination, and the calcination is carried out for 3-10 h;
in the step (3), the calcination comprises pre-calcination and re-calcination, wherein the pre-calcination is performed by heating from room temperature to 300-600 ℃ at the heating rate of 1-10 ℃/min and presintering for 4-10 h; the re-calcination is to heat up to 800-950 ℃ at the heating rate of 1-10 ℃/min, and the calcination is carried out for 6-15 h.
2. The preparation method according to claim 1, wherein the nickel-manganese binary oxide precursor has an onion-like spherical structure and a single-layer thickness of 0.01 to 1 μm; the nickel sodium manganate anode material with the porous spherical structure is porous and spherical, and the particle size is 5-30 mu m; the chemical formula of the porous spherical structure sodium nickel manganese oxide anode material is NaxNiyMn1-yO2(ii) a Wherein: x is more than or equal to 0.44<1，0≤y≤0.5。
3. The preparation method according to claim 1, wherein the manganese salt in the nickel-manganese metal salt solution comprises one or more of manganese sulfate, manganese formate, manganese acetate or manganese nitrate, and the nickel salt is one or more of nickel sulfate, nickel formate, nickel acetate or nickel nitrate; the concentration of metal ions in the nickel-manganese metal salt solution is 0.5-5 mol/L; the sodium salt comprises one or more of sodium carbonate, sodium hydroxide, sodium acetate, sodium nitrate, sodium formate and sodium iodide.
4. The method of claim 1, wherein the carbonate salt in the carbonate precipitant solution comprises one or more of sodium carbonate, sodium bicarbonate, ammonium bicarbonate, or ammonium carbonate; the concentration of the carbonate precipitant solution is 1-5 mol/L.
5. The production method according to claim 1, wherein the concentration of the base solution is 0.1 to 0.5 mol/L; the base solution contains ammonia water and ammonium bicarbonate, and the molar ratio of the ammonium bicarbonate to the ammonia water is (0.1-1): 1.
6. the preparation method according to any one of claims 1 to 5, wherein during the coprecipitation reaction, the molar ratio of the nickel-manganese metal salt solution, the carbonate precipitant solution, and the complexing agent solution is controlled to be 1: 1: (0.1-0.5).
7. The preparation method as claimed in any one of claims 1 to 5, wherein during the coprecipitation reaction, the pH value of the reaction system is controlled to be 7-9, the stirring speed is 500-1200rpm, the temperature is 40-60 ℃, and the reaction time is 5-30 h.
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