X-Ray-Induced Changes to Passivation Layers of Lithium-Ion Battery Electrodes

Abstract

The surface sensitivity available to photoelectron spectroscopies (PESs) makes them popular techniques for characterization of chemical environments at shallower depths than other, more bulk-sensitive techniques and because they are generally thought to be nondestructive. Variable energy, synchrotron radiation (SR), permits access to information not available to common lab-based radiation sources, making high-energy PES studies extremely useful for understanding thin films and interfaces. High-SR photon flux has been useful for developing models of soft X-ray-induced effects, but hard X-ray SR-induced effects are less well studied and will be increasingly important as popularity and availability of SR for thin film analysis continues to grow. We report here on observed modification of the solid electrolyte interphase of a lithium-ion battery electrode during prolonged exposure to 4 keV SR. The effects can be summarized by desorption of oxygen-containing species from the sample surface and by reactions within the film. Also presented is an estimate of the layer thickness’ time evolution during the prolonged SR exposure.

Chemomechanics of Rechargeable Batteries: Status, Theories, and Perspectives

“…Unlike the photon–electron interactions in X-ray, neutrons, as charge-neutral subatomic particles, interact directly with atomic nuclei, and possess dominant penetration power. This leads to complementary characteristics with X-ray such as (1) good capability to distinguish adjacent transitional metals (Ni, Co, and Mn), (2) the capability of detecting light elements like oxygen and carbon that play important roles in LIBs, and (3) negligible damage to tested samples compared to that induced by high-energy X-rays. , Dedicated neutron sources mainly include research reactors and spallation sources. Figure a summarizes various neutron characterization techniques for LIBs, typically for examination of the structural evolution and morphology features.…”

Near‐Atomic‐Scale Evolution of the Surface Chemistry in Li[Ni,Mn,Co]O2 Cathode for Li‐Ion Batteries Stored in Air

“…[ 10–13 ] Similarly, X‐ray illumination of Li containing compounds forces an uncontrollable evolution toward stable lithium oxide, even in the soft X‐ray regime, precluding safe and reliable application of X‐ray‐based spectroscopy techniques. [ 14–17 ] Alternative analytical techniques are now being explored to circumvent these issues. Time‐of‐flight secondary ion mass spectrometer (TOF‐SIMS) and atom probe tomography (APT) which provides quantitative, analytical 3D imaging with subnanometer resolution are currently the most suitable solutions.…”

“…[10][11][12][13] Similarly, X-ray illumination of Li containing compounds forces an uncontrollable evolution toward stable lithium oxide, even in the soft X-ray regime, precluding safe and reliable application of X-ray-based spectroscopy techniques. [14][15][16][17] Alternative analytical techniques are now being…”

Using In-Situ Laboratory and Synchrotron-Based X-ray Diffraction for Lithium-Ion Batteries Characterization: A Review on Recent Developments

“…Moreover, when performing an XRD synchrotron experiment, the beam interaction with the materials of interest also has to be considered. X-ray interaction can influence reaction during cycling and this can alter the material's behavior [64]. The interaction is proportional to the material's X-ray absorption, which is minimized with higher X-ray energies.…”