NH_(4)^(+)插层Mo掺杂MnO_(2)阴极实现强键合作用助力超稳定水系锌锰电池  

Reinforced bonding of Mo-doped MnO_(2)with ammonium-ion as cathodes for durable aqueous MnO_(2)–Zn batteries

作　　者：郑俊杰 石培 陈驰 陈鑫 甘億 李敬迎 姚佳 杨银 吕琳 马国坤 桃李 汪汉斌 张军 沈谅平 万厚钊 王浩 Junjie Zheng;Pei Shi;Chi Chen;Xin Chen;Yi Gan;Jingying Li;Jia Yao;Yin Yang;Lin Lv;Guokun Ma;Li Tao;Hanbin Wang;Jun Zhang;Liangping Shen;Houzhao Wan;Hao Wang(Hubei Yangtze Memory Laboratories,Wuhan 430205,China;School of Microelectronics,Hubei University,Wuhan 430062,China;CAS Key Laboratory of Design and Assembly of Functional Nanostructures,and Fujian Provincial Key Laboratory of Nanomaterials,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China;Xiamen Institute of Rare Earth Materials,Haixi Institute,Chinese Academy of Sciences,Xiamen 361021,China)

机构地区：[1]Hubei Yangtze Memory Laboratories,Wuhan 430205,China [2]School of Microelectronics,Hubei University,Wuhan 430062,China [3]CAS Key Laboratory of Design and Assembly of Functional Nanostructures,and Fujian Provincial Key Laboratory of Nanomaterials,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [4]Xiamen Institute of Rare Earth Materials,Haixi Institute,Chinese Academy of Sciences,Xiamen 361021,China

出　　处：《Science China Materials》2023年第8期3113-3122,共10页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(22109163 and 52002122);China Postdoctoral Science Foundation(2021M690947).

摘　　要：水系可充电锌/二氧化锰电池因其成本低廉、能量密度高而引起了广泛关注.然而,缓慢的反应动力学和MnO_(2)阴极的歧化反应以及不可逆的相变现象对其发展造成了严重阻碍.在此,我们选用了Mo掺杂α-MnO_(2)(Mo–MnO_(2))作为阴极材料,通过铵根离子插层机制所形成的N–H···O强键合作用来稳定Mo–MnO_(2)的2×2隧道结构,并且有效抑制了Mn^(3+)溶解,在质子插入/脱出过程中不会引起晶格的畸变,进一步提高了其循环稳定性.获得的Mo–MnO_(2)正极在100 mA g^(−1)时表现出265.2 mA h g^(−1)的高比容量和364.3 W h kg^(−1)的能量密度.在2.0 A g^(−1)下1000次循环后,容量保持率达95.2%.这项工作有助于深入了解非金属阳离子在电极主体材料间的键合作用,为设计具有高能量密度和长期循环能力的水系锌离子电池提供了新思路.Aqueous rechargeable Zn//MnO_(2)batteries have attracted extensive research interest owing to their low cost and high energy density.However,the slow reaction kinetics,the disproportionation of the MnO_(2)cathode,and the irreversible phase transition mechanism considerably restrict their development.Here,we chose Mo-dopedα-MnO_(2)(Mo–MnO_(2))as the cathode material and proposed a stable N–H···O bond-reinforced interaction formed via NH4+intercalation to stabilize the 2×2 tunnel structure of Mo–MnO_(2).Theoretical and experimental studies were conducted to demonstrate the performance of the cathode.Mn^(3+)dissolution was effectively inhibited,and lattice distortion did not occur during the proton insertion/removal process,which further improved the cyclic stability of the cathode.Specifically,at a current density of 100 mA g^(−1),the Mo–MnO_(2)cathode exhibited a specific capacity of 265.2 mA h g^(−1),the energy density was 364.3 W h kg^(−1),and the cathode exhibited excellent cyclic stability.At a current density of 2.0 A g^(−1),the specific capacity was 95.2%after 1000 cycles.This work provides further insight into the bond interaction between nonmetallic cations in the main materials of electrodes and contributes to the construction of aqueous-based zinc-ion batteries with high energy density and long-term cycling capability.

关 键 词：锌锰电池 锌离子电池 阴极材料 能量密度 Mo掺杂 键合作用 主体材料 超稳定 

分 类 号：TM912[电气工程—电力电子与电力传动]