Affiliation:
1. Institute of Materials Research Tsinghua Shenzhen International Graduate School Tsinghua University Shenzhen 518055 China
2. Institute of High Energy Physics Beijing Synchrotron Radiation Facility Chinese Academy of Sciences Beijing 100049 China
3. Shenzhen Power Supply Co., Ltd Shenzhen 518020 China
4. Future Technology School Shenzhen Technology University Shenzhen 518055 China
5. Faculty of Materials Science and Energy Engineering/Institute of Technology for Carbon Neutrality Shenzhen Institute of Advanced Technology Chinese Academy of Sciences Shenzhen 518055 China
Abstract
AbstractVanadate materials are feasible cathodes for metal–ion batteries due to their stable layered structure, abundant valence states, and high capacity. However, much uncertainty still exists about precisely modulating intercalants to facilitate ion storage. Here, V2O5 pre‐intercalated with various transition metal ions M2+ (M═Ni, Co, Mn) are developed as model materials to analyze the coupling effect between guest ions and host material. Through density functional theory simulations, it is found that M2+ interacts with V–O chain via M 3d‐O 2p covalent bonds, and extended X‐ray absorption fine structure reveals the Ni─O interatomic distance at 1.56 Å shorter than Co─O (1.60 Å) and Mn─O (1.72 Å), suggesting the M–O band type with different covalency degree can optimize VOx polyhedron and local electronic structure. Furthermore, NiVO cathode materials with the smallest layer spacing shows higher redox voltage and better rate/cycling performance for Ca2+ storage than CoVO/MnVO, elucidating that Ni has stronger tendency to attract electrons and bonds with V–O layer tightly, thus supplying a reliable ion diffusion channel for Ca2+. Through ions pre‐intercalated techniques, this work highlights both layer spacing and physicochemical properties of intercalants affect electrochemical process, which is significant for developing high‐performance vanadate cathode materials.
Funder
National Natural Science Foundation of China
Shenzhen Science and Technology Innovation Program
Basic and Applied Basic Research Foundation of Guangdong Province
Subject
Electrochemistry,Condensed Matter Physics,Biomaterials,Electronic, Optical and Magnetic Materials