To enhance battery safety, it is of utmost importance to develop non-flammable electrolytes. An emerging concept within this research field is the development of localized highly concentrated electrolytes (LHCEs). This...
The high voltage spinel LiNi0.5Mn1.5O4 (LNMO) is an attractive positive electrode due to its operating voltage around 4.7 V (vs. Li/Li+) arising from the Ni2+/Ni4+ redox couple. In addition to high voltage operation, a second advantage of this material is its capability for fast lithium diffusion kinetics through 3-D transport paths in the spinel structure. However, the electrode material is prone to side reactions with conventional electrolytes, including electrolyte decomposition and transition metal dissolution, especially at elevated temperatures1. It is important to understand how undesired reactions originating from the high voltage spinel affect the aging of different cell components and overall cycle life. Half-cells are usually considered as an ideal cell configuration in order to get information only from the electrode of interest. However, this cell configuration may not be ideal to understand capacity fading for long-term cycling and the assumption of ‘stable’ lithium negative electrode may not be valid, especially at high current rates2. Also, among the variety of capacity fading mechanisms, the loss of “cyclable” lithium from the positive electrode (or gain of lithium from electrolyte into the negative electrode) due to side reactions in a full-cell can cause significant capacity loss. This capacity loss is not observable in a typical half-cell as a result of an excessive reserve of lithium in the negative electrode. In a full-cell, it is desired that the negative electrode does not contribute to side reactions in a significant way if the interest is more on the positive side. Among candidates on the negative side, Li4Ti5O12 (LTO) is known for its stability since its voltage plateau (around 1.5 V vs. Li/Li+) is in the electrochemical stability window of standard electrolytes and it shows a very small volume change during lithiation. These characteristics make the LNMO-LTO system attractive for a variety of applications (e.g. electric vehicles) but also make it a good model system for studying aging in high voltage spinel-based full cells. In this study, we aim to understand the fundamental mechanisms resulting in capacity fading for LNMO-LTO full cells both at room temperature and elevated temperature (55°C). It is known that electrode interactions occur in this system due to migration of reaction products from LNMO to the LTO side3, 4. For this purpose, three electrode cells have been cycled galvanostatically with short-duration intermittent current interruptions5 in order to observe internal resistance for both LNMO and LTO electrodes in a full cell, separately. Change of voltage curves over cycling has also been observed to get an insight into capacity loss. For comparison purposes, back-to-back cells (a combination of LNMO and LTO cells connected electrically by lithium sides) were also tested similarly. Post-cycling of harvested electrodes in half cells was conducted to determine the degree of capacity loss due to charge slippage compared to other aging factors. Surface characterization of LNMO as well as LTO electrodes after cycling at room temperature and elevated temperature has been done via SEM, XPS, HAXPES and XANES. References A. Kraytsberg, Y. Ein-Eli, Adv. Energy Mater., vol. 2, pp. 922–939, 2012. Aurbach, D., Zinigrad, E., Cohen, Y., & Teller, H. Solid State Ionics, 148(3), 405-416, 2002. Li et al., Journal of The Electrochemical Society, 160 (9) A1524-A1528, 2013. Aktekin et al., Journal of The Electrochemical Society 164.4: A942-A948. 2017. Lacey, M. J., ChemElectroChem. Accepted Author Manuscript. doi:10.1002/celc.201700129, 2017.
Halogen‐Free and Flame‐Retardant Electrolyte for Sodium‐ion Batteries Apart from achieving a greater understanding of fluorine‐free electrolytes, it is essential to create safer electrolytes for the state‐of‐the‐art sodium‐ion batteries. In article number 2101135, Lars Olow Simon Colbin, Reza Younesi, and co‐workers demonstrate that using triethyl phosphate (TEP) with sodium bis(oxalato)borate (NaBOB) as the electrolyte will help to achieve this goal. Imagine if battery electrolytes could also help to fight fires, rather than fueling them—the case today.
Binders are electrochemically inactive components that have a crucial impact in battery ageing although being present in only small amounts, typically 1-3 % w/w in commercial products. The electrochemical performance of a battery can be tailored via these inactive materials by optimizing the electrode integrity and surface chemistry. Polyacrylonitrile (PAN) for LiNi 0.5 Mn 1.5 O 4 (LNMO) half-cells is here investigated as a binder material to enable a stable electrode-electrolyte interface. Despite being previously described in literature as an oxidatively stable polymer, it is shown that PAN degrades and develops resistive layers within the LNMO cathode. We demonstrate continuous internal resistance increase in LNMObased cells during battery operation using intermittent current interruption (ICI) technique. Through a combination of on-line electrochemical mass spectrometry (OEMS) and X-ray photoelectron spectroscopy (XPS) characterization techniques, the degradation products can be identified as solid on the LNMO electrode surface, and no excessive gas formation seen. The increased resistance and parasitic processes are correlated to side-reactions of the PAN, possibly intramolecular cyclization, which can be identified as the main cause of the comparatively fast capacity fade.
An ethylene carbonate‐free electrolyte composed of 1 M lithium bis(fluorosulfonyl) imide (LiFSI) in sulfolane (SL) is studied here for LiNi0.5Mn1.5O4‐graphite full‐cells. An important focus on the evaluation of the anodic stability of the SL electrolyte and the passivation layers formed on LiNi0.5Mn1.5O4 (LNMO) and graphite is being analysed along with intermittent current interruption (ICI) technique to observe the resistance while cycling. The results show that the sulfolane electrolyte shows more degradation at higher potentials unlike previous reports which suggested higher oxidative stability. However, the passivation layers formed due to this electrolyte degradation prevents further degradation. The resistance measurements show that major resistance arises from the cathode. The pressure evolution during the formation cycles suggests that there is lower gas evolution with sulfolane electrolyte than in the conventional electrolyte. The study opens a new outlook on the sulfolane based electrolyte especially on its oxidative/anodic stability.
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