Electrolytes and interphases in Li-ion batteries and beyond.

Ionically conducting polymer membranes (polymer electrolytes) might enhance lithium-battery technology by replacing the liquid electrolyte currently in use and thereby enabling the fabrication of flexible, compact, laminated solid-state structures free from leaks and available in varied geometries1. Polymer electrolytes explored for these purposes are commonly complexes of a lithium salt (LiX) with a high-molecular-weight polymer such as polyethylene oxide (PEO). But PEO tends to crystallize below 60 °C, whereas fast ion transport is a characteristic of the amorphous phase. So the conductivity of PEO–LiX electrolytes reaches practically useful values (of about 10−4 S cm−1) only at temperatures of 60–80 °C. The most common approach for lowering the operational temperature has been to add liquid plasticizers, but this promotes deterioration of the electrolyte's mechanical properties and increases its reactivity towards the lithium metal anode. Here we show that nanometre-sized ceramic powders can perform as solid plasticizers for PEO, kinetically inhibiting crystallization on annealing from the amorphous state above 60 °C. We demonstrate conductivities of around 10−4 S cm−1 at 50 °C and 10−5 S cm−1 at 30 °C in a PEO–LiClO4 mixture containing powders of TiO2 and Al2O3 with particle sizes of 5.8–13 nm. Further optimization might lead to practical solid-state polymer electrolytes for lithium batteries.

Nanocomposite polymer electrolytes for lithium batteries

This critical review presents an overview of the various classes of Li(+) conductors for use as electrolytes in lithium polymer batteries and all-solid state microbatteries. Initially, we recall the main models for ion transport and the structure-transport relationships at the basis of the observed conductivity behaviours. Emphasis is then placed on the physico-chemical and functional parameters relevant for optimal electrolytes preparation, as well as on the techniques of choice for their evaluation. Finally, the state of the art of polymer and ceramic electrolytes is reported, and the most interesting strategies for the future developments are described (121 references).

Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives

Department of Chemical Engineering, University of California, Berkeley, California 94720-1462, USAPast theories of electrode stability assume that the surface tension resists the ampliﬁcation of surface roughness at cathodes andshow that instability at lithium/liquid interfaces cannot be prevented by surface forces alone @Electrochim. Acta, 40, 599 ~1995!#.This work treats interfacial stability in lithium/polymer systems where the electrolyte is solid. Linear elasticity theory is employedto compute the additional effect of bulk mechanical forces on electrode stability. The lithium and polymer are treated as Hookeanelastic materials, characterized by their shear moduli and Poisson’s ratios. Two-dimensional displacement distributions that satisfyforce balances across a periodically deforming interface are derived; these allow computation of the stress and surface-tensionforces. The incorporation of elastic effects into a kinetic model demonstrates regimes of electrolyte mechanical properties whereampliﬁcation of surface roughness can be inhibited. For a polymer material with Poisson’s ratio similar to poly~ethylene oxide!,interfacial roughening is mechanically suppressed when the separator shear modulus is about twice that of lithium.© 2005 The Electrochemical Society. @DOI: 10.1149/1.1850854# All rights reserved.Manuscript submitted January 16, 2004; revised manuscript received July 29, 2004. Available electronically January 11, 2005.

https://iopscience.iop.org/article/10.1149/1.1850854/pdf

The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces

Review of gel-type polymer electrolytes for lithium-ion batteries

Studies of some poly(vinylidene fluoride) electrolytes

Polymer electrolyte membranes comprising poly(vinylidene fluoride)−hexafluoropropene (PVdF−HFP) copolymer plasticized with a solution of LiSO3CF3, LiN(SO2CF3)2, or LiPF6 in oligomeric poly(ethylene glycol) dimethyl ethers (PEGDME, Mw = 250, 400, and 500) were prepared by hot-melt-rolling or solvent-casting techniques. Since the electrolytes containing PEGDME400 and PEGDME500 are “dry” with essentially no volatile components up to 150 °C, we have dubbed them PEO-like. Their thermal stability, mechanical strength, conductivity, electrochemical stability window, and Li/electrolyte interface stability were characterized. Plasticizing PVdF−HFP with the PEGDME/LiX solutions disordered the polymer structure leading to polymer electrolytes having lower crystallinity than the polymer host itself. The mechanical strength of the electrolyte membranes varied depending on the PVdF content. Tensile strength (stress) as high as 420 psi at an elongation-at-break value (strain) of 75% was observed. The conductivities of t...

Highly Conductive PEO-like Polymer Electrolytes

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Studies of some poly(vinylidene fluoride) electrolytes

Highly Conductive PEO-like Polymer Electrolytes