Enhanced stability and rate performance of zinc-doped cobalt hexacyanoferrate (CoZnHCF) by the limited crystal growth and reduced distortion

被引:26
作者
Kim, Jihwan [1 ]
Yi, Seong-Hoon [1 ]
Li, Li [2 ,3 ]
Chun, Sang-Eun [1 ,4 ]
机构
[1] Kyungpook Natl Univ, Sch Mat Sci & Engn, Daegu 41566, South Korea
[2] Northeastern Univ, State Key Lab Rolling & Automat, Shenyang 110819, Liaoning, Peoples R China
[3] Northeastern Univ, Sch Met, Shenyang 110819, Liaoning, Peoples R China
[4] Kyungpook Natl Univ, Sch Ind Technol Adv, Daegu 41566, South Korea
来源
JOURNAL OF ENERGY CHEMISTRY | 2022年 / 69卷
基金
中国国家自然科学基金; 新加坡国家研究基金会;
关键词
Cobalt hexacyanoferrate; Rate capability; Stability; Growth limitation; Structural distortion; Near-surface-limited redox process; PRUSSIAN BLUE ANALOGS; AQUEOUS SODIUM; ELECTROCHEMICAL PROPERTIES; ELECTRODE MATERIALS; CATHODE MATERIALS; SUPERIOR CATHODE; HIGH-CAPACITY; LOW-COST; ION; REDOX;
D O I
10.1016/j.jechem.2022.01.034
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
Cobalt hexacyanoferrate (CoHCF) is a potential cathode for aqueous Na-ion batteries due to its high theoretical specific capacity (170 mAh g(-1)); however, its lower rate capability and cyclability limit its applications. Structural distortion at a weak N-coordinated crystal field during cycling disintegrates Co, yielding an irreversible reaction. Different Zn amounts ranging 0-1 were added to the Co site to suppress the structural irreversibility of CoHCF, yielding Co1-xZnxHCF powder; this Zn (x <= 0.09) addition reduced the powder's dimension because the lower four coordination of Zn-N, not the six coordination of Co-N, limits the powder growth. Simultaneously, a small lattice parameter and interaxial angle (similar to 90 degrees) are obtained, implying that a narrower Co1-xZnxHCF inner structure is formed to accommodate Na ions. Moreover, the electronic conductivity of Co1-xZnxHCF gradually increased within 0-0.09 range. A smaller particle size with a high surface area leads to a near-surface-limited redox process, similar to a capacitive reaction. Both the surface-limited reaction and electronic conductivity enhances the reversibility due to the smaller charge transfer resistance at the electrode/electrolyte interface caused by Zn addition. Replacing redox-active Co with non-active Zn amount of 0.07 (Co0.93Zn0.07HCF) slightly reduces the specific capacity from 127 to 119 mAh g(-1) at 0.1 A g(-1) due to the shrunken Co charging sites. Rate performance is enhanced by compromising the capacity and reduced distortion, resulting in 81% retention at a 20 times-faster charging rate. Notably, the Co0.93Zn0.07HCF sample exhibited the good stability while preserving 74% of the initial capacity at 0.5 A g(-1) after 200 cycles. (c) 2022 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences Published by Elsevier B.V. All rights reserved.
引用
收藏
页码:649 / 658
页数:10
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