Innovative battery electrode made from tin foam

Metal-based electrodes in lithium-ion batteries promise significantly higher capacities than conventional graphite electrodes. Unfortunately, they degrade due to mechanical stress during charging and discharging cycles. A team at HZB has now shown that a highly porous tin foam is much better at absorbing mechanical stress during charging cycles. This makes tin foam an interesting material for lithium batteries.

Modern lithium-ion batteries are typically based on a multilayer graphite electrode, with the counter electrode often made of cobalt oxide. During charging and discharging, lithium ions migrate into the graphite without causing significant volume changes in the material. However, the capacity of graphite is limited, making the search for alternative materials an exciting area of research. Metal-based electrodes, such as aluminium or tin, have the potential to offer higher capacity. However, they tend to expand significantly in volume when lithium is absorbed, which is associated with structural changes and material fatigue. Tin is particularly attractive because it’s capacity per kilogram is almost three times higher than graphite, and it is not a rare raw material but is available in abundance. One option for realising metal electrodes that ‘fatigue’ less quickly involves nanostructuring the thin metal foils. Another option is to use porous metal foams.

A team from the Helmholtz-Zentrum Berlin (HZB) has now studied various types of tin electrodes during the discharge and charging process using operando X-ray imaging, and developed an innovative approach to address this problem. Part of the experiments were carried out at the BAMline at BESSY II. The high-resolution radioscopic X-ray images were taken in collaboration with imaging experts Dr. Nikolai Kardjilov and Dr. André Hilger at HZB. ‘This allowed us to track the structural changes in the investigated Sn-metal-based electrodes during the charging/discharging processes,’ says Dr. Bouchra Bouabadi, first author of the study. With battery expert Dr. Sebastian Risse, she explored how the morphology of the tin electrodes changes during operation due to the inhomogeneous absorption of lithium ions.

Read more on HZB website

Image: Tin can be processed into a highly porous foam. An interdisciplinary team at HZB has investigated how this tin foam (pictured) behaves as a battery electrode.

Credit: B. Bouabadi / HZB

Battery research with the HZB X-ray microscope

New cathode materials are being developed to further increase the capacity of lithium batteries. Multilayer lithium-rich transition metal oxides (LRTMOs) offer particularly high energy density. However, their capacity decreases with each charging cycle due to structural and chemical changes. Using X-ray methods at BESSY II, teams from several Chinese research institutions have now investigated these changes for the first time with highest precision: at the unique X-ray microscope, they were able to observe morphological and structural developments on the nanometre scale and also clarify chemical changes.

Lithium-ion batteries are set to become even more powerful with new materials for the cathodes. For example, layered lithium-rich transition metal (LRTMO) cathodes could further increase the charge capacity and be used in high-performance lithium batteries. However, so far it has been observed that these cathode materials ‘age’ rapidly: the cathode material degrades as a result to the back-and-forth migration of lithium ions during charging and discharging. Until now it was unclear what specific changes these would involve.

Teams from Chinese research institutions have therefore applied for beam time at the world’s only transmission X-ray microscope (TXM) at an undulator beamline at the BESSY II storage ring to investigate their samples using 3D tomography and nanospectroscopy. The HZB-TXM measurements were performed by Dr. Peter Guttmann, HZB, back in 2019, before the coronavirus pandemic. The X-ray microscopic analysis was then supplemented by further spectroscopic and microscopic examinations. After careful evaluation of the extensive data, the results are now available: they provide detailed information on changes in the morphology and structure of the material, but also on chemical processes during discharge.

‘Soft X-ray transmission microscopy allows us to visualise chemical states in LRTMO particles in three dimensions with high spatial resolution and to gain insights into chemical reactions during the electrochemical cycle,’ explains Dr Stephan Werner, who is responsible for the scientific supervision and further development of the instrument.

Read more on HZB website

Image: The left side of the figure shows nanotomography images of an LRTMO particle taken at the TXM of BESSY II before the first charging cycle (top) and after 10 charging cycles (bottom). In the simulation (right side), the isolated pores are highlighted in light blue. After 10 charging cycles, the number of pores and cracks has significantly increased.

Credit: HZB