Monica Marinescu

Lithium sulfur batteries, a mechanistic review

Lithium sulfur (Li–S) batteries are one of the most promising next generation battery chemistries with potential to achieve 500–600 W h kg−1 in the next few years. Yet understanding the underlying mechanisms of operation remains a major obstacle to their continued improvement. From a review of a range of analytical studies and physical models, it is clear that experimental understanding is well ahead of state-of-the-art models. Yet this understanding is still hindered by the limitations of available techniques and the implications of experiment and cell design on the mechanism. The mechanisms at the core of physical models for Li–S cells are overly simplistic compared to the latest thinking based upon experimental results, but creating more complicated models will be difficult, due to the lack of and inability to easily measure the necessary parameters. Despite this, there are significant opportunities to improve models with the latest experimentally derived mechanisms. Such models can inform materials research and lead to improved high fidelity models for controls and application engineers.

Reflection of light by metal nanoparticles at electrodes

We present model calculations for the reflection spectrum of an ordered two dimensional array of metallic nanoparticles located near an electrochemical interface. We consider three cases, nanoparticles at: (i) a metal electrode, (ii) a transparent semiconductor electrode, and (iii) an electrified liquid/liquid interface. In the case of a metal electrode, the presence of nanoparticles introduces dips in reflection, whose position and depth are affected by the distance and size of the nanoparticles. For both a transparent semiconductor electrode and a liquid/liquid interface, the presence of nanoparticles enhances reflectivity. The spectra are sensitive to the particle spacing and size. The response from all three systems exhibits a strong dependence on the polarisation of light. The dependence on the angle of incidence reveals shallow dips typical of surface plasmon resonance spectra. These findings suggest diagnostic tools for the detection and characterisation of nanoparticle monolayers on functionalised electrodes, and enable electrovariable optical devices based on the controlled assembly of nanoparticles at interfaces.

Modeling the voltage loss mechanisms in lithium–sulfur cells: the importance of electrolyte resistance and precipitation kinetics

Understanding of the complex electrochemical, transport, and phase-change phenomena in Li-S cells requires experimental characterization in tandem with mechanistic modeling. However, existing Li-S models currently contradict some key features of experimental findings, particularly the evolution of cell resistance during discharge. We demonstrate that, by introducing a concentration-dependent electrolyte conductivity, the correct trends in voltage drop due to electrolyte resistance and activation overpotentials are retrieved. In addition, we reveal the existence of an often overlooked potential drop mechanism in the low voltage-plateau which originates from the limited rate of Li2S precipitation.