Superoxide Stabilization and a Universal KO2 Growth Mechanism in Potassium-Oxygen Batteries.

Rechargeable potassium-oxygen (K-O2 ) batteries promise to provide higher round-trip efficiency and cycle life than other alkali-oxygen batteries with satisfactory gravimetric energy density (935 Wh kg-1 ). Exploiting a strong electron-donating solvent, for example, dimethyl sulfoxide (DMSO) strongly stabilizes the discharge product (KO2 ), resulting in significant improvement in electrode kinetics and chemical/electrochemical reversibility. The first DMSO-based K-O2 battery demonstrates a much higher energy efficiency and stability than the glyme-based electrolyte. A universal KO2 growth model is developed and it is demonstrated that the ideal solvent for K-O2 batteries should strongly stabilize superoxide (strong donor ability) to obtain high electrode kinetics and reversibility while providing fast oxygen diffusion to achieve high discharge capacity. This work elucidates key electrolyte properties that control the efficiency and reversibility of K-O2 batteries.

[1]  S. Ye,et al.  In Situ Study of Oxygen Reduction in Dimethyl Sulfoxide (DMSO) Solution: A Fundamental Study for Development of the Lithium–Oxygen Battery , 2015 .

[2]  Martin Wilkening,et al.  Singulett‐Sauerstoff in der aprotischen Natrium‐O2‐Batterie , 2017 .

[3]  Daniel Sharon,et al.  Oxidation of Dimethyl Sulfoxide Solutions by Electrochemical Reduction of Oxygen , 2013 .

[4]  Yongsheng Han,et al.  Shaping particles by chemical diffusion and reaction , 2017 .

[5]  Y. Oaki,et al.  Bioinspired Hierarchical Crystals , 2010 .

[6]  W. Tiller.  Dendrites , 1964, Science.

[7]  P. Bruce,et al.  A Reversible and Higher-Rate Li-O2 Battery , 2012, Science.

[8]  D. Bethune,et al.  Limitations in Rechargeability of Li-O2 Batteries and Possible Origins. , 2012, The journal of physical chemistry letters.

[9]  Philipp Adelhelm,et al.  On the Thermodynamics, the Role of the Carbon Cathode, and the Cycle Life of the Sodium Superoxide (NaO2) Battery , 2014 .

[10]  Xiaodi Ren,et al.  Probing Mechanisms for Inverse Correlation between Rate Performance and Capacity in K-O2 Batteries. , 2017, ACS applied materials & interfaces.

[11]  Linda F Nazar,et al.  The importance of nanometric passivating films on cathodes for Li-air batteries. , 2014, ACS nano.

[12]  Mario Leypold,et al.  Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium–oxygen batteries , 2017, Nature Energy.

[13]  M. Wilkening,et al.  Singlet Oxygen during Cycling of the Aprotic Sodium–O2 Battery , 2017, Angewandte Chemie.

[14]  Yiying Wu,et al.  The Long-Term Stability of KO2 in K-O2 Batteries. , 2018, Angewandte Chemie.

[15]  Sanjeev Mukerjee,et al.  Influence of Nonaqueous Solvents on the Electrochemistry of Oxygen in the Rechargeable Lithium−Air Battery , 2010 .

[16]  Yiying Wu,et al.  A low-overpotential potassium-oxygen battery based on potassium superoxide. , 2013, Journal of the American Chemical Society.

[17]  Ye Xu,et al.  Reversibility of Noble Metal-Catalyzed Aprotic Li-O₂ Batteries. , 2015, Nano letters.

[18]  E. Ben-Jacob,et al.  The formation of patterns in non-equilibrium growth , 1990, Nature.

[19]  Xuanxuan Bi,et al.  Understanding side reactions in K-O2 batteries for improved cycle life. , 2014, ACS applied materials & interfaces.

[20]  K. Abraham.  Electrolyte-Directed Reactions of the Oxygen Electrode in Lithium-Air Batteries , 2015 .

[21]  Yi‐Chun Lu,et al.  Critical Role of Redox Mediator in Suppressing Charging Instabilities of Lithium-Oxygen Batteries. , 2016, Journal of the American Chemical Society.

[22]  Kishan Dholakia,et al.  The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li-O2 batteries. , 2014, Nature chemistry.

[23]  Xiaoping Song,et al.  In situ studies of different growth modes of silver crystals induced by the concentration field in an aqueous solution , 2011 .

[24]  Sanjeev Mukerjee,et al.  Studies of Li-Air Cells Utilizing Dimethyl Sulfoxide-Based Electrolyte , 2013 .

[25]  Hubert A. Gasteiger,et al.  A Novel On-Line Mass Spectrometer Design for the Study of Multiple Charging Cycles of a Li-O2 Battery , 2013 .

[26]  Lei Qin,et al.  Dendrite-Free Potassium-Oxygen Battery Based on a Liquid Alloy Anode. , 2017, ACS applied materials & interfaces.

[27]  H. Gasteiger,et al.  Stability of superoxide radicals in glyme solvents for non-aqueous Li-O2 battery electrolytes. , 2013, Physical chemistry chemical physics : PCCP.

[28]  Dan Xu,et al.  Novel DMSO-based electrolyte for high performance rechargeable Li-O2 batteries. , 2012, Chemical communications.

[29]  Tao Yang,et al.  Quantitatively Relating Diffusion and Reaction for Shaping Particles , 2016 .

[30]  Yi‐Chun Lu,et al.  Mechanistic Insights into Catalyst-Assisted Nonaqueous Oxygen Evolution Reaction in Lithium–Oxygen Batteries , 2016 .

[31]  Ralph G. Pearson,et al.  HARD AND SOFT ACIDS AND BASES , 1963 .

[32]  Stefan A Freunberger,et al.  The carbon electrode in nonaqueous Li-O2 cells. , 2013, Journal of the American Chemical Society.