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Manganese-doped modified zinc ion battery positive electrode active material and preparation method and application thereof

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 difficult rapid migration of zinc ions, capacity decline, short cycle life, etc., to improve cycle stability, improve The effect of cycle performance

Active Publication Date: 2020-10-02
HEFEI UNIV OF TECH
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  • Abstract
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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). The problem of rapid migration, however, the severe phase transition and electrochemical dissolution during the constant current cycle make the capacity of ZnHCF seriously drop during the cycle discharge process, and the cycle life is short, which cannot meet the needs of high energy density zinc-ion batteries, hindering its development. Further development

Method used

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  • Manganese-doped modified zinc ion battery positive electrode active material and preparation method and application thereof
  • Manganese-doped modified zinc ion battery positive electrode active material and preparation method and application thereof
  • Manganese-doped modified zinc ion battery positive electrode active material and preparation method and application thereof

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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 comprising 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 comprising the positive electrode active material, the conductive agent and the binder, a dispersant is added, the resulting product is coated on the conductive current collector, and the zinc ion battery electrode 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, nick...

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 of deionized water to prepare 0.0198mol / L ZnSO 4 and 0.0002mol / L Mn(NO 3 ) 2 mixture;

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

[0106] (3) 100mL ZnSO 4 with Mn (NO 3 ) 2 The mixed solution was added 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 kept vigorous stirring (stirring speed was 500rpm) for 12 hours, and then left standstill for 6 hours to obtain the product;

[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 100 mL of deionized water to prepare 0.0194 mol / L ZnSO 4 and 0.0006mol / L Mn(NO 3 ) 2 mixture;

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

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

[0114] (4) the mixture kept vigorous stirring (stirring speed was 800rpm) for 12 hours, and then left standstill for 6 hours to obtain the product;

[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 modified zinc ion battery positive electrode active material and a preparation method and application thereof. The positive electrode active material contains manganese zinc ferricyanide. The X-ray diffraction pattern of manganese zinc ferricyanide has absorption peaks at diffraction angles 2 theta of 9. 68 degrees, 13.42 degrees, 14.00 degrees, 14.78 degrees, 16.16 degrees, 17.08 degrees, 19.46 degrees, 21.42 degrees, 21.64 degrees, 24.26 degrees, 34.60 degrees and 38.82 degrees, and the error of 2 theta is + / - 0.2; preferably, the manganese zinc ferricyanide is prepared by a method comprising the following steps: blending a zinc salt aqueous solution, a manganese salt aqueous solution and a ferricyanide ion solution, and then reacting to obtainthe manganese zinc ferricyanide. The positive electrode active material provided by the invention can improve the performance of the zinc ferricyanide positive electrode active material and obviouslyimprove the cycling 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 positive electrode active material for zinc ion batteries, a preparation method and application thereof. Background technique [0002] With abundant resources, low cost, high capacity and environmental friendliness, zinc is considered to be one of the most promising anode materials for new energy devices. Therefore, aqueous zinc-ion batteries (ZIBs, with zinc as the negative electrode) 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 analog (PBA) with open framework structure, allowing the inclusion of Zn 2+ The fast and reversible insertion / extraction of various cations, including the fast and reversible insertion / extraction of various cations, and the very sim...

Claims

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Application Information

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IPC IPC(8): C01C3/12H01M4/58H01M10/054
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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