Ralf Ziesche

Understanding electrolyte dynamics within lithium-ion batteries is critical for improving performance and longevity, yet remains experimentally challenging due to the difficulty of probing liquid phases inside opaque cells. Here, we employ in situ neutron computed tomography (NCT) and operando neutron radiography to non-destructively visualise liquid electrolyte mobility in commercial Li-ion pouch cells with single-crystal (SC) and polycrystalline (PC) cathodes. The neutron-based techniques enable three-dimensional and time-resolved (4D) tracking of electrolyte distribution, leveraging their strong sensitivity to hydrogen in carbonate-based electrolytes. We find that SC cells exhibit a more homogeneous electrolyte distribution after wetting and the first charge, whereas PC cells retain pronounced heterogeneities and higher overall electrolyte mobility, which could have further implications for cell performance and lifetime. Varying the charge rate reveals that slower rates promote more extensive electrolyte movement, facilitating homogeneous electrolyte wetting throughout the electrode stack. Despite limited spatial resolution, the combination of NCT and radiography provides unprecedented full-cell insight into electrolyte redistribution and electrode motion during formation and cycling. This work highlights the capability of neutron imaging to probe electrolyte behaviour in operando, establishing it as a powerful diagnostic tool for next-generation battery design and optimisation.

A strong societal and political drive is motivating the development and optimization of novel energy conversion and storage systems for decarbonization. The successful implementation of solid state devices such as fuel cells and secondary batteries depends, however, on achieving ambitious targets in terms of performance, reliability and cost competitiveness. Research and technology are addressing these needs through a holistic approach including exploration of new materials and nanoarchitectures, as well as system engineering. These significant efforts require the support of appropriate characterization tools capable of assessing nanometer-scale phenomena such as concentration profiles of ionic and electronic charges, local chemical compositions and their evolution over time across interfaces. This roadmap provides an overview of selected advanced characterization techniques for energy materials and devices. Specific focus is put on in situ/operando methods for probing electrochemical phenomena in real-time under realistic working conditions. Experts in the field provide an extensive review of the current state of the art in 2025 and the current and future challenges for the characterization of local chemistry and kinetics in the bulk of the material, in nanoarchitectures (e.g. thin films) and at the interfaces (e.g. grain boundaries, phase contacts, solid/liquid and solid/gas interfaces) . The aim is to provide a detailed guide to the techniques, describing opportunities and bottlenecks for their practical deployment and examples of successful applications. This roadmap provides an overview of selected advanced characterization techniques for energy materials and devices. Specific focus is put on in situ/operando methods for probing electrochemical phenomena in real time under realistic working conditions. Experts in the field provide an extensive review of the current state of the art in 2024 and the current and future challenges for the characterization of local chemistry and kinetics in the bulk of the material, in nanoarchitectures (e.g. thin films) and at the interfaces (e.g. grain boundaries, phase contacts, solid/liquid and solid/gas interfaces) . The aim is to provide a detailed guide to the techniques, describing opportunities and bottlenecks for their practical deployment and examples of successful applications.

X-ray ptychography is a robust microscopy technique with nanoscale resolution that requires a spatially and temporally coherent illumination. In a typical setup, the temporal coherence requirements are satisfied by monochromating the x-ray source, e.g., using a crystal monochromator. Recent studies have shown that energy resolving, or hyperspectral, detectors can to some extent replace the role of the monochromator to perform, e.g., edge-subtraction ptychographic imaging with broadband radiation in a single acquisition. Scaling this capability from two dimensions (2D) to three dimensions (3D), and from a single absorption edge to multiple edges, is critical for its applications in structural and elemental characterisation. The method is hitherto limited by the inherently lower maximum count rate of hyperspectral detectors and the chromaticity of the optics often used in x-ray ptychography experiments, namely Fresnel zone plates. In this work, we design an optimized broadband spectroscopic ptychography setup and use it to perform 3D hyperspectral imaging of particles of battery material containing various percentages of nickel, manganese, cobalt (NMC). We show that we can identify different compositions based on their spectral response. We discuss the results and provide guidelines for future exploitation of the method in laboratory settings.

