Triethyl and tributyl phosphite as flame-retarding additives in Li-ion batteries

This study examined the influence of triethyl and tributyl phosphite (TEP and TBP) additives on the electrochemical performance of lithium-ion cells. The cell performance of the TEP- and TBP-containing electrolytes was evaluated by cyclic voltammetry, thermogravimetric analysis, electrochemical impedance spectroscopy, Fourier transform infrared spectroscopy and scanning electron microscopy. The flammability of the electrolytes was also investigated by measuring the self-extinguishing time of the electrolytes. The results showed that the TEP and TBP additives suppressed the flammability of the electrolyte, with a significant improvement in cell performance observed for the TEP additive. In addition, TEP and TBP additives improved the thermal stability of the battery and its electrochemical cell performance. Overall, 5 wt% TEP and TBP can be used as a flame-retarding additive to improve the cell performance of Li-ion batteries due to the decrease in cell impedance and SEI formation.

Ionic liquid electrolytes as a platform for rechargeable metal–air batteries: a perspective

Metal-air batteries are a well-established technology that can offer high energy densities, low cost and environmental responsibility. Despite these favourable characteristics and utilisation of oxygen as the cathode reactant, these devices have been limited to primary applications, due to a number of problems that occur when the cell is recharged, including electrolyte loss and poor efficiency. Overcoming these obstacles is essential to creating a rechargeable metal-air battery that can be utilised for efficiently capturing renewable energy. Despite the first metal-air battery being created over 100 years ago, the emergence of reactive metals such as lithium has reinvigorated interest in this field. However the reactivity of some of these metals has generated a number of different philosophies regarding the electrolyte of the metal-air battery. Whilst much is already known about the anode and cathode processes in aqueous and organic electrolytes, the shortcomings of these electrolytes (i.e. volatility, instability, flammability etc.) have led some of the metal-air battery community to study room temperature ionic liquids (RTILs) as non-volatile, highly stable electrolytes that have the potential to support rechargeable metal-air battery processes. In this perspective, we discuss how some of these initial studies have demonstrated the capabilities of RTILs as metal-air battery electrolytes. We will also show that much of the long-held mechanistic knowledge of the oxygen electrode processes might not be applicable in RTIL based electrolytes, allowing for creative new solutions to the traditional irreversibility of the oxygen reduction reaction. Our understanding of key factors such as the effect of catalyst chemistry and surface structure, proton activity and interfacial reactions is still in its infancy in these novel electrolytes. In this perspective we highlight the key areas that need the attention of electrochemists and battery engineers, in order to progress the understanding of the physical and electrochemical processes in RTILs as electrolytes for the various forms of rechargeable metal-air batteries.

Climatic, vegetation and edaphic influences on the probability of fire across mediterranean woodlands of south-eastern Australia

 Aim: We investigated how the probability of burning is influenced by the time since fire (TSF) and gradients of climate, soil and vegetation in the fire-prone mediterranean-climate mallee woodlands of south-eastern Australia. This provided insight into the processes controlling contemporary fuel dynamics and fire regimes across biogeographical boundaries, and the consequent effects of climate change on potential shifts in boundaries between fuel systems and fire regimes, at a subcontinental scale. Location: South-eastern Australia. Methods: A desktop-based GIS was used to generate random sampling points across the study region to collect data on intersecting fire interval, rainfall, vegetation and soil type. We used a Bayesian framework to examine the effects of combinations of rainfall, vegetation and soil type on the hazard-of-burning and survival parameters of the Weibull distribution. These analyses identify the nature of environmental controls on the length of fire intervals and the age-dependence of the hazard of burning. Results: Higher rainfall was consistently associated with shorter fire intervals. Within a single level of rainfall, however, the interaction between soil and vegetation type influenced the length of fire intervals. Higher-fertility sands were associated with shorter fire intervals in grass-dominated communities, whereas lower-fertility sands were associated with shorter fire intervals in shrub-dominated communities. The hazard of burning remained largely independent of TSF across the region, only markedly increasing with TSF in shrub-dominated communities at high rainfall. Main conclusions: Rainfall had a dominant influence on fire frequency in the mediterranean-climate mallee woodlands of south-eastern Australia. Predicted changes in the spatial distribution and amount of rainfall therefore have the potential to drive changes in fire regimes, although the effects of soil fertility and rainfall on fire regimes do not align on a simple productivity gradient. Reduced soil fertility may favour plant traits that increase the rate of woody litter fuel accumulation and flammability, which may alter the overriding influence of rainfall gradients on fire regimes.

Changing dominance of key plant species across a Mediterranean climate region: implications for fuel types and future fire regimes

Herbaceous and woody plants represent different fuel types in flammable ecosystems, due to contrasting patterns of growth and flammability in response to productivity (moisture availability). However, other factors, such as soil type, fire regimes and competitive interactions may also influence the relative composition of herbaceous and woody plants within a community. The Mediterranean climate region of south eastern Australia is transitional between two contrasting fuel systems; herbaceous dominated in the dry north, versus woody plant dominated shrublands in the relatively moist south. Across the rainfall gradient of the region, there are confounded changes in dominant soil types and fire frequency. We used model-subset selection using Akaike's Information Criterion to examine potential driving mechanisms of community compositional change from herbaceous (e.g. Triodia scariosa, Austrostipa sp.) to woody plants (e.g. Beyeria opaca, Leptospermum coriaceum, Acacia ligulata) by measuring relative cover across combinations of rainfall, time since the last fire (TSF) and soil type. We examined the relative influence of environmental versus competitive interactions on determining the cover of perennial hummock grass, T. scariosa, and co-occurring woody shrubs. Rainfall and soil types, rather than competition, were the over-arching determinants of the relative cover of grasses and shrubs. Given the sensitivity to rainfall, our results indicate there is strong potential for the nature of fuel, flammability and fire regimes to be altered in the future via climate change in this region.