Enhancing zinc storage performance of Mn_(3)O_(4)cathode through Ag-doping and-crosslinking dual-modification strategy  

Ag掺杂和交联双修饰策略提升Mn_(3)O_(4)的储锌性能

作　　者：Xin-yuan WANG Tian-zhen JIAN Ya-ting YANG Jian-ping MA Xian-hong LI Zi-long XUE Wen-qing MA Cai-xia XU 王欣媛;简天真;杨雅婷;马建平;李现红;薛子龙;马文庆;徐彩霞(济南大学化学化工学院山东省生物诊断与治疗技术设备协同创新中心前沿交叉科学研究院,济南250022;山东圣阳电源股份有限公司,曲阜273100;山东大学晶体材料国家重点实验室,济南250100)

机构地区：[1]Institute for Advanced Interdisciplinary Research,Collaborative Innovation Center of Technology and Equipment for Biological Diagnosis and Therapy in Universities of Shandong,School of Chemistry and Chemical Engineering,University of Jinan,Jinan 250022,China [2]Shandong Sacred Sun Power Sources Co.,Ltd.,Qufu 273100,China [3]State Key Laboratory of Crystal Materials,Shandong University,Jinan 250100,China

出　　处：《Transactions of Nonferrous Metals Society of China》2024年第11期3693-3706,共14页中国有色金属学报（英文版）

基　　金：financially supported by the Natural Science Foundation of Shandong Province,China (Nos.ZR2023ME155,ZR2023ME085);the National Natural Science Foundation of China (No.52201254);the Project of“20 Items of University”of Jinan,China (No.202228046);the Taishan Scholar Project of Shandong Province,China (No.tsqn202306226)。

摘　　要：Octahedral Mn_(3)O_(4)nanoparticles with an Ag-doping and nanoporous Ag(NPS)framework was simply fabricated through an alloying-etching engineering.The dual-modified Mn_(3)O_(4)(denoted as Ag−Mn_(3)O_(4)/NPS)consists of Ag-doped Mn_(3)O_(4)nanoparticles crosslinked with three dimensional nanoporous Ag framework.The incorporated Ag dopant is effective in improving the intrinsic ionic and electronic conductivities of Mn_(3)O_(4),while the NPS framework is introduced to improve the electron/mass transfer across the entire electrode.Profiting from the dual-modification strategy,the Ag−Mn_(3)O_(4)/NPS exhibits admirable rate capability and cycling stability.A high reversible capacity of 88.7 mA·h/g can still be retained for over 1000 cycles at a current density of 1 A/g.Moreover,a series of ex-situ experimental techniques indicate that for Ag−Mn_(3)O_(4)/NPS electrode during the zinc ion storage,Mn_(3)O_(4)is electrochemically oxidized into various MnOx(e.g.,Mn_(2)O_(3),MnO2)species in the initial charging,and the subsequent battery reaction is actually the intercalation/deintercalation of H+and Zn2+into MnOx.通过合金化-刻蚀工程制备Ag掺杂和纳米多孔Ag(NPS)交联的Mn_(3)O_(4)八面体纳米颗粒。所制备的双修饰Mn_(3)O_(4)(Ag-Mn_(3)O_(4)/NPS)由Ag掺杂的Mn_(3)O_(4)八面体和纳米多孔银骨架交联构成。Ag的晶格掺杂能够有效改善Mn_(3)O_(4)阴极材料的离子和电子电导率,而NPS框架可以改善整个电极的电子/物质传输效率。得益于双修饰策略,Ag-Mn_(3)O_(4)/NPS表现出高的倍率和循环性能,在1 A/g的电流密度下循环1000次后仍可获得88.7 mA·h/g的高可逆容量。此外,一系列非原位实验技术证明了Ag-Mn_(3)O_(4)/NPS的储锌机制:其在首次充电过程中被电化学氧化为多种MnOx(如Mn_(2)O_(3),MnO2),后续的电池反应为H+和Zn2+在MnOx中的嵌入/脱出。

关 键 词：Ag-doped Mn_(3)O_(4) zinc ion battery nanoporous Ag DEALLOYING 

分 类 号：TM912[电气工程—电力电子与电力传动] TB383.1[一般工业技术—材料科学与工程] TQ137.12[化学工程—无机化工]