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Inert transition metal element doped iron-based Prussian blue sodium ion battery positive electrode material

A transition metal element, sodium ion battery technology, applied in the direction of battery electrodes, secondary batteries, metal cyanide, etc., can solve the problems of affecting the cycle stability of materials, affecting the electrochemical performance of materials, reducing the Na content of materials, etc., to achieve improved Effects of cycle stability, volume change reduction, and lattice distortion reduction

Inactive Publication Date: 2021-07-13
CHINA THREE GORGES UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, as a Prussian blue compound, FeHCF materials also exist due to crystal water and Fe(CN) generated during the synthesis process. 6 Structural defects easily occupy sodium storage sites and ion channels, resulting in the reduction of Na content in the material and the reduction of Na content. + Problems such as the reduction of the migration rate seriously affect the electrochemical performance of the material; in addition, it may also cause the structure of the material to collapse during the charging and discharging process, affecting the cycle stability of the material

Method used

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  • Inert transition metal element doped iron-based Prussian blue sodium ion battery positive electrode material
  • Inert transition metal element doped iron-based Prussian blue sodium ion battery positive electrode material
  • Inert transition metal element doped iron-based Prussian blue sodium ion battery positive electrode material

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] 4.5 mmol FeSO 4 ·7H 2 O, 0.5 mmol Zn(CH 3 COO) 2 2H 2 O and 25 mmol Na 3 C 6 h 5 o 7 2H 2 O was dissolved in 50 ml of deionized water to form solution A, 5 mmol Na 4 Fe(CN) 6 10H 2 O and 1 g C 6 h 8 o 6 Dissolve in 50 ml deionized water to form solution B; 1 g polyvinylpyrrolidone PVP and 3 g NaCl are dissolved in deionized water to form solution C; simultaneously add solution A and solution B dropwise to solution C at a rate of 0.167 ml / min During the process, stir and heat while adding dropwise. After the dropwise addition is completed, the solution becomes a white suspension D. After continuing to stir for 12 h, age for 24 h; then use deionized water and Absolute ethanol was centrifuged and washed three times; finally, the dark blue solid was placed in a vacuum oven at 120 o C dried for 24 h to obtain the target zinc-doped Fe-based Prussian blue cathode material, labeled as 10%Zn-FeHCF. The obtained 10% Zn-FeHCF positive electrode material was stirred...

Embodiment 2

[0032] The preparation steps are the same as in Example 1, only FeSO 4 ·7H 2 O is 4.8 mmol, Zn(CH 3 COO) 2 2H 2 O was 0.2 mmol, and the target zinc-doped iron-based Prussian blue cathode material was prepared, which was labeled as 4%Zn-FeHCF. The obtained 4% Zn-FeHCF positive electrode material was stirred with acetylene black and polyvinylidene fluoride (PVDF) to form a slurry, coated on an aluminum foil, dried, punched and pressed to make a positive electrode material pole piece. Using sodium metal as the counter electrode, Grade GF / D as the separator, 1 M NaClO containing 2 wt.% FEC 4 / (EC+DMC+EMC) (EC:DMC:EMC=1:1:1) is assembled into a battery with electrolyte for constant current charge and discharge test, and the voltage range is between 2.0~4.2 V. 4%Zn-FeHCF cathode material at 100 mA g -1 The initial discharge capacity is only 121.8 mAh g at a high current density -1 , and its specific discharge capacity is only 87.6 mAh g after 80 cycles -1 .

Embodiment 3

[0034] The preparation steps are the same as in Example 1, only FeSO 4 ·7H 2 O is 4.4 mmol, Zn(CH 3 COO) 2 2H 2 O was 0.6 mmol, and the target zinc-doped Fe-based Prussian blue cathode material was prepared, labeled as 12%Zn-FeHCF. The obtained 12% Zn-FeHCF positive electrode material was stirred with acetylene black and polyvinylidene fluoride (PVDF) to form a slurry, coated on an aluminum foil, dried, punched and pressed to make a positive electrode material pole piece. Using sodium metal as the counter electrode, Grade GF / D as the separator, 1 MNaClO containing 2 wt.% FEC 4 / (EC+DMC+EMC) (EC:DMC:EMC=1:1:1) is assembled into a battery with electrolyte for constant current charge and discharge test, and the voltage range is between 2.0~4.2 V. 12%Zn-FeHCF cathode material at 100 mA g -1 The initial discharge capacity at a current density of 135.2 mAh g -1 , and its specific discharge capacity after 80 cycles is 108.8 mAh g -1 .

[0035] image 3 It is a comparison ch...

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Abstract

The invention relates to an inert transition metal element doped iron-based Prussian blue sodium ion battery positive electrode material and a preparation method thereof, wherein an inert transition metal element zinc Zn is used for replacing high spin iron connected with N in cyanide in iron-based Prussian blue according to a certain proportion. The preparation method comprises the following steps: dissolving ferrous sulfate heptahydrate, zinc acetate and sodium citrate in deionized water to form a solution A, dissolving sodium ferrocyanide decahydrate and ascorbic acid in deionized water to form a solution B, and dissolving polyvinylpyrrolidone and sodium chloride in deionized water to form a solution C; simultaneously adding the solution A and the solution B into the solution C through a peristaltic pump, and stirring while heating in an N2 atmosphere until the solution becomes white suspension liquid after dropwise adding is completed, namely, a solution D; and continuously stirring the solution D under the same condition, finally aging at room temperature, then centrifugally washing with deionized water and absolute ethyl alcohol three times respectively, and carrying out vacuum drying to obtain the zinc-doped iron-based Prussian blue Zn-FeHCF positive electrode material.

Description

technical field [0001] The invention belongs to the technical field of sodium ion batteries, and relates to an inert transition metal element-doped iron-based Prussian blue sodium-ion battery positive electrode material and a preparation method thereof, in particular to the preparation of a zinc-doped iron-based Prussian blue material prepared by a slow co-precipitation method method. Background technique [0002] Entering the new era of the 21st century, with the rapid development of the global economy and the sharp increase in energy demand, the country has developed a large number of non-renewable fossil energy such as oil and natural gas, and its unrestrained use will inevitably bring about problems that cannot be fundamentally solved now. Problems, such as rising global temperature, resource shortage, acid rain, air pollution, greenhouse effect and other environmental problems. Therefore, people have to put the exploration of clean energy that does not emit pollutants ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C01C3/08C01C3/12H01M4/58H01M4/62H01M10/054
CPCC01C3/08C01C3/12H01M4/58H01M10/054H01M4/62C01P2006/40Y02E60/10
Inventor 张露露陈朝尧魏程傅心远杨学林
Owner CHINA THREE GORGES UNIV
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