Heavy Atom-Induced Spin–Orbit Coupling to Quench Singlet Oxygen in a Li–O2 Battery,Journal of the American Chemical Society

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Heavy Atom-Induced Spin–Orbit Coupling to Quench Singlet Oxygen in a Li–O2 Battery
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2025-03-19 , DOI: 10.1021/jacs.4c15230
Zhuoliang Jiang _{1,

2} , Bo Wen ₁ , Yaohui Huang ₁ , Yuzhe Wang ₁ , Hengyi Fang ₁ , Fujun Li _{1,

3}

Affiliation

Li–O₂ batteries have aroused considerable interest due to high theoretical energy density; however, the singlet oxygen (¹O₂) generated in both discharge and charge processes induces severe parasitic reactions and leads to their low round-trip efficiency and poor rechargeability. Herein, a universal heavy atom-induced quenching mechanism is proposed to suppress ¹O₂ and related side reactions. Br in tris(4-bromophenyl)amine (TBPA) induces strong heavy atom-induced spin–orbit coupling (SOC), enhancing the interaction between the spin angular momentum and the orbital angular momentum of the electron. It enables TBPA to capture electrophilic ¹O₂ to form a singlet complex and then effectively drives the spin-forbidden spin-flip process to form a triplet complex. This accelerates the conversion of ¹O₂ to ground-state ³O₂ through a heavy atom-induced intersystem crossing mechanism, and it efficiently eliminates its attack on organic solvents and carbon cathodes. These endow the Li–O₂ battery with reduced overvoltages and prolonged lifespan for over 350 cycles when coupled with a RuO₂ catalyst. This work highlights the heavy atom-induced SOC to quench ¹O₂ in oxygen evolution reaction-related devices.

中文翻译：

重原子诱导的自旋轨道耦合以淬灭 Li-O2 电池中的单线态氧

Li-O ₂ 电池由于理论能量密度高而引起了相当大的兴趣;然而，在放电和充电过程中产生的单线态氧（ ¹ O ₂ ）会引起严重的寄生反应，并导致它们的往返效率低和可充电性差。在此，提出了一种通用的重原子诱导猝灭机制来抑制 ¹ O ₂ 和相关副反应。三（4-溴苯基）胺（TBPA）中的 Br 诱导强重原子诱导的自旋-轨道耦合（SOC），增强了自旋角动量和电子轨道角动量之间的相互作用。它使 TBPA 能够捕获亲电 ¹ O ₂ 以形成单重态复合物，然后有效地驱动禁止自旋的自旋翻转过程以形成三重态复合物。这通过重原子诱导的系统间交叉机制加速了 ¹ O ₂ 向基态 ³ O ₂ 的转化，并有效地消除了对有机溶剂和碳阴极的攻击。当与 RuO ₂ 催化剂耦合时，它们使 Li-O ₂ 电池具有更低的过电压和更长的使用寿命，循环次数超过 350 次。这项工作突出了重原子诱导的 SOC 在析氧反应相关装置中淬灭 ¹ O ₂ 。

更新日期：2025-03-19

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