Pierini Adriano, Brutti Sergio, Bodo Enrico
Department of Chemistry, University of Rome "La Sapienza", P. A. Moro 5, 00185 Rome, Italy.
GISEL-Centro di Riferimento Nazionale per i Sistemi di Accumulo Elettrochimico di Energia, INSTM, via G. Giusti 9, 50121 Firenze, Italy.
Phys Chem Chem Phys. 2021 Nov 3;23(42):24487-24496. doi: 10.1039/d1cp03188k.
Multivalent aprotic metal-oxygen batteries are a novel concept in the applied electrochemistry field. These systems are variants of the so-called Li-air batteries and up to present are in their research infancy. The superoxide disproportionation reaction is a crucial step for the operation of any metal-oxygen redox system using aprotic solvents: in the best scenario, disproportionation leads to peroxide formation while in the worse one it releases singlet molecular oxygen. In this work we address the fundamental thermodynamics of such reaction for alkali (Li, Na and K) and alkaline earth (Be, Mg and Ca) metal-O systems using multiconfigurational methods. Our aim is to draw a comprehensive description of the disproportionation reaction from superoxides to peroxides and to provide the thermodynamic likelihood of the pathways to singlet oxygen release.
多价非质子金属-氧电池是应用电化学领域的一个新概念。这些体系是所谓锂空气电池的变体，目前仍处于研究初期。超氧化物歧化反应是任何使用非质子溶剂的金属-氧氧化还原体系运行的关键步骤：在最佳情况下，歧化反应会导致过氧化物的形成，而在最坏的情况下，它会释放单线态分子氧。在这项工作中，我们使用多组态方法研究了碱金属（锂、钠和钾）和碱土金属（铍、镁和钙）金属-氧体系中该反应的基本热力学。我们的目的是全面描述从超氧化物到过氧化物的歧化反应，并提供单线态氧释放途径的热力学可能性。
