Solid-state electrolytes are attracting increasing interest for electrochemical energy storage technologies. In this Review, we provide a background overview and discuss the state of the art, ion-transport mechanisms and fundamental properties of solid-state electrolyte materials of interest for energy storage applications. We focus on recent advances in various classes of battery chemistries and systems that are enabled by solid electrolytes, including all-solid-state lithium-ion batteries and emerging solid-electrolyte lithium batteries that feature cathodes with liquid or gaseous active materials (for example, lithium–air, lithium–sulfur and lithium–bromine systems). A low-cost, safe, aqueous electrochemical energy storage concept with a ‘mediator-ion’ solid electrolyte is also discussed. Advanced battery systems based on solid electrolytes would revitalize the rechargeable battery field because of their safety, excellent stability, long cycle lives and low cost. However, great effort will be needed to implement solid-electrolyte batteries as viable energy storage systems. In this context, we discuss the main issues that must be addressed, such as achieving acceptable ionic conductivity, electrochemical stability and mechanical properties of the solid electrolytes, as well as a compatible electrolyte/electrode interface. This Review details recent advances in battery chemistries and systems enabled by solid electrolytes, including all-solid-state lithium-ion, lithium–air, lithium–sulfur and lithium–bromine batteries, as well as an aqueous battery concept with a mediator-ion solid electrolyte.

Lithium battery chemistries enabled by solid-state electrolytes

This chapter introduces the finite element method (FEM) as a tool for solution of classical electromagnetic problems. Although we discuss the main points in the application of the finite element method to electromagnetic design, including formulation and implementation, those who seek deeper understanding of the finite element method should consult some of the works listed in the bibliography section.

Introduction to the Finite Element Method

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

Recent advances in all-solid-state rechargeable lithium batteries

Batteries are electrochemical devices that store electrical energy in the form of chemical energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and electric vehicles. Conventional LiBs use an organic polymer electrolyte, which exhibits several safety issues including leakage, poor chemical stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power density. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compounds are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion conductivity of ∼10−6 at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion conductivity of 10−3 S cm−1 at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chemically stable at higher temperatures and voltages compared to polymer electrolytes. Here, we discuss the chemical composition–structure–ionic conductivity relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.

Garnet-type solid-state fast Li ion conductors for Li batteries: critical review

The Role of Al and Li Concentration on the Formation of Cubic Garnet Solid Electrolyte of Nominal Composition Li7La3Zr2O12

https://apps.dtic.mil/dtic/tr/fulltext/u2/a579638.pdf

Effect of substitution (Ta, Al, Ga) on the conductivity of Li7La3Zr2O12

Cubic garnet Li6.24La3Zr2Al0.24O11.98 (LLZO) is a candidate material for use as an electrolyte in Li–Air and Li–S batteries. The use of LLZO in practical devices will require LLZO to have good mechanical integrity in terms of scratch resistance (hardness) and an adequate stiffness (elastic modulus). In this paper, the powders were fabricated by powder processing of cast ingots. All specimens were then densified via hot pressing. The room temperature elastic moduli (Young’s modulus, shear modulus, bulk modulus, and Poisson’s ratio) and hardness were measured by resonant ultrasound spectroscopy, and Vickers indentation, respectively. For volume fraction porosity, P, the Young’s modulus was 149.8 ± 0.4 GPa (P = 0.03) and 132.6 ± 0.2 GPa (P = 0.06). The mean Vickers hardness was 6.3 ± 0.3 GPa for P = 0.03 and 5.2 ± 0.4 for P = 0.06.

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Ezhiyl Rangasamy

Papers

The Role of Al and Li Concentration on the Formation of Cubic Garnet Solid Electrolyte of Nominal Composition Li7La3Zr2O12

Effect of substitution (Ta, Al, Ga) on the conductivity of Li7La3Zr2O12

Room temperature elastic moduli and Vickers hardness of hot-pressed LLZO cubic garnet

Synthesis and high Li-ion conductivity of Ga-stabilized cubic Li7La3Zr2O12

High conductivity of dense tetragonal Li7La3Zr2O12