Abstract

In this study, we designed a novel differential electrochemical mass spectrometry (DEMS) system to in-situ quantify the gas generation in batteries. While a lot of battery gas analyses were carried out by DEMS previously, most of those studies were based on small coin cells or EL cells. The fluid electrolyte and limited amount of active material may make it challenging to quantify the gas generation. The DEMS we designed here can continually sample gas from a small 2.5Ah pouch cell, and it has a similar electrolyte to capacity ratio, 1.8g/Ah, with our production cell. To the best of our knowledge, this is the first DEMS design based on a pouch cell.Moreover, by using flowrate-controlled Ar carrier gas and a reasonable residence time setup, our DEMS design not only can identify volatile electrolyte degradation products throughout battery cycling but also quantify the gaseous species production rates as a function of the state of charge. We found that cell chemistry and operation protocol greatly impact gas product species, the production profile of different gases during cycling, and the total gas quantity. For example, the gas evolution of oxidation products, such as CO2 and CO, is exacerbated by the elevated upper cutoff voltage, while reduction products are only minimally affected. Furthermore, changing the electrolyte SEI former, from EC to FEC, or adding different electrolyte additives can affect the gas product species generation dramatically as well.Therefore, we successfully demonstrated DEMS as a powerful tool to probe the gas evolution behavior in different applications-based batteries, provided valuable data for battery reactivity simulation, and most importantly, provided guidance for electrolyte optimization.

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