生物活性小分子基水系锌有机电池实现长寿命和快充  

Bioactive small-molecule-based aqueous zinc-organic battery enables long-life and fast-charge performance

作　　者：张萌 丁超剑 李超博 王永辉 黄苇苇 Meng Zhang;Chaojian Ding;Chaobo Li;Yonghui Wang;Weiwei Huang(Hebei Key Laboratory of Applied Chemistry,Yanshan University,Qinhuangdao 066004,China;Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),College of Chemistry,Nankai University,Tianjin 300071,China)

机构地区：[1]Hebei Key Laboratory of Applied Chemistry,Yanshan University,Qinhuangdao 066004,China [2]Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education),College of Chemistry,Nankai University,Tianjin 300071,China

出　　处：《Science China Materials》2023年第8期3104-3112,共9页中国科学（材料科学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (21875206 and 21403187);the Subsidy for Hebei Key Laboratory of Applied Chemistry after Operation Performance (22567616H);the Open Project in the Key Laboratory of Advanced Energy Materials Chemistry (Nankai University);the Postgraduate Innovation Funding Project of Hebei Province (CXZZBS2022144)

摘　　要：因具有高安全性和高性价比的优势,水系锌离子电池(AZIBs)成为了当前研究的热点.然而,电极材料溶解、固有电导率低、反应动力学慢等问题严重阻碍了其实际应用.在本文中,我们合成了一种在黑色素瘤治疗中发挥重要作用的含硫有机小分子(seriniquinone,SQ),将其作为电极材料应用于锌离子电池.通过导电碳修饰的方法制备了SQ/CMK-3复合电极,进一步解决了活性物质SQ的溶解问题并提高了其导电性.在Zn||SQ/CMK-3半电池中,SQ/CMK-3正极在100 mA g^(−1)电流密度下的初始放电比容量达到234.4 mA h g^(−1).在1 A g^(−1)的高电流密度下经过5000次超长循环后,比容量仍保持100.2 mA h g^(−1).此外,通过密度泛函理论计算,我们提出了在两个SQ分子之间嵌入四个Zn^(2+)的储存机理,并通过多种非原位表征测试进行了证实.在采用SQ/CMK-3复合材料作为正负两极的全有机对称电池中,SQ不仅在100 mA g^(−1)的电流密度下获得高达110.9 mA h g^(−1)的可逆比容量,而且在循环2500次后具有82.4%的稳定容量保持率和99.5%的平均库仑效率.Aqueous zinc-ion batteries(AZIBs)have become a current research hotspot owing to their high security and cost-effectiveness.However,the dissolution of electrode materials,low intrinsic conductivity,and slow reaction kinetics seriously hinder their practical application.Herein,a sulfur-containing organic small molecule(seriniquinone,SQ),which plays a significant role in melanoma treatment,was synthesized and used as electrodes for AZIBs.To address the dissolution problem as well as enhance the electrical conductivity,SQ was further optimized by conductive carbon modification to prepare SQ/CMK-3 composite electrodes.In Zn||SQ/CMK-3 half-battery,SQ/CMK-3 cathode delivered an initial discharge capacity of 234.4 mA h g^(−1)at 100 mA g^(−1)and maintained 100.2 mA h g^(−1)after ultra-long cycles(5000)at the high current density of 1 A g^(−1).Moreover,a zinc storage mechanism with four Zn^(2+)between two SQ molecules was proposed based on the density functional theory calculation and confirmed by various ex-situ measurements.Assembled with SQ/CMK-3 composite as both the anode and cathode,the allorganic symmetric battery not only displayed a high reversible capacity of 110.9 mA h g^(−1)at 100 mA g^(−1)but also possessed a stable capacity retention rate of 82.4%after 2500 cycles with an average coulombic efficiency of 99.5%.

关 键 词：密度泛函理论计算 反应动力学 原位表征 有机小分子 复合电极 锌离子电池 半电池 电极材料 

分 类 号：TB332[一般工业技术—材料科学与工程] TM912[电气工程—电力电子与电力传动]