Hollow spherical sodium nickel manganate and preparation method thereof, sodium ion battery positive electrode, and sodium ion battery

A technology of sodium nickel manganese oxide and spherical shape, which is applied in the field of hollow spherical sodium nickel manganese oxide and its preparation, and the positive electrode sheet of sodium ion battery, which can solve the problems of limited cycle performance, complicated preparation process, capacity decay, etc., and save the stirring process , waste liquid treatment is simple, the effect of reducing energy consumption

Inactive Publication Date: 2019-04-09
XIANGTAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Sodium nickel manganate has a high theoretical specific capacity and has great potential to be a cathode material for sodium-ion batteries, but it faces a serious capacity fading problem, mainly due to the reversible intercalation / extraction of sodium ions during charge and discharge. , causing the collapse of the crystal structure
There are literatures (Manikandan P, Ramasubramonian D, Shaijumon MM. Electrochimica Acta, 2016, 206:199-206.) proposed to use nickel and manganese acetate to form a gel, and then mix it with sodium salt and directly react at high temperature to obtain Na 0.5 Ni 0.25 mn 0.75 o 2 , has a typical P2-type layered structure, but its cycle life is short and its capacity fades seriously. The main reason is that nickel-manganese has different solubility products. The nickel-manganese in the original solution cannot precipitate according to the stoichiometric ratio, resulting in The stoichiometric ratio of nickel-manganese elements deviates from the design value; the patent CN105692721A uses the hydroxide precipitation of nickel and manganese mixed with sodium salt, and calcines at 750-900°C for 4-24 hours to obtain layered Na x Ni 0.5+ y mn 0.5-y o 2 Material (x=0.9~1.1, y=0~0.2); patent CN103922427A utilizes nickel, manganese compound and complexing agent reaction, has prepared a kind of complex metal oxide Na 2 / 3 Ni 1 / 3 mn 2 / 3 o 2 , although the existing technology has improved the cycle stability of sodium nickel manganese oxide by changing the preparation method, the improved cycle performance is still relatively limited, and the preparation process is complicated

Method used

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  • Hollow spherical sodium nickel manganate and preparation method thereof, sodium ion battery positive electrode, and sodium ion battery
  • Hollow spherical sodium nickel manganate and preparation method thereof, sodium ion battery positive electrode, and sodium ion battery
  • Hollow spherical sodium nickel manganate and preparation method thereof, sodium ion battery positive electrode, and sodium ion battery

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preparation example Construction

[0031] The present invention provides a method for preparing the hollow spherical sodium nickel manganate described in the above scheme, which includes the following steps:

[0032] (1) Provide a nickel-manganese mixed solution including nickel salt, manganese salt, water and alcohol solvent;

[0033] (2) Mixing the nickel-manganese mixed solution with the carbonate aqueous solution and standing still to obtain a nickel-manganese carbonate composite salt;

[0034] (3) Pre-burning the nickel-manganese carbonate composite salt to obtain a nickel-manganese composite oxide;

[0035] (4) Mix and grind the nickel-manganese composite oxide and sodium salt, and obtain a hollow spherical sodium nickel manganate after calcination.

[0036] The present invention provides a nickel-manganese mixed solution including nickel salt, manganese salt, water and alcohol solvent. In the present invention, the nickel salt preferably includes nickel chloride, nickel nitrate or nickel sulfate, and the manganes...

Embodiment 1

[0050] Dissolve 0.22g nickel nitrate hexahydrate and 0.56g manganese nitrate tetrahydrate in 200mL deionized water, add 15mL glycerol, and stir for 20min to obtain a nickel-manganese mixed solution;

[0051] Heat the nickel-manganese mixed solution at 40°C; at 40°C, dissolve 2.37 g of ammonium bicarbonate in 200 mL of deionized water and stir for 20 minutes to obtain an aqueous carbonate solution; pour the nickel-manganese mixed solution Put it into the carbonate aqueous solution, keep it at 40°C for 4 hours, use a vacuum suction pump for suction filtration, wash with distilled water 3 to 5 times, and vacuum dry at 80°C for 12 hours to obtain a nickel-manganese carbonate composite salt;

[0052] The nickel-manganese carbonate composite salt is placed in a muffle furnace for pre-sintering to obtain a nickel-manganese composite oxide, wherein the pre-sintering parameters are: a temperature of 400°C, a heating rate of 1°C / min, and a pre-sintering time: 5h;

[0053] The nickel-manganese...

Embodiment 2

[0058] Dissolve 0.2 g nickel sulfate and 0.56 g manganese nitrate tetrahydrate in 200 mL deionized water, add 15 mL isopropanol, and stir for 30 min to obtain a nickel-manganese mixed solution;

[0059] Heat the nickel-manganese mixed solution at 60°C; at 60°C, dissolve 1.8g sodium bicarbonate in 200mL deionized water and stir for 30min to obtain a carbonate aqueous solution; pour the nickel-manganese mixed solution into the carbon In the acidic acid solution, keep it at 60℃ for 5h, use a vacuum suction filter to filter, and rinse with deionized water and 99.7% ethanol solution for 2 to 3 times, and vacuum dry at 80℃ 12h, obtain nickel manganese carbonate composite salt;

[0060] The hollow spherical nickel-manganese carbonate composite salt is placed in a muffle furnace for pre-sintering to obtain a nickel-manganese composite oxide, wherein the pre-sintering parameters are: a temperature of 500°C, a heating rate of 1°C / min, and a pre-sintering Time is 5h;

[0061] The nickel-manga...

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Abstract

The present invention provides a hollow spherical sodium nickel manganate and a preparation method thereof, a sodium ion battery positive electrode, and a sodium ion battery, which belongs to the technical field of sodium ion batteries. The present invention provides a hollow spherical sodium nickel manganate having a particle diameter of 2.5-3.5 micrometer, a wall thickness of 0.5-1.0 micrometer,and a smooth outer surface. A chemical composition of the hollow spherical sodium nickel manganite is NaxNiyMnzO2, where x:y:z=2:1:3. The sodium nickel manganate provided by the present invention hasa hollow spherical structure with regular morphology and high crystallinity, which is beneficial for sodium ions to rapidly enter a solid phase medium from the surface, a diffusion path between solidphase particles is shortened. The sodium ion battery assembled from the sodium ion battery positive electrode obtained by using the hollow spherical sodium nickel manganate as a raw material has excellent cycle stability and rate performance.

Description

Technical field [0001] The invention relates to the technical field of sodium ion batteries, in particular to a hollow spherical sodium nickel manganate and a preparation method thereof, a sodium ion battery positive sheet and a sodium ion battery. Background technique [0002] In recent years, with the rapid development of electronic equipment, power tools, and low-power electric vehicles, research on energy-efficient, resource-rich and environmentally friendly energy storage materials is a necessary condition for human society to achieve sustainable development. Lithium-ion batteries are widely used in various electronic devices due to their advantages of high energy density, long cycle life, high working voltage, no memory effect, small self-discharge, and wide operating temperature range. However, with the widespread application of lithium-ion batteries, the consumption of metal lithium has been accelerated, and lithium is facing a shortage of resources. The research and dev...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/485H01M4/505H01M4/58H01M10/054
CPCH01M4/485H01M4/505H01M4/5825H01M10/054Y02E60/10
Inventor 肖启振任晓丽
Owner XIANGTAN UNIV
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