Li-Ion Battery Active Material Impedance Analysis I: Comparison of Measured NCM 111 Kinetics with Butler-Volmer Equation Based Predictions

Abstract

The expression for the exchange current density to describe the intercalation kinetics of Li-ion battery materials proposed by Newman and coworkers has been used extensively for battery modeling, however its applicability to existing battery materials should be validated. Here we show an electrochemical impedance spectroscopy (EIS) analysis of the kinetic behavior of NCM 111 as a function of electrolyte salt concentration and state-of-charge (SOC) and compare it to the proposed theory. An areal capacity dependent EIS analysis first gives insights into the feasibility of measuring kinetic and transport parameters, including the solid diffusion resistance of lithium, showing that low-areal capacity electrodes are required to predominantly probe the kinetics. We then show how the charge transfer kinetics follow a Butler-Volmer type concentration dependent behavior for lower concentrated electrolytes (≤1.5 M) but deviate from the proposed theory at higher salt concentrations. A further SOC dependent analysis shows how NCM 111 generally follows the proposed theory of U-shaped symmetric kinetics, but the limited oxidative stability window leads to practically asymmetric kinetics for charging and discharging. This asymmetry is visible in NCM 111 lithiation and delithiation rate tests, where upon lithiation the kinetics generally become slower for higher degrees of lithiation, limiting the performance.

Key findings

• ▸NCM 111 follows Butler-Volmer type concentration dependent behavior at lower electrolyte salt concentrations (≤1.5 M)
• ▸The material deviates from the proposed theory at higher salt concentrations
• ▸The limited oxidative stability window leads to practically asymmetric kinetics

Keywords

Identifiers

DOI

10.1149/1945-7111/acf161

Journal

Journal of The Electrochemical Society

Year

2023