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Manganese-doped modified zinc-ion battery cathode active material and its preparation method and application

A positive electrode active material, zinc ion battery technology, applied in the direction of battery electrodes, positive electrodes, secondary batteries, etc., can solve the problems of capacity decline, difficulty in rapid migration of zinc ions, and inability to meet high energy density zinc ion batteries, etc., to achieve improvement Effects of improving cycle performance and cycle stability

Active Publication Date: 2022-03-11
HEFEI UNIV OF TECH
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  • Description
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Problems solved by technology

[0005] The technical problem solved by the present invention is: the inventors have found that zinc hexacyanoferrate (zinc ferricyanide, ZnHCF) is used as battery active material to improve the difficulty of zinc ions in the existing water-based rechargeable zinc-ion batteries (ARZIBs). However, the severe phase transition and electrochemical dissolution during the constant current cycle make ZnHCF seriously drop in capacity and short cycle life during cyclic discharge, which cannot meet the needs of high energy density zinc-ion batteries, hindering its Further development

Method used

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  • Manganese-doped modified zinc-ion battery cathode active material and its preparation method and application
  • Manganese-doped modified zinc-ion battery cathode active material and its preparation method and application
  • Manganese-doped modified zinc-ion battery cathode active material and its preparation method and application

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preparation example Construction

[0061] The present invention also provides a method for preparing the above positive electrode material, which is characterized in that it comprises the following steps:

[0062] After mixing the raw materials including the positive electrode active material, the conductive agent and the binder, a dispersant is added, and the positive electrode material is formed after mixing.

[0063] Preferably, in the above preparation method, the dispersant is selected from water, ethanol, N-methylpyrrolidone, isopropanol or methanol.

[0064] After mixing the raw materials including the positive electrode active material, the conductive agent and the binder, a dispersant is added, the obtained product is coated on the conductive current collector, and the electrode of the zinc ion battery is obtained after drying.

[0065] Preferably, the conductive current collector is selected from carbon paper, carbon cloth, carbon felt, titanium foil, stainless steel foil, copper foil, aluminum foil, ...

Embodiment 1

[0103] Preparation of Mn 0.03 Zn 2.97 [Fe(CN) 6 ] 2 ·yH 2 O (referred to as MZHCF), the steps are as follows:

[0104] (1) Weigh 0.5693g ZnSO 4 ·7H 2 O and 0.0035g Mn(NO 3 ) 2 Add 100mL deionized water to make 0.0198mol / L ZnSO 4 and 0.0002mol / L of Mn(NO 3 ) 2 mixture;

[0105] (2) Weigh 0.6585g K 3 Fe(CN) 6 , add 100mL of deionized water to make a K of 0.02mol / L 3 Fe(CN) 6 aqueous solution;

[0106] (3) 100mL ZnSO 4 with Mn(NO 3 ) 2 Add the mixed solution to 100mL K at a rate of 50mL / h 3 Fe(CN) 6 In the aqueous solution, and maintain vigorous stirring (stirring speed is 500rpm), form a mixture;

[0107] (4) The mixture was kept under vigorous stirring (stirring speed was 500rpm) for 12 hours, and after standing for 6 hours, the product was obtained;

[0108] (5) Wash the reaction product with deionized water and ethanol, and dry it at 70°C for 12 hours to obtain Mn 0.03 Zn 2.97 [Fe(CN) 6 ] 2 ·yH 2 O solid.

Embodiment 2

[0110] Preparation of Mn 0.09 Zn 2.91 [Fe(CN) 6 ] 2 ·yH 2 O, the steps are as follows:

[0111] (1) Weigh 0.5579g ZnSO 4 ·7H 2 O and 0.0107g Mn(NO 3 ) 2 Add 100mL deionized water to make 0.0194mol / L ZnSO 4 and 0.0006mol / L of Mn(NO 3 ) 2 mixture;

[0112] (2) Weigh 0.6585g K 3 Fe(CN) 6 , add 100mL of deionized water to make a K of 0.02mol / L 3 Fe(CN) 6 aqueous solution;

[0113] (3) 100mL ZnSO 4 with Mn(NO 3 ) 2 The mixed solution was added to 100mL K at a rate of 100mL / h 3 Fe(CN) 6 In the aqueous solution, and maintain vigorous stirring (stirring speed is 800rpm), form a mixture;

[0114] (4) The mixture was kept under vigorous stirring (stirring speed was 800rpm) for 12 hours, and after standing for 6 hours, the product was obtained;

[0115] (5) Wash the reaction product with deionized water and ethanol, and dry it at 70°C for 12 hours to obtain Mn 0.09 Zn 2.91 [Fe(CN) 6 ] 2 ·yH 2 O solid.

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Abstract

The invention relates to a manganese-doped and modified zinc-ion battery cathode active material and its preparation method and application. The cathode active material comprises manganese zinc ferricyanide, and the X-ray diffraction spectrum of manganese zinc ferricyanide is at diffraction angle 2θ=9.68 °, 13.42°, 14.00°, 14.78°, 16.16°, 17.08°, 19.46°, 21.42°, 21.64°, 24.26°, 34.60° and 38.82° have absorption peaks, and the 2θ error is ±0.2; preferably, ferricyanide Manganese zinc is prepared by a method comprising the following steps: the zinc salt solution, the manganese salt solution and the ferricyanide ion solution are blended and then reacted. The positive electrode active material of the invention can improve the performance of the zinc ferricyanide positive electrode active material, and obviously improve the cycle stability of the positive electrode material.

Description

technical field [0001] The invention belongs to the field of zinc-ion batteries, and in particular relates to a manganese-doped modified zinc-ion battery cathode active material and its preparation method and application. Background technique [0002] Zinc is considered as one of the most promising anode materials for new energy devices due to its abundant resources, low cost, high capacity, and environmental friendliness. Therefore, aqueous zinc-ion batteries (ZIBs, with zinc as the anode) have been considered as very promising alternatives in next-generation energy storage technologies. The development of high-performance cathode materials has become the key to the development of zinc-ion batteries. Prussian blue analogue (PBA) with an open framework structure allowing the inclusion of Zn 2+ The rapid and reversible insertion / extraction of various cations, and the very simple fabrication process of PBA, all these features make PBA a positive electrode material for zinc-i...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M4/58
CPCC01C3/12H01M4/58H01M10/054C01P2002/72C01P2004/03C01P2006/40H01M2004/028Y02E60/10
Inventor 倪刚徐修文郝照
Owner HEFEI UNIV OF TECH
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