TY - JOUR
T1 - Water Contributes to Higher Energy Density and Cycling Stability of Prussian Blue Analogue Cathodes for Aqueous Sodium-Ion Batteries
AU - Guo, Xingyu
AU - Wang, Zhenbin
AU - Deng, Zhi
AU - Li, Xiangguo
AU - Wang, Bo
AU - Chen, Xi
AU - Ong, Shyue Ping
PY - 2019/8/13
Y1 - 2019/8/13
N2 - In this work, we performed a comprehensive study of Prussian blue and its analogues (PBAs), one of the most promising cathode materials for aqueous sodium-ion batteries for large-scale energy-storage systems, using first-principles calculations. It is confirmed that dry PBAs generally undergo a phase transition from a rhombohedral Na2PR(CN)6 (where P and R are transition metals) to a tetragonal/cubic PR(CN)6 during Na extraction, in agreement with experimental observations. Using a grand potential phase diagram construction, we show that water and Na co-intercalation result in fundamentally different phase transition behavior and, hence, electrochemical voltage profiles in wet versus dry electrolytes. Lattice water increases the average voltage and reduces the volume change during electrochemical cycling, resulting in both higher energy density and better cycling stability. Finally, we identified four new PBA compositions, Na2CoMn(CN)6, Na2NiMn(CN)6, Na2CuMn(CN)6, and Na2ZnMn(CN)6, that show great promise as cathodes for aqueous rechargeable Na-ion batteries. © 2019 American Chemical Society.
AB - In this work, we performed a comprehensive study of Prussian blue and its analogues (PBAs), one of the most promising cathode materials for aqueous sodium-ion batteries for large-scale energy-storage systems, using first-principles calculations. It is confirmed that dry PBAs generally undergo a phase transition from a rhombohedral Na2PR(CN)6 (where P and R are transition metals) to a tetragonal/cubic PR(CN)6 during Na extraction, in agreement with experimental observations. Using a grand potential phase diagram construction, we show that water and Na co-intercalation result in fundamentally different phase transition behavior and, hence, electrochemical voltage profiles in wet versus dry electrolytes. Lattice water increases the average voltage and reduces the volume change during electrochemical cycling, resulting in both higher energy density and better cycling stability. Finally, we identified four new PBA compositions, Na2CoMn(CN)6, Na2NiMn(CN)6, Na2CuMn(CN)6, and Na2ZnMn(CN)6, that show great promise as cathodes for aqueous rechargeable Na-ion batteries. © 2019 American Chemical Society.
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U2 - 10.1021/acs.chemmater.9b02269
DO - 10.1021/acs.chemmater.9b02269
M3 - RGC 21 - Publication in refereed journal
SN - 0897-4756
VL - 31
SP - 5933
EP - 5942
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 15
ER -
