TY - JOUR
T1 - Unexpected electrochemical behavior of an anolyte redoxmer in flow battery electrolytes
T2 - Solvating cations help to fight against the thermodynamic-kinetic dilemma
AU - Zhao, Yuyue
AU - Yu, Zhou
AU - Robertson, Lily A.
AU - Zhang, Jingjing
AU - Shi, Zhangxing
AU - Bheemireddy, Sambasiva R.
AU - Shkrob, Ilya A.
AU - Y Z, Z
AU - Li, Tao
AU - Zhang, Zhengcheng
AU - Cheng, Lei
AU - Zhang, Lu
N1 - Publisher Copyright:
© 2020 The Royal Society of Chemistry.
PY - 2020/7/21
Y1 - 2020/7/21
N2 - Redoxmers are redox-active molecules that can store energy in electrolytes for redox flow batteries (RFBs), and their electrochemical properties are significantly affected by the choice of supporting electrolytes. Herein, we use 2,1,3-benzothiadiazole (BzNSN) as a model system to scrutinize the supporting electrolyte impact. By systemically varying the components of supporting salts, BzNSN not only shows substantial redox potential shifts but also exhibits varying electrochemical stabilities. Specifically, changing the size of cations can effectively alter the coordination between the supporting salt and BzNSN species. From Li+, Na+, K+, to NEt4+, the redox potential of BzNSN shifts negatively, from -1.63 V to -1.82 V vs. Ag/Ag+. Molecular dynamics and density functional theory simulations revealed that smaller cations, like Li+, are closer to the charged BzNSN when coordinated, implying stronger coordination, while larger cations, like K+ and NEt4+, are farther away. Interestingly, the large cation electrolytes also lead to much improved electrochemical stability, evidenced by the extraordinarily enhanced kinetic lifetime from electron paramagnetic resonance measurement. This study demonstrates the first example of tuning an anolyte redoxmer toward a concurrent improvement of lowered redox potentials AND enhanced calendar lives via solvation means, which is usually constrained by the thermodynamic-kinetic relation.
AB - Redoxmers are redox-active molecules that can store energy in electrolytes for redox flow batteries (RFBs), and their electrochemical properties are significantly affected by the choice of supporting electrolytes. Herein, we use 2,1,3-benzothiadiazole (BzNSN) as a model system to scrutinize the supporting electrolyte impact. By systemically varying the components of supporting salts, BzNSN not only shows substantial redox potential shifts but also exhibits varying electrochemical stabilities. Specifically, changing the size of cations can effectively alter the coordination between the supporting salt and BzNSN species. From Li+, Na+, K+, to NEt4+, the redox potential of BzNSN shifts negatively, from -1.63 V to -1.82 V vs. Ag/Ag+. Molecular dynamics and density functional theory simulations revealed that smaller cations, like Li+, are closer to the charged BzNSN when coordinated, implying stronger coordination, while larger cations, like K+ and NEt4+, are farther away. Interestingly, the large cation electrolytes also lead to much improved electrochemical stability, evidenced by the extraordinarily enhanced kinetic lifetime from electron paramagnetic resonance measurement. This study demonstrates the first example of tuning an anolyte redoxmer toward a concurrent improvement of lowered redox potentials AND enhanced calendar lives via solvation means, which is usually constrained by the thermodynamic-kinetic relation.
UR - http://www.scopus.com/inward/record.url?scp=85089548888&partnerID=8YFLogxK
U2 - 10.1039/d0ta02214d
DO - 10.1039/d0ta02214d
M3 - Article
AN - SCOPUS:85089548888
SN - 2050-7488
VL - 8
SP - 13470
EP - 13479
JO - Journal of Materials Chemistry A
JF - Journal of Materials Chemistry A
IS - 27
ER -