Didier Devaux

Nonflammable perfluoropolyether-based electrolytes for lithium batteries

Significance This research article describes a unique class of nonflammable electrolytes for lithium-ion batteries that are based on functionalized perfluoropolyethers (PFPEs). It demonstrates that PFPEs may be used as a major component in operating batteries. These electrolytes not only are completely nonflammable, but they also exhibit unprecedented high transference numbers and low electrochemical polarization, indicative of longer battery life. The results in this work may represent a significant step toward a lithium-ion battery with improved safety and pave the way for the development of new electrolytes that can address the persisting challenges of current battery technologies. The flammability of conventional alkyl carbonate electrolytes hinders the integration of large-scale lithium-ion batteries in transportation and grid storage applications. In this study, we have prepared a unique nonflammable electrolyte composed of low molecular weight perfluoropolyethers and bis(trifluoromethane)sulfonimide lithium salt. These electrolytes exhibit thermal stability beyond 200 °C and a remarkably high transference number of at least 0.91 (more than double that of conventional electrolytes). Li/LiNi1/3Co1/3Mn1/3O2 cells made with this electrolyte show good performance in galvanostatic cycling, confirming their potential as rechargeable lithium batteries with enhanced safety and longevity.

Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries

Significance This study describes hybrid single ion-conducting electrolytes based on inorganic sulfide glasses and perfluoropolyether polymers for lithium batteries. Herein, it is shown that hybrid electrolytes provide a compelling alternative to the traditional glass, ceramic, or polymer battery electrolytes. These electrolytes present high transference numbers, unprecedented ionic conductivities at room temperature, and excellent electrochemical stability, and they limit the dissolution of lithium polysulfides. The results in this work represent a significant step toward addressing the challenges of enabling the next generation cathodes, such as lithium nickel manganese cobalt oxide and sulfur. Despite high ionic conductivities, current inorganic solid electrolytes cannot be used in lithium batteries because of a lack of compliance and adhesion to active particles in battery electrodes as they are discharged and charged. We have successfully developed a compliant, nonflammable, hybrid single ion-conducting electrolyte comprising inorganic sulfide glass particles covalently bonded to a perfluoropolyether polymer. The hybrid with 23 wt% perfluoropolyether exhibits low shear modulus relative to neat glass electrolytes, ionic conductivity of 10−4 S/cm at room temperature, a cation transference number close to unity, and an electrochemical stability window up to 5 V relative to Li+/Li. X-ray absorption spectroscopy indicates that the hybrid electrolyte limits lithium polysulfide dissolution and is, thus, ideally suited for Li-S cells. Our work opens a previously unidentified route for developing compliant solid electrolytes that will address the challenges of lithium batteries.

Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ∼30° below the expected freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.