Metal organophosphates:electronic structure tuning from inert materials to universal alkali-metal-ion battery cathodes  

作　　者：Wu-Jie Dong Jia-Bo Le Yan Jin Guo-Qing Zhang Bin Ye Peng Qin Fu-Qiang Huang 

机构地区：[1]State Key Laboratory of High Performance Ceramics and Superfine Microstructure,Shanghai Institute of Ceramics,Chinese Academy of Sciences,Shanghai,200050,China [2]Beijing National Laboratory for Molecular Sciences and State Key Laboratory of Rare Earth Materials Chemistry and Applications,College of Chemistry and Molecular Engineering,Peking University,Beijing,100871,China [3]Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences,Ningbo,315201,China

出　　处：《Rare Metals》2023年第1期122-133,共12页稀有金属（英文版）

基　　金：financially supported by the Science and Technology Commission of Shanghai Municipality (No. 22ZR1471300);the National Science Foundation of China (Nos. 21871008,51922103 and 21801247);the Key Research Program of Chinese Academy of Sciences (No.QYZDJ-SSW-JSC013);China Postdoctoral Science Foundation (Nos.2020M671242 and 2021T140688)。

摘　　要：Organic cathodes for alkali-metal-ion batteries attract great attentions in recent years,but the ion storage sites are limited to some finite functional groups.This is because an organic cathode must have proper lowest unoccupied molecular orbitals(LUMO) to accept electrons at high potential.Herein,a novel type of organophosphate-based cathode has successfully been explored by tuning the LUMO energy level of organophosphates through metal ions with an inert electron pair.For the first time,the P=O of phytate(PA),N,N,N’,N’-ethylenediaminetetrakis(methylene phytate)(EDTMP),and diethylenetriaminepentakis(methyl phytate)(DTPMP) is activated by lead/bismuth(with 6s2electron pair) to storage Li/Na/K ions reversibly.Typically,density functional theory calculations indicate that the LUMO energy of Bi-PA is greatly reduced from-0.99(PA) to-4.61 eV,which shows the first discharge capacity of 173,182 and 206mAh·g-1and the reversibly capacity of 102,102 and 101mAh·g-1with the discharge platform of 2.4,2.1 and 2.4 V for Li/Na/K-ion battery cathodes,respectively.Similarly,with proper LUMO energy level,Pb-PA(-4.63 eV),Pb-EDTMP(-3.71 eV),and Pb-DTPMP(-4.45 eV) all exhibit admirable performance.This unique strategy of organic materials to alkali-metal-ion battery cathodes offers a new avenue for future energy storage systems.

关 键 词：Organic cathodes Alkali-metal-ion battery Lowest unoccupied molecular orbitals(LUMO) Organophosphates 

分 类 号：TM912[电气工程—电力电子与电力传动]