Toward adequate control of internal interfaces utilizing nitrile-based electrolytes.

Methods to control internal interfaces in lithium ion batteries often require sophisticated procedures to deposit coating layers or introduce interphases, which are typically difficult to apply. This particularly holds for protection from parasitic reactions at the current collector, which reflects an internal interface for the electrode composite material and the electrolyte. In this work, electrolyte formulations based on aliphatic cyclic nitriles, cyclopentane-1-carbonitrile and cyclohexane-1-carbonitrile, are introduced that allow for successful suppression of aluminum dissolution and control of internal interfaces under application-relevant conditions. Such nitrile-based electrolytes show higher intrinsic oxidative and thermal stabilities as well as similar capacity retentions in lithium nickel-manganese-cobalt oxide LiNi3/5Mn1/5Co1/5O2 (NMC622)||graphite based full cells compared to the state-of-the-art organic carbonate-based electrolytes, even when bis(trifluoro-methane)sulfonimide lithium salt is utilized. Moreover, the importance of relative permittivity, degree of ion dissociation, and viscosity of the applied electrolyte formulations for the protection of current collector interfaces is emphasized.

Understanding transport mechanisms in ionic liquid/carbonate solvent electrolyte blends.

To unravel mechanistic details of the ion transport in liquid electrolytes, blends of the ionic liquid (IL) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI), ethylene carbonate (EC) and dimethyl carbonate (DMC) with the conducting salts lithium hexafluorophosphate (LiPF6) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) were investigated as a function of the IL concentration. Electrochemical impedance, Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR) and Raman spectroscopy supported by Molecular Dynamics (MD) simulations allowed the structural and dynamic correlations of the ion motions to be probed. Remarkably, we identified that though the individual correlations among different ion types exhibit a clear concentration dependence, their net effect is nearly constant throughout the entire concentration range, resulting in approximately equal transport and transference numbers, despite a monitored cross-over from carbonate-based lithium coordination to a TFSI-based ion coordination. In addition, though dynamical ion correlation could be found, the absolute values of the ionic conductivity are essentially determined by the overall viscosity of the electrolyte. The IL/carbonate blends with a Pyr14TFSI fraction of ∼10 wt% are found to be promising electrolyte solvents, with ionic conductivities and lithium ion transference numbers comparable to those of standard carbonate-based electrolytes while the thermal and electrochemical stabilities are considerably improved. In contrast, the choice of the conducting salt only marginally affects the transport properties.

On the interaction of water-soluble binders and nano silicon particles: alternative binder towards increased cycling stability at elevated temperatures.

Silicon based composites are among the most promising negative electrodes for lithium ion battery applications due to their high theoretical capacities. One major drawback of silicon based anodes are their large volume changes during lithiation and delithiation. Although many efforts have been made in view of new binder materials and improved electrolytes, the resulting battery cell suffers from severe capacity fading at ambient or elevated temperatures, respectively. The strong reactivity with the electrolyte is considered to be responsible for the reduced cycle life at elevated temperatures. In this work we introduce silicon composite anodes with a novel composition based on a gellan gum binder material that show an improved cycling performance at ambient temperature and at 60 °C. To elucidate the influence of the binder material, we investigated the structure of the silicon based composite anodes in order to understand the nature of the interaction of the gellan gum based binder polymers with the silicon particles in comparison with a common CMC binder. Also the influence of the choice of binder on the interactions at the interface between electrode surface and electrolyte were studied. A combination of powerful techniques including solid state NMR, TEM and EELS, XPS as well as FTIR were applied.

(7)Li in situ 1D NMR imaging of a lithium ion battery.

The spatial distribution of charge carriers in lithium ion batteries during current flow is of fundamental interest for a detailed understanding of transport properties and the development of strategies for future improvements of the electrolyte-electrode interface behaviour. In this work we explored the potential of (7)Li 1D in situ NMR imaging for the identification of concentration gradients under constant current load in a battery cell. An electrochemical cell based on PTFE body and a stack of glass microfiber discs that are soaked with a technically relevant electrolyte suitable for high-temperature application and squeezed between a Li metal and a nano-Si-graphite composite electrode was assembled to acquire (7)Li 1D in situ NMR profiles with an improved NMR pulse sequence as function of time and state of charge, thereby visualizing the course of ion concentration during charge and discharge. Surface localized changes of Li concentration were attributed to processes such as solid electrolyte interphase formation or full lithiation of the composite electrode. The method allows the extraction of lithium ion transport properties.

Intermediate temperature proton conductors for PEM fuel cells based on phosphonic acid as protogenic group: a progress report.

The melting behaviour and transport properties of straight chain alkanes mono- and difunctionalized with phosphonic acid groups have been investigated as a function of their length. The increase of melting temperature and decrease of proton conductivity with increasing chain length is suggested to be the consequence of an increasing ordering of the alkane segments which constrains the free aggregation of the phosphonic acid groups. However, the proton mobility is reduced to a greater extent than the proton diffusion coefficient indicating an increasing cooperativity of proton transport with increasing length of the alkane segment. The results clearly indicate that the "spacer concept", which had been proven successful in the optimization of the proton conductivity of heterocycle based systems, fails in the case of phosphonic acid functionalized polymers. Instead, a very high concentration of phosphonic acid functional groups forming "bulky" hydrogen bonded aggregates is suggested to be essential for obtaining very high proton conductivity. Aggregation is also suggested to reduce condensation reactions generally observed in phosphonic acid containing systems. On the basis of this understanding, the proton conductivities of poly(vinyl phosphonic acid) and poly(meta-phenylene phosphonic acid) are discussed. Though both polymers exhibit a substantial concentration of phosphonic acid groups, aggregation seems to be constrained to such an extent that intrinsic proton conductivity is limited to values below sigma = 10(-3) S cm(-1) at T = 150 degrees C. The results suggest that different immobilization concepts have to be developed in order to minimize the conductivity reduction compared to the very high intrinsic proton conductivity of neat phosphonic acid under quasi dry conditions. In the presence of high water activities, however, (as usually present in PEM fuel cells) the very high ion exchange capacities (IEC) possible for phosphonic acid functionalized ionomers (IEC >10 meq g(-1)) may allow for high proton conductivities in the intermediate temperature range (T approximately 120 -160 degrees C).