Special issue on Synchrotron- and FEL-based X-ray Methods for Battery Studies

Most battery positive electrodes operate with a 3d transition-metal (TM) reaction centre. A direct and quantitative probe of the TM states upon electrochemical cycling is valuable for understanding the detailed cycling mechanism and charge diffusion in the electrodes, which is related with many practical parameters of a battery. This review includes a comprehensive summary of our recent demonstrations of five different types of quantitative analysis of the TM states in battery electrodes based on soft x-ray absorption spectroscopy and multiplet calculations. In LiFePO₄, a system of a well-known two-phase transformation type, the TM redox could be strictly determined through a simple linear combination of the two end-members. In Mn-based compounds, the Mn states could also be quantitatively evaluated, but a set of reference spectra with all the three possible Mn valences needs to be deliberately selected and considered in the fitting. Although the fluorescence signals suffer the self-absorption distortion, the multiplet calculations could consider the distortion effect, which allows a quantitative determination of the overall Ni oxidation state in the bulk. With the aid of multiplet calculations, one could also achieve a quasi-quantitative analysis of the Co redox evolution in LiCoO₂ based on the energy position of the spectroscopic peak. The benefit of multiplet calculations is more important for studying electrode materials with TMs of mixed spin states, as exemplified by the quantitative analysis of the mixed spin Na_2−xFe₂(CN)₆ system. At the end, we showcase that such quantitative analysis could provide valuable information for optimizing the electrochemical performance of Na_0.44MnO₂ electrodes for Na-ion batteries. The methodology summarized in this review could be extended to other energy application systems with TM redox centre for detailed analysis, for example, fuel cell and catalytic materials.

Computed tomography with x-rays is a powerful tool to analyze the complex reaction and transport processes that occur inside electrochemical storage devices. To this day, a better insight into the occurring processes is needed and will yield improvements in energy density and cycling stability of next-generation batteries. Herein we present general considerations for the use of x-ray tomography of batteries to gain a detailed insight during operation. Furthermore, we present examples for the tomography of zinc–oxygen batteries, sodium–oxygen batteries and metal–sulfur batteries, elucidating performance limiting degradation processes such as dendrite formation and loss of liquid electrolyte. With the method applied, we aim to establish an effective link between the battery and x-ray community by offering a guideline on how to apply x-ray tomography to propel research on battery materials and entire batteries.

Flow batteries represent a possible grid-scale energy storage solution, having many advantages such as scalability, separation of power and energy capabilities, and simple operation. However, they can suffer from degradation during operation and the characteristics of the felt electrodes are little understood in terms of wetting, compression and pressure drops. Presented here is the design of a miniature flow cell that allows the use of x-ray computed tomography (CT) to study carbon felt materials in situ and operando, in both lab-based and synchrotron CT. Through application of the bespoke cell it is possible to observe felt fibres, electrolyte and pore phases and therefore enables non-destructive characterisation of an array of microstructural parameters during the operation of flow batteries. Furthermore, we expect this design can be readily adapted to the study of other electrochemical systems.

Synchrotron radiation-based near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) has recently become a powerful tool for the investigation of interfacial phenomena in electrochemical power sources such as batteries and fuel cells. Here we present an in situ NAP-XPS study of the anode of a high-temperature direct methanol fuel cell with a phosphoric acid-doped hydrocarbon membrane, which reveals an enhanced flooding of the Pt₃Ru anode with phosphoric acid in the presence of methanol. An analysis of the electrode surface composition depending on the cell voltage and on the presence of methanol reveals the strong influence of the latter on the extent of Pt oxidation and on the transformation of Ru into Ru (IV) hydroxide.

