Reducing the Self-Discharge Rate of Supercapacitors by Suppressing Electron Transfer in the Electric Double Layer

Designing supercapacitors with suppressed self-discharge for long-term energy storage has been a challenge. In this work, we demonstrate that substantially reduced self-discharge rate can be achieved by using highly concentrated electrolytes. Specifically, when supercapacitors with 14 M LiCl electrolyte are charged to 0.80 V, the open circuit voltage (OCV) drops to 0.65 V in 24 h. In stark contrast, when the electrolyte concentration is reduced to 1 M, the OCV drops from 0.80 to 0.65 V within only 0.3 h, which was 80 times faster than that with 14 M LiCl. Decreased OCV decay rate at high electrolyte concentration is also confirmed for supercapacitors with different electrolytes (e.g., LiNO3) or at higher charging voltages (1.60 V). The slow self-discharge in highly concentrated electrolyte can be largely attributed to impeded electron transfer between the electrodes and electrolyte due to the formation of hydration clusters and reduced amount of free water molecules, thereby faradaic reactions that cause fast self-discharge are reduced. Our study not only supports the newly revised model about the formation of electric double layer with the inclusion of electron transfer, but also points a direction for substantially reducing the self-discharge rate of supercapacitors.

Investigating on physical and electrochemical properties of high concentrated electrolytes based on LiBF4 salt for 5 V Li-ion rechargeable batteries

In this work, highly concentrated electrolytes were prepared by dissolving tetrafluoroborate (LiBF4) salt in the two solvents including tetramethylene sulfone (TMS) and trimethyl phosphate (TMP) with different mole ratios. The results indicated that the electrolyte LiBF4/TMS (1:3) (~3.4 M) possessed the highest oxidation stability of 6.2 V (vs. Li+/Li) and high ionic conductivity of 1.0 mS/cm that could be promising for high voltage Li-ion batteries operated in the voltage range of 3.5-4.9 V. The electrolyte compatibility with high voltage cathode Li || LiNi0.5Mn1.5O4 (LNMO) was evaluated in coin-cell configuration, which displayed high reversible discharge capacity of 113 mAh/g in the first cycle and high initial Coulombic efficiency >91% and remained >80% of the initial capacity at the 100th cycle. By using the cyclic voltammetry (CV) method, the diffusion coefficient was also calculated as about 4.51×10-11 cm2/s.

Ionic Screening in Bulk and under Confinement

Recent experiments have shown that the repulsive force between atomically flat, like-charged surfaces confining room-temperature ionic liquids or concentrated electrolytes exhibits an anomalously large decay length. In our previous publication [Zeman et al., Chem. Commun. 56, 15635 (2020)], we showed by means of extremely large-scale molecular dynamics simulations that this so-called underscreening effect might not be a feature of bulk electrolytes. Herein, we corroborate these findings by providing additional results with more detailed analyses and expand our investigations to ionic liquids under confinement. Unlike in bulk systems, where screening lengths are computed from the decay of interionic potentials of mean force (PMFs), we extract such data in confined systems from cumulative charge distributions. At high concentrations, our simulations show increasing screening lengths with increasing electrolyte concentration, consistent with classical liquid state theories. However, our analyses demonstrate that---also for confined systems---there is no anomalously large screening length. As expected, the screening lengths determined for ionic liquids under confinement are in good quantitative agreement with the screening lengths of the same ionic systems in bulk. In addition, we show that some theoretical models used in the literature to relate the measured screening lengths to other observables are inapplicable to highly concentrated electrolytes.

Charge transport modelling of Lithium-ion batteries

This paper presents the current state of mathematical modelling of the electrochemical behaviour of lithium-ion batteries (LIBs) as they are charged and discharged. It reviews the models developed by Newman and co-workers, both in the cases of dilute and moderately concentrated electrolytes and indicates the modelling assumptions required for their development. Particular attention is paid to the interface conditions imposed between the electrolyte and the active electrode material; necessary conditions are derived for one of these, the Butler–Volmer relation, in order to ensure physically realistic solutions. Insight into the origin of the differences between various models found in the literature is revealed by considering formulations obtained by using different measures of the electric potential. Materials commonly used for electrodes in LIBs are considered and the various mathematical models used to describe lithium transport in them discussed. The problem of upscaling from models of behaviour at the single electrode particle scale to the cell scale is addressed using homogenisation techniques resulting in the pseudo-2D model commonly used to describe charge transport and discharge behaviour in lithium-ion cells. Numerical solution to this model is discussed and illustrative results for a common device are computed.