High-temperature solid-phase synthesis method of one-dimensional nano-sodion cell anode material NaxMnO2

A technology for ion batteries and cathode materials, applied in battery electrodes, non-aqueous electrolyte storage batteries, circuits, etc., can solve the problems of uneven product morphology, long reaction time, and large sodium consumption, and achieve good electrochemical performance and synthesis The effect of shortening time and reducing sodium consumption

Inactive Publication Date: 2014-02-19
SOUTHWEST UNIVERSITY
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Problems solved by technology

Among them, the manganese source mainly used in the solid phase method is MnCO 3 and Mn 2 o 3 , the sodium source is Na 2 CO 3 , the reaction temperature is 800-900°C, and the reaction time is less than 12h, but the morphology of the products all presents an uneven thick rod-like structure and is bonded to each other. The particles are too large, which is likely to cause poor contact between particles and diffusion of sodium ions. The distance increases, and at a charge-discharge rate of 0.1C, the discharge specific capacity of the product is only 80mA·h / g, and the discharge specific capacity after adding carbon nanotubes is only 113mA·h / g
And the hydrothermal method, when the reaction temperature is above 200°C and the reaction time is 72 hours, sodium manganese oxygen nanowires can be obtained and have good electrochemical properties, but the reaction time of 72 hours is too long, the output per unit time is low, and the amount of sodium consumed Larger (sodium-manganese ratio is generally greater than 150), not suitable for large-scale industrial production. In addition, the manganese source Mn used in the hydrothermal method 2 o 3 and Mn 3 o 4 It also needs to be in the form of fine particles, otherwise it is difficult to obtain nanowires even after 72 hours of reaction

Method used

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  • High-temperature solid-phase synthesis method of one-dimensional nano-sodion cell anode material NaxMnO2
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  • High-temperature solid-phase synthesis method of one-dimensional nano-sodion cell anode material NaxMnO2

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Experimental program
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Effect test

Embodiment 1

[0040] Embodiment 1, one-dimensional nanometer sodium ion battery cathode material Na x MnO 2 Synthesis

[0041] Take 11.6ml50%(w / w)Mn(NO 3 ) 2 solution and 2.295g NaNO 3 Dissolve in 18ml of deionized water, stir to fully dissolve to obtain liquid I; dissolve 14.795g of citric acid in 24.6ml of deionized water to obtain liquid II; slowly drop liquid I into liquid II, stir for 10min, heat and evaporate at 90°C Remove the solvent, transfer the residue to an oven at 120°C for heat treatment for 24 hours, cool to room temperature, and grind it into a powder. The obtained powder continues to be heat treated at 450°C for 6 hours, cooled to room temperature, and ground into a powder, and then heat the obtained powder at 900°C 15h, cooled to room temperature to obtain the final product.

[0042] The shape of the final product is as figure 1 As shown, the crystallinity is very high, and it is in the form of thin flakes, and the existence of nanowires can be seen; the composition ...

Embodiment 2

[0043] Embodiment 2, one-dimensional nanometer sodium ion battery cathode material Na x MnO 2 Synthesis

[0044] Take 11.6ml50%(w / w)Mn(NO3 ) 2 solution and 1.912g NaNO 3 Dissolve in 15ml of deionized water, stir to fully dissolve to obtain liquid I; dissolve 13.930g of citric acid in 23ml of deionized water to obtain liquid II; slowly drop liquid I into liquid II, stir for 10min, heat and evaporate at 80°C to remove Solvent, the residue was transferred to a 120°C oven for heat treatment for 12 hours, cooled to room temperature, and ground into a powder. The obtained powder continued to be heat treated at 400°C for 3 hours, cooled to room temperature, and ground into a powder, and then the obtained powder was treated at 850°C for 15 hours. Cool to room temperature to obtain the final product.

[0045] The shape of the final product is as figure 2 As shown, it is uniform ultra-thin sheet; the component analysis results are as follows image 3 (solid line), Na x MnO 2 Th...

Embodiment 3

[0046] Embodiment 3, the preparation of battery and one-dimensional nano-sodium ion battery cathode material Na x MnO 2 Electrochemical performance test of

[0047] Get the product obtained in Example 2, conduction carbon black, and PVDF binder in a mass ratio of 80:10:10, add a certain amount of 1-methyl-2-pyrrolidone (NMP), grind it into a paste with an agate mortar, Then coated on aluminum foil with a diameter of 12mm, each piece of active material load is about 1mg, dried in a vacuum oven at 120°C for 12h, cooled to below 40°C, taken out and weighed, transferred to an argon glove box for assembly . The button battery model is CR2025, the negative electrode is sodium sheet, the diaphragm is Celgard2325, and the electrolyte is 1M NaClO 4 solution (the solvent is EC and DMC in a volume ratio of 1:1). The assembled battery is placed for more than 6 hours to be tested. Electrochemical tests were performed on a Land test system. The voltage range is 2-4V, and the current s...

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Abstract

The invention discloses a high-temperature solid-phase synthesis method of a one-dimensional nano-sodion cell anode material NaxMnO2. The high-temperature solid-phase synthesis method comprises the following steps of 1, dissolving a sodium salt and a manganese salt in water according to a mole ratio of sodium to manganese of 0.44-0.56 to obtain a solution I, 2, dissolving citric acid in water to obtain a solution II, wherein a mole ratio of citric acid to the total metal ions is in a range 0.5-1, 3, dropwisely adding the solution I into the solution II and carrying out stirring for 10-60min, 4, carrying out heating evaporation on the mixed solution at a temperature of 60-90 DEG C to remove a solvent, heating the residues at a temperature of 120 DEG C for 6-24h, cooling the heated residues to a temperature of 10-30 DEG C, and grinding the cooled residues into powder, 5, heating the powder at a temperature of 350-500 DEG C for 3-10h, cooling the powder to a temperature of 10-30 DEG C, and grinding the cooled powder into fine powder, and 6, heating the fine powder at a temperature of 800-950 DEG C for 10-45h, and carrying out cooling to obtain the one-dimensional nano-sodion cell anode material NaxMnO2. The high-temperature solid-phase synthesis method has short synthesis time and a high yield in unit time. The one-dimensional nano-sodion cell anode material NaxMnO2 has uniform, dispersive, thin and long product morphology and good electrochemical properties (of a specific discharge capacity of 114mA.h/g at 0.1C charging-discharging multiplying power).

Description

technical field [0001] The invention belongs to the field of battery materials, and in particular relates to a method for synthesizing battery anode materials. Background technique [0002] There are many similarities between Na-ion and Li-ion batteries, and Na-ion batteries have some distinct advantages over Li-ion batteries, such as low raw material costs and the use of electrolyte systems with lower decomposition potentials. So far, the main cathode materials for sodium-ion batteries are NaVPO 4 F. Na x CoO 2 、Na x MnO 2 Layered crystalline compounds and their doped compounds. [0003] Na x MnO 2 The preparation methods of materials mainly include solid phase method, hydrothermal method, sol-gel method and so on. Among them, the manganese source mainly used in the solid phase method is MnCO 3 and Mn 2 o 3 , the sodium source is Na 2 CO 3 , the reaction temperature is 800-900°C, and the reaction time is less than 12h, but the morphology of the products all pre...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/505
CPCY02E60/122C01G45/12H01M4/505H01M10/05Y02E60/10
Inventor 徐茂文牛玉斌李长明
Owner SOUTHWEST UNIVERSITY
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