TY - JOUR
T1 - The identification of stable solvents for nonaqueous rechargeable li-air batteries
AU - Bryantsev, Vyacheslav S.
AU - Uddin, Jasim
AU - Giordani, Vincent
AU - Walker, Wesley
AU - Addison, Dan
AU - Chase, Gregory V.
PY - 2013
Y1 - 2013
N2 - Solvent plays a major role in determining the nature of discharge products and the extent of rechargeability of the nonaqueous lithium-air (oxygen) battery. Here we investigate chemical stability for a number of aprotic solvents against superoxide, including N,N-dialkyl amides, aliphatic and aromatic nitriles, oxygenated phosphorus (V) compounds, substituted 2-oxazolidinones, and fluorinated ethers. The free energy barriers for nucleophilic attack by superoxide and the C-H acidity constants in dimethyl sulfoxide are reported, which provide a theoretical framework for computational screening of stable solvents for Li-air batteries. Theoretical results are complemented bycyclic voltammetryto study the electrochemical reversibilityof the O2/O 2- couple containing tetrabutylammonium salt and GCMS measurements to monitor solvent stability in the presence of KO2 and a Li salt. Excellent agreement among all quantum chemical, electrochemical, and chemical methods has been obtained in evaluating solvent stability against superoxide. The combined theoretical and experimental methodology provides a comprehensive testing ground to identify electrolyte solvents stable in the air cathode. Based upon this knowledge we report on the use of an amide-based electrolyte for rechargeable oxygen electrodes in Li-O2 secondary cells.
AB - Solvent plays a major role in determining the nature of discharge products and the extent of rechargeability of the nonaqueous lithium-air (oxygen) battery. Here we investigate chemical stability for a number of aprotic solvents against superoxide, including N,N-dialkyl amides, aliphatic and aromatic nitriles, oxygenated phosphorus (V) compounds, substituted 2-oxazolidinones, and fluorinated ethers. The free energy barriers for nucleophilic attack by superoxide and the C-H acidity constants in dimethyl sulfoxide are reported, which provide a theoretical framework for computational screening of stable solvents for Li-air batteries. Theoretical results are complemented bycyclic voltammetryto study the electrochemical reversibilityof the O2/O 2- couple containing tetrabutylammonium salt and GCMS measurements to monitor solvent stability in the presence of KO2 and a Li salt. Excellent agreement among all quantum chemical, electrochemical, and chemical methods has been obtained in evaluating solvent stability against superoxide. The combined theoretical and experimental methodology provides a comprehensive testing ground to identify electrolyte solvents stable in the air cathode. Based upon this knowledge we report on the use of an amide-based electrolyte for rechargeable oxygen electrodes in Li-O2 secondary cells.
UR - http://www.scopus.com/inward/record.url?scp=84873134364&partnerID=8YFLogxK
U2 - 10.1149/2.027302jes
DO - 10.1149/2.027302jes
M3 - Article
AN - SCOPUS:84873134364
SN - 0013-4651
VL - 160
SP - A160-A171
JO - Journal of the Electrochemical Society
JF - Journal of the Electrochemical Society
IS - 1
ER -
