In this work, a data-driven identification method, based on polynomial nonlinear autoregressive models with exogenous inputs (NARX) and the Volterra series, is proposed to describe the dynamic and nonlinear voltage and current characteristics of polymer electrolyte membrane fuel cells (PEMFCs). The structure selection and parameter estimation of the NARX model is performed on broad-band voltage/current data. By transforming the time-domain NARX model into a Volterra series representation using the harmonic probing algorithm, a frequency-domain description of the linear and nonlinear dynamics is obtained. With the Volterra kernels corresponding to different operating conditions, information from existing diagnostic tools in the frequency domain such as electrochemical impedance spectroscopy (EIS) and total harmonic distortion analysis (THDA) are effectively combined. Additionally, the time-domain NARX model can be utilized for fault detection by evaluating the difference between measured and simulated output. To increase the fault detectability, an optimization problem is introduced which maximizes this output residual to obtain proper excitation frequencies. As a possible extension it is shown, that by optimizing the periodic signal shape itself that the fault detectability is further increased. (C) 2017 Elsevier B.V. All rights reserved.