We activated gold electrodes for their use as electrocatalyst for water splitting by electrodepositing Cu, Ni and Co. A combination of operando x-ray absorption spectroscopy and potentiometric control under aqueous conditions revealed the trends in reactivity yielded by these electrodes, which are directly associated with the cross- and overpotentials as well as the occupancy of the 3d orbitals. It was found that under anodic polarization the materials electrodeposited on gold suffer from a lack of stability, while under cathodic polarization they exhibit stable behavior. The observed activity is strongly related to the lack of stability shown by these composites under anodic polarization revealing a dynamic process ruled by corrosion. By operando x-ray absorption, we established that the overall enhancement of the activity for the oxygen evolution reaction is directly attributable to the cross-potential and corrosion process of the electrodeposited materials. It is associated with the high potential deposition, which is the origin of the incipient oxidation-corrosion resistance of the lattice. We conclude that the observed trends in the total current are directly associated with the loss of oxygen in the metal-oxide lattice and the subsequent dissolution of metallic ions in the electrolyte under anodic polarization.

X-ray absorption spectroscopy is a synchrotron radiation based technique that is able to provide information on both local structure and electronic properties in a chemically selective manner. It can be used to characterize the dynamic processes that govern the electrochemical energy storage in batteries, and to shed light on the redox chemistry and changes in structure during galvanostatic cycling to design cathode materials with improved properties. Operando XAS studies have been performed at beamline XAFS at Elettra on different systems. For Li-ion batteries, a multiedge approach revealed the role of the different cathode components during the charge and discharge of the battery. In addition, Li-S batteries for automotive applications were studied. Operando sulfur K-edge XANES and EXAFS analysis was used to characterize the redox chemistry of sulfur, and to relate the electrochemical mechanism to its local structure.

This paper describes two novel in situ microspectroscopic approaches to the dynamic study of electrodeposition processes: x-ray fluorescence (XRF) mapping with submicrometric space resolution and keyhole coherent diffractive imaging (kCDI) with nanometric lateral resolution. As a case study, we consider the pulse-plating of nanocomposites with polypyrrole matrix and Mn_xCo_yO_z dispersoids, a prospective cathode material for zinc-air batteries. This study is centred on the detailed measurement of the elemental distributions developing in two representative subsequent growth steps, based on the combination of in situ identical-location XRF microspectroscopy—accompanied by soft-x ray absorption microscopy—and kCDI. XRF discloses space and time distributions of the two electrodeposited metals and kCDI on the one hand allows nanometric resolution and on the other hand provides complementary absorption as well as phase contrast modes. The joint information derived from these two microspectroscopies allows measurement of otherwise inaccessible observables that are a prerequisite for electrodeposition modelling and control accounting for dynamic localization processes.

The electrochemical lithiation of the mixed metal olivine LiFe_0.75Mn_0.25PO₄ was followed by operando x-ray absorption spectroscopy (XAS) at both Fe and Mn K edges. XAS data were interpreted using an innovating chemometric approach, allowing the detailed reconstruction of the rather complicated reaction mechanism involving two different metal centres. In this way it was possible to precisely describe the Jahn–Teller effect occurring upon oxidation of the manganese centres. The thorough comprehension of the electrochemical mechanism is of high interest for studying the effect of lithium extraction in the olivine structure in the presence of Mn, which is known to partially hamper the complete lithiation of such mixed metal systems.

In this paper we focus on the following map identification problem (MIP): given a morphochemical reaction–diffusion (RD) PDE system modeling an electrodepostion process, we look for a time t^*, belonging to the transient dynamics and a set of parameters $\mathbf{p}$, such that the PDE solution, for the morphology $h\left(x,y,{{t}^{\ast}};\mathbf{p}\right)$ and for the chemistry $\theta \left(x,y,{{t}^{\ast}};\mathbf{p}\right)$ approximates a given experimental map M^*. Towards this aim, we introduce a numerical algorithm using singular value decomposition (SVD) and Frobenius norm to give a measure of error distance between experimental maps for h and θ and simulated solutions of the RD-PDE system on a fixed time integration interval. The technique proposed allows quantitative use of microspectroscopy images, such as XRF maps. Specifically, in this work we have modelled the morphology and manganese distributions of nanostructured components of innovative batteries and we have followed their changes resulting from ageing under operating conditions. The availability of quantitative information on space-time evolution of active materials in terms of model parameters will allow dramatic improvements in knowledge-based optimization of battery fabrication and operation.