Coulombic efficiency and capacity retention are not universal descriptors of cell aging

TL;DR

This paper demonstrates that capacity and coulombic efficiency are unreliable universal indicators of Li-ion battery aging, as electrode properties and testing conditions significantly influence these measurements and can mask true degradation.

Contribution

It reveals how electrode-specific voltage profiles and testing variables affect capacity-based aging assessments, challenging their universal applicability.

Findings

Capacity measurements can underestimate side reactions due to accessible Li+ reservoirs.

Different electrode chemistries show varying capacity fade rates despite similar SEI growth.

Testing conditions like depth of discharge influence perceived aging effects.

Abstract

Capacity and coulombic efficiency are often used to assess the performance of Li-ion batteries, under the assumption that these quantities can provide direct insights about the rate of electron consumption due to growth of the solid electrolyte interphase (SEI). Here, we show that electrode properties can actually change the amount of information about aging that can be directly retrieved from capacity measurements. During cycling of full-cells, only portions of the voltage profiles of the cathode and anode are accessible, leaving a reservoir of cyclable Li+ stored at both electrodes. The size and availability of this reservoir depends on the shape of the voltage profiles, and accessing this extra Li+ can offset some of the capacity that is consumed by the SEI. Consequently, capacity and efficiency measurements can, at times, severely underestimate the rate of side reactions experienced by the cell. We show, for example, that a same rate of SEI growth would cause faster capacity fade in LiFePO4 than in NMC cells, and that the perceived effects of aging depend on testing variables such as depth of discharge. Simply measuring capacity may be insufficient to gauge the true extent of aging endured by Li-ion batteries.