This Review is focused on ion-transport mechanisms and fundamental properties of solid-state electrolytes to be used in electrochemical energy-storage systems. Properties of the migrating species significantly affecting diffusion, including the valency and ionic radius, are discussed. The natures of the ligand and metal composing the skeleton of the host framework are analyzed and shown to have large impacts on the performance of solid-state electrolytes. A comprehensive identification of the candidate migrating species and structures is carried out. Not only the bulk properties of the conductors are explored, but the concept of tuning the conductivity through interfacial effects—specifically controlling grain boundaries and strain at the interfaces—is introduced. High-frequency dielectric constants and frequencies of low-energy optical phonons are shown as examples of properties that correlate with activation energy across many classes of ionic conductors. Experimental studies and theoretical results are...

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Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction

Development of high conductivity solid-state electrolytes for lithium ion batteries has proceeded rapidly in recent years, but incorporating these new materials into high-performing batteries has proven difficult. Interfacial resistance is now the limiting factor in many systems, but the exact mechanisms of this resistance have not been fully explained - in part because experimental evaluation of the interface can be very difficult. In this work, we develop a computational methodology to examine the thermodynamics of formation of resistive interfacial phases. The predicted interfacial phase formation is well correlated with experimental interfacial observations and battery performance. We calculate that thiophosphate electrolytes have especially high reactivity with high voltage cathodes and a narrow electrochemical stability window. We also find that a number of known electrolytes are not inherently stable but react in situ with the electrode to form passivating but ionically conducting barrier layers. A...

http://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.5b04082

Interface Stability in Solid-State Batteries

Review on solid electrolytes for all-solid-state lithium-ion batteries

The new crystalline material family, lithium superionic conductor (thio-LISICON), was found in the Li 2 S-GeS 2 -P 2 S 5 system. The solid solution member x x 0.75 in Li 4-x Ge 1-x P x S 4 shows the highest conductivity of 2.2 x 10 -3 S cm -1 at 25°C of any sintered ceramic together with negligible electronic conductivity, high electrochemical stability, no reaction with lithium metal, and no phase transition up to 500°C. Its material design concepts of changing constituent ions with various ionic radii, valence, and polarizability are described.

https://iopscience.iop.org/article/10.1149/1.1379028/pdf

Lithium Ionic Conductor Thio-LISICON: The Li2 S ­ GeS2 ­ P 2 S 5 System

All-solid-state lithium batteries (ASSLBs) have the potential to revolutionize battery systems for electric vehicles due to their benefits in safety, energy density, packaging, and operable temperature range. As the key component in ASSLBs, inorganic lithium-ion-based solid-state electrolytes (SSEs) have attracted great interest, and advances in SSEs are vital to deliver the promise of ASSLBs. Herein, a survey of emerging SSEs is presented, and ion-transport mechanisms are briefly discussed. Techniques for increasing the ionic conductivity of SSEs, including substitution and mechanical strain treatment, are highlighted. Recent advances in various classes of SSEs enabled by different preparation methods are described. Then, the issues of chemical stabilities, electrochemical compatibility, and the interfaces between electrodes and SSEs are focused on. A variety of research addressing these issues is outlined accordingly. Given their importance for next-generation battery systems and transportation style, a perspective on the current challenges and opportunities is provided, and suggestions for future research directions for SSEs and ASSLBs are suggested.

Michel Tachez

Papers

Ionic conductivity of and phase transition in lithium thiophosphate Li3PS4