Magnesium Anode Protection by an Organic Artificial Solid Electrolyte Interphase for Magnesium-Sulfur Batteries.

In the search for post-lithium battery systems, magnesium-sulfur batteries have attracted research attention in recent years due to their high potential energy density, raw material abundance, and low cost. Despite significant progress, the system still lacks cycling stability mainly associated with the ongoing parasitic reduction of sulfur at the anode surface, resulting in the loss of active materials and passivating surface layer formation on the anode. In addition to sulfur retention approaches on the cathode side, the protection of the reductive anode surface by an artificial solid electrolyte interphase (SEI) represents a promising approach, which contrarily does not impede the sulfur cathode kinetics. In this study, an organic coating approach based on ionomers and polymers is pursued to combine the desired properties of mechanical flexibility and high ionic conductivity while enabling a facile and energy-efficient preparation. Despite exhibiting higher polarization overpotentials in Mg-Mg cells, the charge overpotential in Mg-S cells was decreased by the coated anodes with the initial Coulombic efficiency being significantly increased. Consequently, the discharge capacity after 300 cycles applying an Aquivion/PVDF-coated Mg anode was twice that of a pristine Mg anode, indicating effective polysulfide repulsion from the Mg surface by the artificial SEI. This was backed by operando imaging during long-term OCV revealing a non-colored separator, i.e. mitigated self-discharge. While SEM, AFM, IR and XPS were applied to gain further insights into the surface morphology and composition, scalable coating techniques were investigated in addition to ensure practical relevance. Remarkably therein, the Mg anode preparation and all surface coatings were prepared under ambient conditions, which facilitates future electrode and cell assembly. Overall, this study highlights the important role of Mg anode coatings to improve the electrochemical performance of magnesium-sulfur batteries.

Toward Operando Structural, Chemical, and Electrochemical Analyses of Solid-State Batteries Using Correlative Secondary Ion Mass Spectrometry Imaging.

The global transition from fossil fuels to green energy underpins the need for efficient and reliable energy storage systems. Advanced analysis and characterization of battery materials is not only important to understand fundamental battery properties but also crucial for their continued development. A deep understanding of these systems is often difficult to obtain through only pre- and/or post-mortem analyses, with the full complexity of a battery being hidden in its operational state. Thus, we have developed an operando methodology to analyze solid-state batteries (SSBs) structurally as well as chemically before, during, and after cycling. The approach is based on a specially designed sample holder, which enables a variety of electrochemical experiments. Since the entire workflow is performed within a single focused ion beam scanning electron microscope equipped with an in-house developed magnetic sector secondary ion mass spectrometer, we are able to pause the cycling at any time, perform analysis, and then continue cycling. Microstructural analysis is performed via secondary electron imaging, and the chemical mapping is performed using the secondary ion mass spectrometer. In this proof-of-concept study, we were able to identify dendrites in a short-circuited symmetric cell and to chemically map dendritic structures. While this methodology focuses on SSBs, the approach can directly be adapted to different battery systems and beyond. Our technique clearly has an advantage over many alternatives for battery analysis as no transfer of samples between instruments is needed and a correlation between the microstructure, chemical composition, and electrochemical performance is obtained directly.

Solid Electrolyte Interphase Evolution on Lithium Metal in Contact with Glyme-Based Electrolytes.

The formation of a stable solid electrolyte interphase (SEI) is a prerogative for functional lithium metal batteries. Herein, the formation and evolution of such SEI in contact with glyme-based electrolytes is investigated under open circuit voltage and several constant current cycles. An important conclusion of the study is that Lix Sy species are nonbeneficial SEI components, compared to the Li3 N counterpart. In addition, chemical (X-ray photoelectron spectroscopy, XPS) and electrochemical (impedance spectroscopy) evolution of SEI under galvanostatic conditions are comprehensively tracked.

Interfacial Layering and Screening Behavior of Glyme-Based Lithium Electrolytes.

Understanding of electrical double layers is essential to all electrochemical devices, particularly at high charge carrier concentrations. Using a combined approach (surface force apparatus, zeta potential, infrared spectroscopy), we propose a model for the interfacial structure of triglyme electrolytes on muscovite mica. In contact with the pure triglyme, a brush-like polymeric structure grows on the mica surface. When lithium triflate is present in the triglyme, this structure is suppressed by anion adsorption and an extended double layer is formed. A surprising result of great fundamental significance is that the effective screening length measured by surface force apparatus at considerable lithium triflate concentrations (above 0.2 M) is substantially higher than expected from the Debye-Hückel theory. This suggests a high degree of complex salt association as a novel characteristic feature of salt-containing electrolytes.