To understand fracture behaviour in battery materials, X-ray computed tomography (X-ray CT) has become the primary technique for non-destructive particle analysis. Cracking causes performance decline in polycrystalline NMC811 by exposing new surfaces for parasitic electrolyte reactions and disconnecting active material from the electrode matrix. First cycle crack formation has been documented, but definitive electrochemically induced particle fracture is challenging to assess due to complex sample preparation and high-resolution X-ray imaging requirements. Presented here is an operando X-ray CT technique that enables accurate observation of fracture behaviour during de-/lithiation. A non-linear relationship between fracture behaviour and cell voltage was uncovered, and evidence of particle reformation during re-lithiation. Using a grey level analysis algorithm for fracture detection, we expedite damage evaluation in several thousands of particles throughout the electrochemical process, understanding crack initiation, propagation, and closure on a large, statistical scale and give the ability to track any one of the thousands of particles through its individual electrochemical history. Additionally, we explore the effects of continued volumetric hysteresis on particle damage. For the first time, we demonstrate the complex plurality of fracture behaviour in commercial lithium-ion battery materials, aiding in designing mitigation strategies against particle fracture.

Water management plays a key role in ensuring optimum polymer electrolyte fuel cell (PEFC) performance, and flow field design can influence the ability of a cell to balance maintaining hydration, whilst avoiding flooding and cell failure. This work deepens the understanding of water evolution in different PEFC flow channel designs, namely single serpentine (SS), double serpentine (DS) and parallel, using our novel high-speed neutron computed tomography method. We developed our previously-reported method by introducing continuous cell rotation, enabling 18 s per tomogram during 1 h holds at 300, 400 and 500 mA cm⁻². The volume of water evolved in the cathode, membrane electrode assembly and anode was quantified, and key mechanisms for water droplet formation in the different flow channel designs were elucidated. The parallel flow field design had the poorest water management, with 47% of the cathode flow channel becoming filled after 1 h at 400 mA cm⁻². This significant flooding blocked reactant sites and contributed to unstable cell performance and, ultimately, cell failure at higher current densities. The SS cell displayed the best water management, with only 11% of the cathode channel filled with water after 1 h at 500 mA cm⁻², compared with 28% of the DS cathode channel. 3D visualisation and analysis of droplet behaviour elucidated how water ‘slugs’ in the SS were removed in the gas stream, whereas three of the four parallel cathode flow channels became entirely filled with water plugs, blocking gas flow and exacerbating cell flooding. The new insights gained here are expected to extend to novel flow field designs and image-based models, with the use of operando neutron CT demonstrated as a powerful technique for both visualising and quantifying water management in operating PEFCs, as well as deepening the knowledge of droplet behaviour in different flow field types.

Laser-plasma accelerators are compact linear accelerators based on the interaction of high-power lasers with plasma to form accelerating structures up to 1000 times smaller than standard radiofrequency cavities, and they come with an embedded X-ray source, namely betatron source, with unique properties: small source size and femtosecond pulse duration. A still unexplored possibility to exploit the betatron source comes from combining it with imaging methods able to encode multiple information like transmission and phase into a single-shot acquisition approach. In this work, we combine edge illumination-beam tracking (EI-BT) with a betatron X-ray source and present the demonstration of multimodal imaging (transmission, refraction, and scattering) with a compact light source down to the femtosecond timescale. The advantage of EI-BT is that it allows multimodal X-ray imaging technique, granting access to transmission, refraction and scattering signals from standard low-coherence laboratory X-ray sources in a single shot.

Demand for low carbon energy storage has highlighted the importance of imaging techniques for the characterization of electrode microstructures to determine key parameters associated with battery manufacture, operation, degradation, and failure both for next generation lithium and other novel battery systems. Here, recent progress and literature highlights from magnetic resonance, neutron, X‐ray, focused ion beam, scanning and transmission electron microscopy are summarized. Two major trends are identified: First, the use of multi‐modal microscopy in a correlative fashion, providing contrast modes spanning length‐ and time‐scales, and second, the application of machine learning to guide data collection and analysis, recognizing the role of these tools in evaluating large data streams from increasingly sophisticated imaging experiments.

In recent years, low-temperature polymer electrolyte fuel cells have become an increasingly important pillar in a zero-carbon strategy for curbing climate change, with their potential to power multiscale stationary and mobile applications. The performance improvement is a particular focus of research and engineering roadmaps, with water management being one of the major areas of interest for development. Appropriate characterisation tools for mapping the evolution, motion and removal of water are of high importance to tackle shortcomings. This article demonstrates the development of a 4D high-speed neutron imaging technique, which enables a quantitative analysis of the local water evolution. 4D visualisation allows the time-resolved studies of droplet formation in the flow fields and water quantification in various cell parts. Performance parameters for water management are identified that offer a method of cell classification, which will, in turn, support computer modelling and the engineering of next-generation flow field designs.