Transition-metal(TM)-based Prussian blue and its analogues(TM-PBAs)have attracted considerable attention as cathode materials owing to their versatile ion storage capability with tunable working volt-ages.TM-PBAs with different crystal structures,morphologies,and TM combinations can exhibit excel-lent electrochemical properties because of their unique and robust host frameworks with well-defined<100>ionic diffusion channels.Nonetheless,there is still a lack of understanding regarding the perfor-mance dependence of TM-PBAs on structural changes during charging/discharging processes.In this study,in situ X-ray diffraction and X-ray absorption fine structure analyses elucidate the TM-dependent structural changes in a series of TM-PBAs during the charging and discharging processes.During the discharging process,the lattice volume of Fe-PBA increased while those of Ni-and Cu-PBAs decreased.This discrepancy is attributed to the extent of size reduction of the cyanometallate complex([Fe(CN)6])via pi-backbonding from Fe to C due to redox flips of the low-spin Fe3+/2+ion.This study pre-sents a comprehensive understanding of how TM selection affects capacity acquisition and phase transi-tion in TM-PBAs,a promising class of cathode materials.

Ju-Hyeon Lee;Jin-Gyu Bae;Hyeon Jeong Lee;Ji Hoon Lee

School of Materials Science and Engineering,Kyungpook National University,Daegu 41566,Republic of Korea;Department of Materials,University of Oxford,Oxford OX1 3PH,United Kingdom

能源化学

[1]Ju-Hyeon Lee;Jin-Gyu Bae;Hyeon Jeong Lee;Ji Hoon Lee-.Unveiling anomalous lattice shrinkage induced by Pi-backbonding in Prussian blue analogues)[J].能源化学,2022(07):121-128

backbonding,cyanometallate,flips,2+ion

Unveiling,anomalous,lattice,shrinkage,induced,by,Pi,Prussian,blue,analogues,Transition,TM,its,PBAs,have,attracted,considerable,attention,cathode,materials,owing,their,versatile,storage,capability,tunable,working,volt,ages,different,crystal,structures,morphologies,combinations,can,exhibit,excel,lent,electrochemical,properties,because,unique,robust,host,frameworks,well,defined,ionic,diffusion,channels,Nonetheless,there,still,lack,understanding,regarding,perfor,mance,dependence,structural,changes,during,discharging,processes,In,this,study,situ,ray,diffraction,absorption,analyses,elucidate,dependent,series,During,volume,increased,while,those,decreased,This,discrepancy,attributed,extent,size,reduction,complex,CN,via,from,due,redox,low,spin,Fe3+,sents,comprehensive,how,selection,affects,capacity,acquisition,phase,transi,promising,class

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