Influence of the Discretization Methods on the Distribution of Relaxation Times Deconvolution: Implementing Radial Basis Functions with DRTtools

Increasing the specific energy, energy density, specific power, energy efficiency and energy retention of electrochemical storage devices are major incentives for the development of all-solid-state batteries. However, a general evaluation of all-solid-state battery performance is often difficult to derive from published reports, mostly due to the interdependence of performance measures, but also due to the lack of a basic reference system. Here, we present all-solid-state batteries reduced to the bare minimum of compounds, containing only a lithium metal anode, β-Li3PS4 solid electrolyte and Li(Ni0.6Co0.2Mn0.2)O2 cathode active material. We use this minimalistic system to benchmark the performance of all-solid-state batteries. In a Ragone-type graph, we compare literature data for thiophosphate-, oxide-, phosphate- and polymer-based all-solid-state batteries with our minimalistic cell. Using fundamental equations for key performance parameters, we identify research targets towards high energy, high power and practical all-solid-state batteries. Considering the interdependence of performance measures and the lack of a basic reference system for all-solid-state batteries, Jurgen Janek and co-workers analyse literature performance data for major types of all-solid-state batteries and benchmark them against minimalistic reference cells.

Benchmarking the performance of all-solid-state lithium batteries

The impedance of anode-supported single cells [Ni/8 yttria-stabilized zirconia (YSZ) anode; La 0.58 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ cathode; 8YSZ electrolyte; area 1 cm 2 ] was characterized in a broad measuring range of temperature and air/fuel gas composition. The data has been analyzed by calculating the distribution function of relaxation times (DRTs). DRT computations enabled us to separate five different loss mechanisms occurring inside the cathode and anode without the need of an equivalent circuit. Two processes exhibit a systematic dependency on changes in the oxygen partial pressure of the cathode gas and thus can be attributed to diffusional and electrochemical losses on the cathode side. The remaining three processes are very sensitive to changes in the fuel gas but are not affected by variations of the cathode gas. These resistances are classified as a gas diffusion polarization within the anode-substrate and as an electro-oxidation reaction at the triple-phase boundary, respectively.

https://iopscience.iop.org/article/10.1149/1.2801372/pdf

Evaluation and Modeling of the Cell Resistance in Anode-Supported Solid Oxide Fuel Cells

Co-electrolysis of CO2 and H2O in solid oxide cells: Performance and durability

Studies on LiFePO4 as cathode material using impedance spectroscopy

The polarization processes occurring at the electrode–electrolyte interfaces of solid oxide fuel cells (SOFC) were investigated by electrochemical impedance spectra measured at single cells under realistic operating conditions. The approach presented is based on distributions of relaxation times which are the basic quantity of interest in electrochemical impedance data analysis. A deconvolution method was developed and implemented that yields these characteristic distribution patterns directly from the impedance spectra. In contrast to nonlinear least squares curve fit of equivalent circuit models, no a priori circuit choice has to be made. Even more importantly, the excellent resolving capacity allows the untangling of the impedance contributions of up to three physically distinct processes within one frequency decade. With the method, processes with the highest polarization losses can be identified and targeted to improve cell performance. Based on the distributions, a general strategy for the identification of the reaction mechanisms is given. The evaluation of the distributions in terms of peak parameters is illustrated by a physical model for oxygen reduction at the SOFC cathode–electrolyte interface. The method is expected to find many applications in electrochemistry beyond the field of solid oxide fuel cell development.

Deconvolution of electrochemical impedance spectra for the identification of electrode reaction mechanisms in solid oxide fuel cells

The polarization processes occurring at the electrode-electrolyte interfaces of solid oxide fuel cells (SOFC) were investigated by electrochemical impedance spectra measured at single cells under realistic operating conditions. The approach presented is based on distributions of relaxation times which are the basic quantity of interest in electrochemical impedance data analysis. A deconvolution method was developed and implemented that yields these characteristic distribution patterns directly from the impedance spectra. In contrast to nonlinear least squares curve fit of equivalent circuit models, no a priori circuit choice has to be made. Even more importantly, the excellent resolving capacity allows the untangling of the impedance contributions of up to three physically distinct processes within one frequency decade. With the method, processes with the highest polarization losses can be identified and targeted to improve cell performance. Based on the distributions, a general strategy for the identification of the reaction mechanisms is given. The evaluation of the distributions in terms of peak parameters is illustrated by a physical model for oxygen reduction at the SOFC cathode-electrolyte interface. The method is expected to find many applications in electrochemistry beyond the field of solid oxide fuel cell development.

H. Schichlein

Papers

Deconvolution of electrochemical impedance spectra for the identification of electrode reaction mechanisms in solid oxide fuel cells

Deconvolution of electrochemical impedance spectra for the identification of electrode reaction mechanisms in solid oxide fuel cells