Highly conductive, ionic liquid-based polymer electrolytes

In this manuscript is reported a thermal and impedance spectroscopy investigation carried out on quaternary polymer electrolytes, to be addressed as separators for lithium solid polymer batteries, containing large amount of the N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide ionic liquid. The target is the development of Li+ conducting membranes with enhanced ion transport even below room temperature. Polyethylene oxide and polymethyl methacrylate were selected as the polymeric hosts. A fully dry, solvent-free procedure was followed for the preparation of the polymer electrolytes, which were seen to be self-consistent and handled even upon prolonged storage periods (more than 1 year). Appealing ionic conductivities were observed especially for the PEO electrolytes, i.e., 1.6 × 10-3and 1.5 × 10-4 S cm-1 were reached at 20 and -20°C, respectively, which are ones the best, if not the best ion conduction, never detected for polymer electrolytes

Hot-pressed, Dry, Nanocomposite, PEO-based Electrolyte Membranes. Ionic Conductivity Characterization and Battery Tests

http://www.electrochem.org/dl/ma/203/pdfs/0098.pd

Li1.4Al0.4Ge0.4Ti1.4(PO4)3 promising NASICON-structured glass-ceramic electrolyte for all-solid-state Li-based batteries: Unravelling the effect of diboron trioxide

Li-ion batteries (LIBs) are the ubiquitous technology to power portable electronics; however, for the next-generation of high-performing electrochemical energy storage systems for electric vehicles and smart grid facilities, breakthroughs are needed, particularly in the development of solid-state electrolytes, which may allow for enhanced energy density while enabling lithium metal anodes, combined with unrivalled safety and operative reliability. In this respect, here we present the successful synthesis of a glass-ceramic Li1.4Al0.4Ge0.4Ti1.4(PO4)3 NASICON-type solid-state electrolyte (SSE) through a melt-casting technique. Being grain boundaries crucial for the total ionic conductivity of SSEs, the effect of the addition of diboron trioxide (B2O3, 0.05 wt.%) to promote their liquefaction and restructuring is investigated, along with the effects on the resulting microstructures and ionic conductivities. By the thorough combination of structural-morphological and electrochemical techniques, we demonstrate that bulk materials show improved performance compared to their powder sintered counterpart, achieving remarkable ion mobility (> 0.1 mS cm–1 at –10 °C) and anodic oxidation stability (> 4.8 V vs Li+/Li). The addition of B2O3 positively affects the grain cohesion and growth, thus reducing the extension of the grain boundaries (and the related grain/grain interface resistance) and, therefore, increasing the overall ion mobility. In addition, B2O3 is seen to contrast the microcracks formation in the LAGTP system under study which, overall, shows very promising prospects as SSE for the next-generation of high-energy density, safe lithium-based batteries

safety assessment of ionic liquid based lithium ion battery prototypes

In this paper we report the results of combined cycle- and life-aging and abuse tests carried out under severe conditions on Li4Ti5O12/LiFePO4 lithium-ion stacked prototypes using a PYR14 FSI-LiTFSI ionic liquid electrolyte. No relevant degradation phenomena took place within ionic liquid electrolyte during prolonged inactivity period or overcharging. No fire/explosion or venting event as well as no gas development occurred during abuse tests, which led only to modest raise in temperature. Therefore, electrodes based on Li4Ti5O12 and LiFePO4 active materials can be favorably combined with non-volatile and non-flammable pyrrolidinium FSI ionic liquid electrolytes to realize highly safe lithium-ion battery systems

Ionic Liquid Electrolytes for Safer Lithium Batteries – I. Investigation around Optimal Formulation

In this paper we report on the investigation of ionic liquid-based electrolytes with enhanced characteristics. In particular, we have studied ternary mixtures based on the lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt and two ionic liquids sharing the same cation (N-methyl-N-propyl pyrrolidinium, PYR13), but different anions, bis(trifluoromethanesulfonyl)imide (TFSI) and bis(fluorosulfonyl)imide (FSI). The LiTFSI-PYR13TFSI-PYR13FSI mixtures, found to be ionically dissociated, exhibit better ion transport properties (about 10−3 S cm−1 at −20°C) with respect to similar ionic liquid electrolytes till reported in literature. An electrochemical stability window of 5 V is observed in carbon working electrodes. Preliminary battery tests confirm the good performance of these ternary electrolytes with high-voltage NMC cathodes and graphite anodes

Liquid Structure of a Water-in-Salt Electrolyte with a Remarkably Asymmetric Anion

Water-in-salt systems, i.e., super-concentrated aqueous electrolytes, such as lithium bis(trifluoromethanesulfonyl)imide (21 mol/kgwater), have been recently discovered to exhibit unexpectedly large electrochemical windows and high lithium transference numbers, thus paving the way to safe and sustainable charge storage devices. The peculiar transport features in these electrolytes are influenced by their intrinsically nanoseparated morphology, stemming from the anion hydrophobic nature and manifesting as nanosegregation between anions and water domains. The underlying mechanism behind this structure-dynamics correlation is, however, still a matter of strong debate. Here, we enhance the apolar nature of the anions, exploring the properties of the aqueous electrolytes of lithium salts with a strongly asymmetric anion, namely, (trifluoromethylsulfonyl)(nonafluorobutylsulfonyl) imide. Using a synergy of experimental and computational tools, we detect a remarkable level of structural heterogeneity at a mesoscopic level between anion-rich and water-rich domains. Such a ubiquitous sponge-like, bicontinuous morphology develops across the whole concentration range, evolving from large fluorinated globules at high dilution to a percolating fluorous matrix intercalated by water nanowires at super-concentrated regimes. Even at extremely concentrated conditions, a large population of fully hydrated lithium ions, with no anion coordination, is detected. One can then derive that the concomitant coexistence of (i) a mesoscopically segregated structure and (ii) fully hydrated lithium clusters disentangled from anion coordination enables the peculiar lithium diffusion features that characterize water-in-salt systems

An electrochemical compatibility investigation of RTIL-based electrolytes with Si-based anodes for advanced Li-ion batteries

Silicon is amongst the most attractive anode materials for Li-ion batteries because of its high gravimetric and volumetric capacity; importantly, it is also abundant and cheap, thus sustainable. For a widespread practical deployment of Si-based electrodes, research efforts must focus on significant breakthroughs to addressing the major challenges related to their poor cycling stability. In this work, we focus on the electrolyte-electrode relationships to support the scientific community with a systematic overview of Si-based cell design strategies reporting a thorough electrochemical study of different room temperature ionic liquid (RTIL)-based electrolytes, which contain either lithium bis(fluorosulfonyl)imide (LiFSI) or lithium bis(trifluoromethylsulfonyl)imide (LiTFSI). Their galvanostatic cycling performance with mixed silicon/graphite/few-layer graphene electrodes are evaluated, with first cycle coulombic efficiency approaching 90% and areal capacity ≈2 mAh/cm2 in the limited cut-off range of 0.1–2 V vs. Li+/Li0. The investigation evidences the superior characteristics of the FSI-based RTILs with respect to the TFSI-based one, which is mostly associated with the superior SEI forming ability of FSI-based systems, even without the use of specific additives. In particular, the LiFSI-EMIFSI electrolyte composition shows the best performance in both Li-half cells and Li-ion cells in which the Si-based electrodes are coupled with 4V-class composite NMC-based cathodes