Nanoparticles in lithium-sulphur batteries detected with neutron experiment
The operando cell was developed at HZB and allows to analyse processes inside the battery during charging cycles with neutrons. © S. Risse/HZB
An HZB team has for the first time precisely analysed how nanoparticles of lithium sulphide and sulphur precipitate onto battery electrodes during the course of the charging cycle. The results can help increase the service life of lithium-sulphur batteries.
Lithium-sulphur batteries are regarded as one of the most promising candidates for the next generation of energy storage devices. They have a theoretical gravimetric energy density that is five times higher than that of the best lithium-ion batteries currently available. And they even work at sub-zero temperatures of down to -50 °C. In addition, sulphur is inexpensive and environmentally friendly.
Capacity loss
However, their capacity so far has fallen sharply with every charge-discharge cycle, so that such batteries are not yet long-lasting. The loss of capacity is caused by complicated reaction processes at the electrodes inside the battery cell. It is therefore particularly important to understand exactly how the charge (sulphur) and discharge (lithium sulphide) products precipitate and dissolve. While sulphur precipitates macroscopically and therefore lends itself to examination by imaging techniques or X-ray diffraction during cycling, lithium sulphide is difficult to detect due to its sub-10-nm particle size.
"Operando" observations with neutrons
Insight into this has now been provided for the first time by investigations with the BER II neutron source at the HZB. Dr. Sebastian Risse used a measuring cell he developed to illuminate lithium-sulphur batteries with neutrons during charging and discharging cycles (operando) and simultaneously performed additional measurements with impedance spectroscopy.
This enabled him and his team to analyse the dissolution and precipitation of lithium sulphide with extreme precision during ten discharge/charging cycles. Since neutrons interact strongly with deuterium (heavy hydrogen), the researchers used a deuterated electrolyte in the battery cell to make both the solid products (sulphur and lithium sulphide) visible.
Surprising insight
Their conclusion: “We observed that the lithium sulphide and sulphur precipitation does not take place inside the microporous carbon electrodes, but instead on the outer surface of the carbon fibres”, says Risse. These results provide a valuable guide for the development of better battery electrodes.
The study is published in ACS Nano, (2019): Operando Analysis of a Lithium/Sulfur Battery by Small Angle Neutron Scattering. Sebastian Risse, Eneli Härk, Ben Kent and Matthias Ballauff
DOI: http://dx.doi.org/10.1021/acsnano.9b03453
- BESSY II: How intrinsic oxygen shortens the lifespan of solid-state batteriesAlthough solid-state batteries (SSBs) demonstrate high performance and are intrinsically safe, their capacity currently declines rapidly. A team from the TU Wien, Humboldt-University Berlin and HZB has now analysed a TiS₂|Li₃YCl₆ solid-state half-cell in operando at BESSY II using a special sample environment that allows for non-destructive investigation under real operating conditions. Data obtained by combination of soft and hard X-ray photoelectron spectroscopy (XPS and HAXPES) revealed a new degradation mechanism that had not previously been identified in solid-state batteries. They have gained some surprising insights, particularly regarding the harmful role played by intrinsic oxygen. This study provides valuable information for improving design and handling of such batteries.
- Spintronics at BESSY II: Real-time analysis of magnetic bilayer systemsSpintronic devices enable data processing with significantly lower energy consumption. They are based on the interaction between ferromagnetic and antiferromagnetic layers. Now, a team from Freie Universität Berlin, HZB and Uppsala University has succeeded in tracking, for each layer separately, how the magnetic order changes after a short laser pulse has excited the system. They were also able to identify the main cause of the loss of antiferromagnetic order in the oxide layer: the excitation is transported from the hot electrons in the ferromagnetic metal to the spins in the antiferromagnet.
- Electrocatalysts: New model for charge separation at the solid-liquid interfaceHydrogen is at the heart of the transition to carbon neutrality, as both an energy carrier and a reagent for green chemistry. However, large-scale production of hydrogen via electrolysis, as well as the production of many other chemical products, requires significantly cheaper and more efficient catalysts. A precise understanding of the electrochemical processes that take place at the interface between the solid catalyst and the liquid medium is highly useful for developing better electrocatalysts. In the journal Nature Communications, an European team has now presented a powerful model that determines charge separation at the interface, the formation of the electric double layer and local electric potential variations, and the resulting influence on the catalytic activity.