Investigating Cathode Dynamics in Realistic Desalination Reactors Using Operando High-Energy Synchrotron X-Ray Microscopy
Authors: Huck Marten , Kuhlmann Andreas , Skrentny Emil , Steinruck Hans-Georg , Vinci Valentin , Drnec Jakub 
Published: August 2024

Four billion people suffer from lack of clean water at least one month of the year.[1] This critical water shortage applies not only to the supply of potable water, but also to water for use in industrial, agricultural, and energy applications. While water resources like seawater are abundant, hardly any water resource is clean enough for direct use. Desalination provides a methodology to render unusable waters from such water resources fit for use. An innovative and particularly energy-efficient electrochemistry-based approach is the Desalination Battery (DB), which stores the energy input during desalination in chemical bonds between ions and faradaic electrode, allowing for its recovery during the salination process. DBs are at the forefront of the water-energy nexus[2]. While they are promising for seawater desalination (e.g., for seawater to brackish water conversion), practical implementation and their full potential still need to be unlocked. To this end, foundational understanding of the atomic- to electrode-scale physics/chemistry underlying functionality and degradation must be unraveled.

Towards this end, we utilized our unique flow-by reactor setup to combine electrochemistry, conductivity, and temperature measurements with high-energy (75 keV) operando synchrotron X-ray diffraction (HEXRD) microscopy. Our investigation encompasses both the atomic and electrode levels, using a 3-electrodes setup with LiMn2O4 and Na0.44MnO2 as electrode active materials. As such, we were able to simulate a realistic electrode environment for operando measurements, as well as observe spatially resolved structural changes by scanning the beam across the electrodes surface. These phenomena are manifested through changes in unit cell parameters and the emergence of new phases during desalination cycles. Specifically, we tracked the changes in XRD patterns over the course of several desalination cycles in LiCl and NaCl solutions, as well as synthetic seawater and mixed solutions of LiCl/MgCl2. We were able to observe high selectivity of LiMn2O4 towards Li+, even in the highly concentrated synthetic seawater solutions, and could not observe the emergence of a new Mg+ rich phase down to potentials of 0 V vs. AgCl. Na0.44MnO2 exhibited good cycling behavior in synthetic seawater akin to pure NaCl solutions, and apart from the Na+ rich phase showed no signs of additional new phases, suggesting a highly selective nature towards Na+. Furthermore, we compared constant current and constant potential protocols and observed distinct differences in peak shift behavior. Ongoing analysis of the unit cell parameters and atomic positions allows us to allocate specific intercalation sites to specific potentials, providing foundational insight into the chemistry and physics underlying the selectivity of these materials.

Literature:

[1] M. M. Mekonnen, et al., Sci Adv
2016, 2, e1500323.

[2] Q. Li, et al., Adv Sci (Weinh)
2020, 7, 2002213.