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Prussian blue positive electrode material, preparation method and application thereof, and battery

A positive electrode material, Prussian blue technology, applied in the direction of battery electrodes, circuits, electrical components, etc., can solve the problems of increasing manufacturing costs and inability to carry out large-scale production, and achieve improved cycle performance, good electrochemical performance, and simple preparation methods Effect

Active Publication Date: 2022-04-01
宜宾锂宝新材料有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the strong water absorption of this type of material, the Prussian blue positive electrode material powder or the electrode sheet prepared by it is also very easy to re-absorb the moisture in the air after it is taken out of the vacuum drying oven.
If the manufacturing process of the electrode sheet is placed in a dry room, it will greatly increase the manufacturing cost and cannot be mass-produced

Method used

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Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0061] Correspondingly, the present application also provides a method for preparing the aforementioned Prussian blue positive electrode material, including the following steps:

[0062] put molecular formula as A x M[M'(CN) 6 ] 1-y 6yH 2 O y z(H 2 The cathode material of O)' undergoes ligand exchange with the ligand L to obtain the molecular formula A x M[M'(CN) 6 ] 1-y (6y-d)H 2 OdL□ y z(H 2 O)' Prussian blue cathode material.

[0063] For reference, the above molecular formula is A x M[M'(CN) 6 ] 1-y 6yH 2 O y z(H 2 The mass ratio of the cathode material of O)' to the ligand can be 1:0.3-2, such as 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1 :1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, etc., can also be 1:0.3 Any other value in the range of -2.

[0064] In some preferred embodiments, the above molecular formula is A x M[M'(CN) 6 ] 1-y 6yH 2 O y z(H 2 The mass ratio of the cathode material of O)' to the ligand is ...

Embodiment 1

[0082] This embodiment provides a kind of Prussian blue positive electrode material, and its preparation method is as follows:

[0083] put molecular formula as A x M[M'(CN) 6 ] 1-y 6yH 2 O y z(H 2 The positive electrode material of O)' was dispersed in methanesulfonic acid solution at a mass ratio of 1:1, and was stirred at 25°C and 100r / min for 10h for ligand exchange, then centrifuged, and the solid phase was dried to obtain formazan The molecular formula after sulfonic acid ligand exchange is A x M[M'(CN) 6 ] 1-y (6y-d)H 2 OdL□ y z(H 2 O)' Prussian blue cathode material.

[0084] In the above molecular formula, A is Na + , both M and M' are Fe, the value of x is 1.78, the value of y is 0.08, 0<d≤0.48, the value of z is 1.71, and L is methanesulfonic acid.

[0085] Among them, the molecular formula is A x M[M'(CN) 6 ] 1-y 6yH 2 O y z(H 2 O)' positive electrode material is prepared in the following way:

[0086] (1) Sodium ferrocyanide, sodium citrate and...

Embodiment 2

[0091] This embodiment provides a kind of Prussian blue positive electrode material, and its preparation method is as follows:

[0092] put molecular formula as A x M[M'(CN) 6 ] 1-y 6yH 2 O y z(H 2 The positive electrode material of O)' was dispersed in methanesulfonic acid solution at a mass ratio of 1:1, and was stirred at 25°C and 100r / min for 10h for ligand exchange, then centrifuged, and the solid phase was dried to obtain formazan The molecular formula after sulfonic acid ligand exchange is A x M[M'(CN) 6 ] 1-y (6y-d)H 2 OdL□ y z(H 2 O)' Prussian blue cathode material.

[0093] In the above molecular formula, A is Na + , M is manganese, M' is iron, the value of x is 1.76, the value of y is 0.07, 0<d≤0.42, the value of z is 1.88, and L is methanesulfonic acid.

[0094] Among them, the molecular formula is A x M[M'(CN) 6 ] 1-y 6yH 2 O y z(H 2 O)' positive electrode material is prepared in the following way:

[0095] (1) Sodium ferrocyanide, sodium citra...

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Abstract

The invention discloses a Prussian blue positive electrode material, a preparation method and application thereof, and a battery, and belongs to the technical field of battery materials. The molecular formula of the material is AxM [M '(CN) 6] 1-y (6y-d) H2OdL-y. Z (H2O)', a is at least one of alkali metal cations, alkaline earth metal cations, Zn < 2 + > and Al < 3 + >; m and M'are independently selected from at least one of transition metals; h2O is used as coordination water; -is an M '(CN) 6 hole; l is a ligand; (H2O) 'is interstitial water; 0 < x < = 2; 0 < y < 1; 0 < d < = 6; 0 < z < = 16; the ligand is a compound containing a sulfonic acid group. The water content and the water absorption performance of the material are low, and the material has good structural stability and excellent electrochemical performance, such as the characteristic of high-temperature cycle performance. The preparation method is simple, easy to operate and suitable for industrial production. When the material is used for preparing a battery, the battery has good electrochemical performance.

Description

technical field [0001] The invention relates to the technical field of battery materials, in particular to a Prussian blue positive electrode material, a preparation method and application thereof, and a battery. Background technique [0002] Prussian blue cathode materials are usually prepared by adding a transition metal cyanide anion [M′(CN) 6 m- ] with a transition metal cation (M n+ ) are co-precipitated in aqueous solution. [0003] The carbon ligand in the cyanide complexes with the transition metal M′ to form a hexacoordinated octahedral structure [M′(CN) 6 ], [M'(CN) 6 The uncoordinated nitrogen ligands in the octahedron and the transition metal M also form a hexacoordinated octahedral structure [M(CN) 6 ], so [M′(CN) 6 ] octahedron and [M(CN) 6 ] Octahedrons are alternately connected to each other to form a three-dimensional skeleton crystal structure. At the same time, for the sake of charge balance, it is very easy to produce [M′(CN) 6 ] hole. For examp...

Claims

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Application Information

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IPC IPC(8): C07F15/02H01M4/60
CPCY02E60/10
Inventor 薛鹏范未峰张彬王政强刘强万光瑞
Owner 宜宾锂宝新材料有限公司
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