Anion-cation doped P2 type sodium ion battery positive electrode material

A sodium ion battery, anion and cation technology, applied in the direction of battery electrodes, positive electrodes, secondary batteries, etc., can solve the problems of reducing the overall performance of the battery, poor material cycle stability, and low reversible specific capacity, and achieve good industrial application prospects. Excellent electrochemical performance, the effect of improving specific capacity

Pending Publication Date: 2021-10-19
TIANJIN UNIVERSITY OF TECHNOLOGY
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Problems solved by technology

But for P2-Na 0.67 MnO 2 For example, when the material is exposed to air, water molecules will occupy Na + position, resulting in increased interlayer spacing and reduced overall performance of the cell
In 2015, Hu Yongsheng's research group discovered that Cu 2+ The doped P2-type layered sodium-ion battery cathode material can effectively improve the air stability of the material, but the reversible specific capacity of the material is low, about 90mAh / g, and the cycle stability of the material is poor
[0004] The above-mentioned doping mainly focuses on the single doping or multi-cation doping of transition metal sites and oxygen sites, but there are few reports on the co-doping of anions and cations.

Method used

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  • Anion-cation doped P2 type sodium ion battery positive electrode material
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  • Anion-cation doped P2 type sodium ion battery positive electrode material

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preparation example Construction

[0029] Another typical embodiment of the present invention provides a method for preparing the anode and cation doped P2 type sodium ion battery cathode material, which includes the following steps.

[0030] Step 1, according to the chemical formula Na 0.67 Cu x mn 1-x o 2-y f y In the molar ratio of Mn, Cu and F elements, weigh manganese salt, copper salt and sodium fluoride and dissolve them in deionized water, then add sodium salt, stir and dissolve, and prepare mixed metal salt solution, and citric acid solution is used as complexing agent.

[0031] Preferably, the total molar concentration of metal ions is 1-3 mol / L; a citric acid solution with a mass concentration of 2%-20% is prepared as a complexing agent.

[0032]Preferably, the manganese salt described in step 1 is one or more of manganese sulfate, manganese nitrate, manganese acetate or manganese chloride; the copper salt is one or more of copper sulfate, copper nitrate or copper chloride multiple, and the sodi...

Embodiment 1

[0053] (1) According to the synthesis of 2g of Na 0.67 Cu 0.1 mn 0.9 o 1.9 f 0.1 The molar ratio of Na, Cu, Mn and F elements in Na, Cu, Mn and F elements were weighed and dissolved in deionized water with sodium acetate (5% excess), copper acetate, manganese acetate and sodium fluoride, so that the total concentration of metal ions was 2mol / L, and kept stirring until the metal salt solution dissolves. Prepare a citric acid solution with a mass concentration of 10%, slowly add the metal salt solution into the citric acid solution, adjust the pH value of the mixed solution to 9 with ammonia water, stir and evaporate to dryness at 85°C to obtain a gel substance.

[0054] (2) Dry the gel obtained in step (1) at 115°C, crush it, raise the temperature to 250°C at a rate of 2°C / min in an air atmosphere, keep it for 3 hours, and then continue to heat it up to 550°C for 5 hours. Then increase the temperature to 850°C at a rate of 2°C / min, keep it warm for 11 hours, and cool to ro...

Embodiment 2

[0056] (1) According to the synthesis of 2g of Na 0.67 Cu 0.1 mn 0.9 o 1.85 f 0.15 The molar ratio of Na, Cu, Mn and F elements in the medium is weighed and dissolved in deionized water with sodium nitrate (5% excess), copper nitrate, manganese nitrate and sodium fluoride, so that the total concentration of metal ions is 2mol / L, and kept stirring until the metal salt solution dissolves. Prepare a citric acid solution with a mass concentration of 15%, slowly add the metal salt solution into the citric acid solution, adjust the pH value of the mixed solution to 10 with ammonia water, stir and evaporate to dryness at 90°C to obtain a gel substance.

[0057] (2) Dry the gel obtained in step (1) at 100°C, break it up, heat it up to 300°C at a rate of 3°C / min in an air atmosphere, keep it warm for 3.5 hours, and then continue to heat it up to 600°C and keep it warm for 5.5 hours . Then increase the temperature to 900°C at a rate of 3°C / min, keep it warm for 12 hours, and cool ...

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Abstract

The invention relates to an anion-cation doped P2 type sodium ion battery positive electrode material and a preparation method thereof. The chemical formula of the cathode material is Na0.67CuxMn1-xO2-yFy, x is more than 0 and less than or equal to 0.35, y is more than 0 and less than or equal to 0.3, a manganese salt, a copper salt and sodium fluoride are weighed according to the molar ratio of Mn, Cu and F elements and dissolved in deionized water, then a sodium salt is added and stirred to be dissolved, a mixed metal salt solution is prepared, and a citric acid solution is used as a complexing agent; the mixed metal salt solution is added into the complexing agent, ammonia water is added to adjust the PH value of the solution to be 8-11, the heating temperature is 60-90 DEG C, and gel is obtained after drying by distillation under the stirring condition; and the obtained gel is dried and crushed, presintered in an air atmosphere, sintered, and cooledto room temperature to obtain the positive electrode material. Through the synergistic effect of Cu ions and F ions, excellent electrochemical performance is shown, for example, the specific capacity of the material is improved, and the rate capability and the cycling stability are good.

Description

technical field [0001] The invention belongs to the field of preparation of electrode materials for sodium ion batteries, in particular to an anion and cation co-doped modified P2 type layered sodium ion battery positive electrode material and a preparation method thereof. Background technique [0002] With the continuous development of new energy technologies, lithium-ion batteries have achieved great success in the past two decades due to their advantages such as high energy density, high stability, and long life. However, the reserves of lithium resources in the earth's crust are low and cannot become The key to large-scale energy storage. Therefore, sodium-ion batteries have attracted the attention of a large number of researchers. Due to the advantages of low production cost, high safety and abundant raw materials, Na-ion batteries are considered as an ideal large-scale energy storage device. [0003] Layered transition metal oxide sodium ion battery cathode materials...

Claims

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Application Information

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IPC IPC(8): H01M4/505H01M4/62H01M10/054C01G45/00
CPCH01M4/505H01M4/628H01M10/054C01G45/006C01P2004/03C01P2002/72C01P2006/40H01M2004/021H01M2004/028Y02E60/10
Inventor 胡章贵陈以蒙龙震郭帅郭世宏韩华玮姜修宝
Owner TIANJIN UNIVERSITY OF TECHNOLOGY
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