ABSTRACT
Li metal secondary batteries known for their high energy and power density are the much-awaited energy storage systems owing to the high specific capacity of Li metal. However, due to the instability of Li metal with common Li-ion battery electrolytes, a combination with a polymer electrolyte seems to be an effective strategy to alleviate the safety issues of employing Li metal and provide design conformity to the system. Current trends show improvements in different aspects, such as improving ionic conductivity, single-ion conductivity, mechanical stability, and electrochemical stability. A combination of all these properties has been a bottleneck for the development of polymer electrolytes for safe and efficient operation of all solid-state batteries. Herein, a multifunctional polysalt has been synthesized from green and sustainable materials, namely, ethyl cellulose, plasticized with adiponitrile, that contributes to meeting the critical properties enabling high compatibility with Li metal and a quasi-single-ion-conducting property while simultaneously acting as a matrix/filler for efficient operation of the cells. This multifunctional polymer matrix inhibits further decomposition of nitrile-based plasticizers on Li metal anodes with the formation of a favorable Li metal anode interface, thus enabling the utilization of high-voltage stable nitrile-based plasticizers (4.2 V) to be implemented as an electrolyte component for realization of high-voltage Li metal anode polymer batteries.
ABSTRACT
Unlocking the full potential of solid-state electrolytes (SSEs) is key to enabling safer and more-energy dense technologies than today's Li-ion batteries. In particular, composite materials comprising a conductive, flexible polymer matrix embedding ceramic filler particles are emerging as a good strategy to provide the combination of conductivity and mechanical and chemical stability demanded from SSEs. However, the electrochemical activity of these materials strongly depends on their polymer/ceramic interfacial Li-ion dynamics at the molecular scale, whose fundamental understanding remains elusive. While this interface has been explored for nonconductive ceramic fillers, atomistic modeling of interfaces involving a potentially more promising conductive ceramic filler is still lacking. We address this shortfall by employing molecular dynamics and enhanced Monte Carlo techniques to gain unprecedented insights into the interfacial Li-ion dynamics in a composite polymer-ceramic electrolyte, which integrates polyethylene oxide plus LiN(CF3SO2)2 lithium imide salt (LiTFSI), and Li-ion conductive cubic Li7La3Zr2O12 (LLZO) inclusions. Our simulations automatically produce the interfacial Li-ion distribution assumed in space-charge models and, for the first time, a long-range impact of the garnet surface on the Li-ion diffusivity is unveiled. Based on our calculations and experimental measurements of tensile strength and ionic conductivity, we are able to explain a previously reported drop in conductivity at a critical filler fraction well below the theoretical percolation threshold. Our results pave the way for the computational modeling of other conductive filler/polymer combinations and the rational design of composite SSEs.
ABSTRACT
Developing multifunctional polymeric binders is key to the design of energy storage technologies with value-added features. We report that a multigram-scale synthesis of perylene diimide polymer (PPDI), from a single batch via polymer analogous reaction route, yields high molecular weight polymers with suitable thermal stability and minimized solubility in electrolytes, potentially leading to improved binding affinity toward electrode particles. Further, it develops strategies for designing copolymers with virtually any desired composition via a subsequent grafting, leading to purpose-built binders. PPDI dye as both binder and electroactive additive in lithium half-cells using lithium iron phosphate exhibits good electrochemical performance.
