Battery research with the HZB X-ray microscope
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. © HZB
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.
The results provide insights into local lattice distortions associated with phase transitions and nanopore formation. The oxidation states of individual elements could also be determined locally. The speed of the charging processes plays an important role here: slow charging favours phase transitions and oxygen loss, while fast charging leads to lattice distortions and inhomogeneous lithium diffusion.
‘Here at the TXM, we have a unique capability: we can offer energy-resolved transmission X-ray tomography,’ says Werner. ’This gives us a 3D image with structural information at every element-specific energy level – energy is the fourth dimension here.’
The results from this study provide valuable information for the development of high-performance cathodes that remain stable over the long term and are resistant to cycling. ‘The TXM is excellently suited to provide new insights into morphological and chemical changes in battery materials in the future through in-operando studies – that is, during charging and discharging,’ says Prof. Gerd Schneider, who developed the TXM.
- Long-term stability for perovskite solar cells: a big step forwardPerovskite solar cells are inexpensive to produce and generate a high amount of electric power per surface area. However, they are not yet stable enough, losing efficiency more rapidly than the silicon market standard. Now, an international team led by Prof. Dr. Antonio Abate has dramatically increased their stability by applying a novel coating to the interface between the surface of the perovskite and the top contact layer. This has even boosted efficiency to almost 27%, which represents the state-of-the-art. After 1,200 hours of continuous operation under standard illumination, no decrease in efficiency was observed. The study involved research teams from China, Italy, Switzerland and Germany and has been published in Nature Photonics.
- Energy of charge carrier pairs in cuprate compoundsHigh-temperature superconductivity is still not fully understood. Now, an international research team at BESSY II has measured the energy of charge carrier pairs in undoped La₂CuO₄. Their findings revealed that the interaction energies within the potentially superconducting copper oxide layers are significantly lower than those in the insulating lanthanum oxide layers. These results contribute to a better understanding of high-temperature superconductivity and could also be relevant for research into other functional materials.
- Electrocatalysis with dual functionality – an overviewHybrid electrocatalysts can produce green hydrogen, for example, and valuable organic compounds simultaneously. This promises economically viable applications. However, the complex catalytic reactions involved in producing organic compounds are not yet fully understood. Modern X-ray methods at synchrotron sources such as BESSY II, enable catalyst materials and the reactions occurring on their surfaces to be analysed in real time, in situ and under real operating conditions. This provides insights that can be used for targeted optimisation. A team has now published an overview of the current state of knowledge in Nature Reviews Chemistry.