TY - JOUR
T1 - Practicality assessment
T2 - Temperature-governed performance of CO2-containing Li–O2 batteries
AU - Marques Mota, Filipe
AU - Allam, Omar
AU - Chae, Kyunghee
AU - Che Mohamad, Nur Aqlili Riana
AU - Jang, Seung Soon
AU - Kim, Dong Ha
N1 - Funding Information:
This work was supported by the National Research Foundation of Korea (NRF) Grant funded by the Korean Government (2020R 1A 2C 3003958), by the Basic Science Research Program (Priority Research Institute) through the NRF of Korea funded by the Ministry of Education (2021R1A6A1A10039823), by the Korea Basic Science Institute (National Research Facilities and Equipment Center) grant funded by the Ministry of Education (2020R 1A 6C 101B194) and by the Creative Materials Discovery Program through the NRF funded by the Ministry of Science and ICT (2018M 3D 1A 1058536). F.M.M. acknowledges the support by the Brain Pool Program through NRF funded by the Ministry of Science and ICT (2017H1D3A1A02054206).
Publisher Copyright:
© 2022
PY - 2022/12/1
Y1 - 2022/12/1
N2 - Practical lithium–oxygen batteries require a shift from pure O2 to air. CO2 traces, however, fundamentally alter the O2 electrochemistry towards Li2CO3 formation via peroxocarbonate intermediates in highly-solvating electrolytes e.g., tetraethylene glycol dimethyl ether (G4). Here, we reveal that operating temperatures (0∼70 °C) critically dictate Li2CO3-associated cell overcharges (4.60∼3.77 V), by determining temperature-dependent reaction kinetics and evolving species mobility, as analogously witnessed under pure O2-conditions. Against what is observed for Li2O2 formation in the Li–O2 cell, however, cell temperatures do not govern the crystallinity of the Li2CO3 discharge product. In agreement with experimental observations, comprehensive density functional theory calculations also uncover the effect of the temperature on the Li2CO3 precipitation mechanism and shed light on the dwindling stabilization of metastable peroxocarbonate intermediates during discharge at increasing cycling temperatures. On the other hand, during extended operation, the temperature-dependent reactants mobility in the viscous G4 electrolyte and remnant Li-deficient carbonate surfaces from precedent recharge steps play equally prominent roles on the Li2CO3 precipitation mechanism and the resulting cell capacity. Our study highlights the complexity of practical Li–O2 cells with temperature-dependent performances.
AB - Practical lithium–oxygen batteries require a shift from pure O2 to air. CO2 traces, however, fundamentally alter the O2 electrochemistry towards Li2CO3 formation via peroxocarbonate intermediates in highly-solvating electrolytes e.g., tetraethylene glycol dimethyl ether (G4). Here, we reveal that operating temperatures (0∼70 °C) critically dictate Li2CO3-associated cell overcharges (4.60∼3.77 V), by determining temperature-dependent reaction kinetics and evolving species mobility, as analogously witnessed under pure O2-conditions. Against what is observed for Li2O2 formation in the Li–O2 cell, however, cell temperatures do not govern the crystallinity of the Li2CO3 discharge product. In agreement with experimental observations, comprehensive density functional theory calculations also uncover the effect of the temperature on the Li2CO3 precipitation mechanism and shed light on the dwindling stabilization of metastable peroxocarbonate intermediates during discharge at increasing cycling temperatures. On the other hand, during extended operation, the temperature-dependent reactants mobility in the viscous G4 electrolyte and remnant Li-deficient carbonate surfaces from precedent recharge steps play equally prominent roles on the Li2CO3 precipitation mechanism and the resulting cell capacity. Our study highlights the complexity of practical Li–O2 cells with temperature-dependent performances.
KW - CO
KW - Cycling conditions
KW - Energy storage
KW - Li–O
KW - O electrochemistry
UR - http://www.scopus.com/inward/record.url?scp=85133227822&partnerID=8YFLogxK
U2 - 10.1016/j.cej.2022.137744
DO - 10.1016/j.cej.2022.137744
M3 - Article
AN - SCOPUS:85133227822
SN - 1385-8947
VL - 449
JO - Chemical Engineering Journal
JF - Chemical Engineering Journal
M1 - 137744
ER -