Nonlinear frequency response analysis (NFRA), also known as nonlinear impedance spectroscopy is the younger, less well-known sibling of impedance spectroscopy (EIS). In contrast to EIS, a large sinusoidal current or potential input is used; the output signal then contains higher harmonics, which are a nonlinear fingerprint of the electrochemical system under investigation. Why is this nonlinear response of practical relevance? Because electrochemical reactions have typically a nonlinear relation of current and potential. NFRA thus allows to discriminate between different reactions that give a similar linear response (i.e. EIS), to identify and parameterise reaction kinetics or surface/degradation changes, or to simply check if a process in EIS is nonlinear. Recent applications comprise batteries, electrosyntheses, and fuel cells. [1] This talk thrives to make NFRA more accessible to the electrochemistry and battery community. It introduces the NFRA technique (left Fig.) and its application to Li-ion batteries [3-6]. It gives an insight how to conduct reliable measurements, and which nonlinearities can be expected from reaction and transport processes [2]. Applied to Li-ion batteries, i.a. the potential for state-of-health estimation [3], for uniquely detecting Li-Plating (right Fig) or in-depth analysis on the impact of particle size on aging [5] is demonstrated. Models are shown to aid interpreting the NFR spectra. [6] Figure. Illustration of nonlinear frequency response analysis [2] (left) and spectra showing clear changes between plating (-10°C) vs. classical aging (25°C) [4](right).
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