Issue 43, 2023

In situ detection of reactive oxygen species spontaneously generated on lead acid battery anodes: a pathway for degradation and self-discharge at open circuit

Abstract

Prospects for refurbishing and recycling energy storage technologies such as lead acid batteries (LABs) prompt a better understanding of their failure mechanisms. LABs suffer from a high self-discharge rate accompanied by deleterious hard sulfation processes which dramatically decrease cyclability. Furthermore, the evolution of H2, CO, and CO2 also poses safety risks. Despite the maturity of LAB technologies, the mechanisms behind these degradation phenomena have not been well established, thus hindering attempts to extend the cycle life of LABs in a sustainable manner. Here, we investigate the effect of the oxygen reduction reaction (ORR) on the sulfation of LAB anodes under open circuit (OC). For the first time, we found that the sulfation reaction is significantly enhanced in the presence of oxygen. Interestingly, we also report the formation of reactive oxygen species (ROS) during this process, known to hamper cycle life of batteries via corrosion. Electron spin resonance (ESR) and in situ scanning electrochemical microscopy (SECM) unambiguously demonstrated the presence of OH˙ and of H2O2 as the products of spontaneous ORR on LAB anodes. High temporal resolution SECM measurements of the hydrogen evolution reaction (HER) during LAB anode corrosion displayed a stochastic nature, highlighting the value of the in situ experiment. Balancing the ORR and HER prompts self-discharge while reaction of the carbon additives with highly oxidizing ROS may explain previously reported parasitic reactions generating CO and CO2. This degradation mode implicating ROS and battery corrosion impacts the design, operation, and recycling of LABs as well as upcoming chemistries involving the ORR.

Graphical abstract: In situ detection of reactive oxygen species spontaneously generated on lead acid battery anodes: a pathway for degradation and self-discharge at open circuit

Supplementary files

Article information

Article type
Edge Article
Submitted
07 9 2023
Accepted
17 10 2023
First published
18 10 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 12292-12298

In situ detection of reactive oxygen species spontaneously generated on lead acid battery anodes: a pathway for degradation and self-discharge at open circuit

A. Asserghine, A. Baby, S. T. Putnam, P. Qian, E. Gao, H. Zhao and J. Rodríguez-López, Chem. Sci., 2023, 14, 12292 DOI: 10.1039/D3SC04736A

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