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Prussian white analog cathode material and preparation method and application thereof

A cathode material, Prussian white technology, applied in the field of Prussian white analog cathode materials, can solve problems such as defects, low water content, poor electrochemical performance, etc., achieve a perfect crystal structure, facilitate large-scale industrial production, and large particle size. Effect

Active Publication Date: 2019-07-12
HUAZHONG UNIV OF SCI & TECH
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Problems solved by technology

[0005] In view of the above defects or improvement needs of the prior art, the present invention provides a Prussian white analog positive electrode material, its preparation method and application, which increases the content of potassium citrate and controls the crystallization process by adopting a citric acid-assisted method, The prepared Prussian white analog cathode material has a more perfect crystal structure, fewer defects and lower water content. As a cathode material for lithium-ion, sodium-ion and potassium-ion batteries, it shows a high charge-discharge platform, high specific capacity, High rate performance and high cycle stability, thereby solving the technical problem of poor electrochemical performance when using Prussian white analogue positive electrode materials as positive electrode materials for sodium-ion, potassium-ion batteries and lithium-ion batteries in the prior art

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preparation example Construction

[0039] The preparation method of a kind of Prussian white analog cathode material provided by the present invention, the chemical formula of this cathode material is K x Mn[Fe(CN) 6 ] 1-y □ y .nH 2 O, where 0≤x≤2, 0≤y≤1, □ is [Fe(CN) 6 ] vacancies; the preparation method of the positive electrode material comprises the following steps:

[0040] (1) Get K 4 Fe(CN) 6 The aqueous solution, denoted as solution A;

[0041] (2) Obtain the mixed aqueous solution of the transition metal salt of Mn and potassium citrate, denoted as solution B;

[0042] (3) Add the solution A dropwise to the solution B, continue to heat and stir after the dropwise addition, and age for several hours, separate the solid from the liquid, collect and wash the precipitate, and dry to obtain the positive electrode of the Prussian white analog Material.

[0043] In some embodiments, the Mn transition metal salt is one or more of Mn chloride, sulfate, carbonate, nitrate and acetate.

[0044] In some ...

Embodiment 1

[0059] A kind of Prussian white analog cathode material, the chemical formula of this cathode material is expressed as K x Mn[Fe(CN) 6 ] 1-y □ y ·nH 2 O, where 0≤x≤2, 0≤y≤1, □ is [Fe(CN) 6 ] vacancies; the crystal water content of the material is 3.39 wt%. The preparation method of this cathode material comprises the steps:

[0060] 1) Weigh 4mmol of K 4 Fe(CN) 6 , dispersed in 200mL deionized water, stirred to form a uniform solution A;

[0061] 2) Weigh 6mmol of MnSO 4 and 15g of potassium citrate, dispersed in 200mL deionized water, stirred to form a uniform solution B;

[0062] 3) Use a peristaltic pump to add solution A to solution B at a rate of 5 mL / min, heat and stir at 60°C for 24 hours, and after aging for 20 hours, separate the precipitate from the product through a high-speed centrifuge, and use deionized water and ethanol for 3 times, and then vacuum-dried at a pressure of 20kPa and a temperature of 100°C for 24h to obtain the Prussian white analog catho...

Embodiment 2

[0065] A kind of Prussian white analog cathode material, the chemical formula of this cathode material is expressed as K x Mn[Fe(CN) 6 ] 1-y □ y ·nH 2 O, where 0≤x≤2, 0≤y≤1, □ is [Fe(CN) 6 ] vacancies; the crystal water content of this material is 3.54wt%, and the defect content is 10%, that is, y=0.1, and the molecular formula is K 1.82 Mn[Fe(CN) 6 ] 0.90 □ 0.1 .nH 2 O. The preparation method of this cathode material comprises the steps:

[0066] 1) Weigh 4mmol of K 4 Fe(CN) 6 , dispersed in 200mL deionized water, stirred to form a uniform solution A;

[0067] 2) Weigh 6mmol of MnSO 4 and 25g of potassium citrate, dispersed in 200mL of deionized water, stirred to form a uniform solution B;

[0068] 3) Use a peristaltic pump to add solution A to solution B at a rate of 5 mL / min, heat and stir at 60°C for 24 hours, and after aging for 15 hours, separate the precipitate from the product through a high-speed centrifuge, and use deionized water and ethanol for 3 tim...

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Abstract

The invention belongs to the field of new-energy batteries, and particularly relates to a Prussian white analog cathode material and a preparation method and application thereof. The preparation method of the Prussian white analog cathode material comprises the following steps: (1), acquiring an aqueous solution of K4Fe (CN)6, which is recorded as a solution A; (2), acquiring a mixed aqueous solution of a transition metal salt of Mn and potassium citrate, which is recorded as a solution B; and (3), dropwise adding the solution A into the solution B, continuing heating and stirring after completion of dropwise addition, aging for several hours, performing solid-liquid separation, collecting and washing a precipitate, and drying to obtain the Prussian white analog cathode material. The Prussian white analog cathode material adopts an open three-dimensional network frame structure, has a large gap position, and can guarantee free deintercalation of various ions such as Li<+>, Na<+> and K<+>.

Description

technical field [0001] The invention belongs to the field of new energy batteries, and more specifically relates to a Prussian white analog positive electrode material, its preparation method and application. Background technique [0002] As an emerging green electrochemical energy source, lithium-ion batteries have the advantages of high energy density, long cycle life, and no memory effect. They have been widely used in various portable devices and power batteries. However, lithium resources have limited reserves and uneven distribution, which limits its application. Compared with lithium resources, sodium and potassium have more abundant reserves in the earth's crust, accounting for about 2.74% and 1.5% respectively, and are widely distributed, which has a greater cost advantage. And lithium, sodium and potassium are in the same main group and have similar physical and chemical properties, so that the working principle of sodium ion and potassium ion batteries is similar...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01C3/12C01G49/00H01M4/58H01M10/0525H01M10/054
CPCC01C3/12C01G49/009C01P2002/72C01P2002/88C01P2004/03C01P2006/40H01M4/58H01M10/0525H01M10/054H01M2004/028Y02E60/10
Inventor 蒋凯唐云周敏王康丽李浩秒
Owner HUAZHONG UNIV OF SCI & TECH
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