The is a comprehensive review on the needs and potential storage technologies for electrical grid that is expected to integrate significant levels of renewables. This review offers details of the technologies, in terms of needs, status, challenges and future R&d directions.

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Electrochemical Energy Storage for Green Grid

Fast Na+-ion transport in skeleton structures

Computer simulation of grain growth—I. Kinetics

The influence of grain size and water content on the high-temperature plasticity of olivine aggregates was studied, using a gas-medium high-pressure deformation apparatus. The specimens used were hot-pressed, dense olivine aggregates with controlled grain size ranging from a few to 70 μm, with or without added water. Mechanical tests were made at 1573 K and 300 MPa confining pressure and at strain rates of 10−3 to 10−6 s−1. The results reveal two distinct mechanisms of deformation, depending on stress level and grain size. At relatively high stress and large grain size, the strain rate is proportional to about the cube power of the stress and is nearly independent of grain size. In this regime, microstructural observations gave evidence of intragranular deformation involving dislocation motion. At low stress and small grain size, the strain rate depends almost linearly on stress and decreases markedly with increase in grain size. In the latter regime, little evidence was found for intragranular deformation. These observations suggest that the deformation mechanism in the grain size insensitive regime is dislocation creep, while that in the grain size sensitive regime is diffusion creep. In both regimes, water was found to enhance the creep rate. The absence of grain size sensitivity in the dislocation creep regime and comparison with single-crystal data indicate that the water weakening effect is mainly an intragranular process. However, the existence also of a water weakening effect in the diffusion creep regime indicates that water also enhances diffusion. The extrapolation of the present results to coarser grain sizes indicates that the transition from dislocation to diffusion creep occurs at 0.1–1 MPa for 10-mm grain size. Therefore it is suggested that this transition may occur in the upper mantle and that, in both regimes, the presence of trace amounts of water will result in significantly lower creep strength than under strictly “dry” conditions.

Rheology of synthetic olivine aggregates: Influence of grain size and water

Among the contenders in the new generation energy storage arena, all-solid-state batteries (ASSBs) have emerged as particularly promising, owing to their potential to exhibit high safety, high energy density and long cycle life. The relatively low conductivity of most solid electrolytes and the often sluggish charge transfer kinetics at the interface between solid electrolyte and electrode layers are considered to be amongst the major challenges facing ASSBs. This review presents an overview of the state of the art in solid lithium and sodium ion conductors, with an emphasis on inorganic materials. The correlations between the composition, structure and conductivity of these solid electrolytes are illustrated and strategies to boost ion conductivity are proposed. In particular, the high grain boundary resistance of solid oxide electrolytes is identified as a challenge. Critical issues of solid electrolytes beyond ion conductivity are also discussed with respect to their potential problems for practical applications. The chemical and electrochemical stabilities of solid electrolytes are discussed, as are chemo-mechanical effects which have been overlooked to some extent. Furthermore, strategies to improve the practical performance of ASSBs, including optimizing the interface between solid electrolytes and electrode materials to improve stability and lower charge transfer resistance are also suggested.

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New horizons for inorganic solid state ion conductors

An analysis of strains and stresses in four-point bending creep tests in the limit of small beam deflections resulted in a general equation which relates the load-point deflection, the applied load, the creep exponent (N), and the geometrical parameters of the loading system. Measurements of load-point deflection rates, which are experimentally easy to accomplish in ceramic systems, vs the applied load lead to the direct determination of the creep exponent and the creep compliance in a steady-state creep test. The creep compliance is a function of the temperature, grain size, and all other factors except stress. The elastic equation relating the load-point deflection and the outer fiber strain is strictly valid for viscous creep and approximately valid for nonviscous creep (i.e. N>1) if the ratio of the distance between the support points to the distance between the load points is not very large.

Calculation of Stresses and Strains in Four-Point Bending Creep Tests

All data available in the literature regarding oxygen activities and composition limits for the wustite phase were analyzed critically. The most reliable activity data were collected into a composite in which (1) the partial molal free energy of oxygen varied linearly with composition and reciprocal temperature and (2) the partial molal enthalpy and entropy of oxygen varied linearly with composition and were independent of temperature. These linear variations of the thermodynamic properties are inconsistent with the presence of additional phases which have been reported within the wustite phase field. The composition limits of the wustite phase, which were computed from the composite, were in excellent agreement with Darken and Gurry's original phase diagram.

Review of Oxygen Activities and Phase Boundaries in Wustite as Determined by Electromotive-Force and Gravimetric Methods

Grain size effects were used to evaluate the relative contributions of aluminium lattice and oxygen grain boundary diffusion to the high temperature (1350 to 1550° C) steady state creep of polycrystalline alumina, pure and doped with transition metal impurities (Cr, Fe). Divalent iron in solid solution was found to enhance both aluminium lattice and oxygen grain-boundary diffusion. Large concentrations of divalent iron led to viscous Coble creep which was rate-limited entirely by oxygen grain-boundary diffusion. Nabarro-Herring creep which was rate-limited by aluminium lattice diffusion was observed in pure and chromium-doped material. Chromium additions had no effect on diffusional creep rates but significantly depressed non-viscous creep modes of deformation. Creep deformation maps were constructed at various iron dopant concentrations to illustrate the relative contributions of aluminium grain boundary, aluminium lattice, and oxygen grain-boundary diffusion to the diffusional creep of polycrystalline alumina.

Creep of polycrystalline alumina, pure and doped with transition metal impurities

A mass transport equation which takes into account parallel diffusion paths for both anions and cations was derived and applied to the diffusional creep of polycrystalline ionic solids. From the results of the analysis, several limiting conditions were found for grain-boundary- and lattice-diffusion-controlled kinetics. These conditions depend on temperature, grain size, and type and concentration of cation impurities. Examples of these limiting situations are given for the creep of polycrystalline Fe-doped MgO and transition-metal-doped Al2O3.

Summary
A mass transport equation which takes into account parallel diffusion paths for anions and cations was derived and applied to the diffusional creep of polycrystalline ionic solids. The effect of grain size and cation impurities of variable valence in solid solution on the relative contributions of lattice and grain-boundary diffusion of different ionic species in polycrystalline MgO and Al2O3 was examined. Depending on the temperature, grain size, impurity level, and O2 partial pressure, several limiting conditions were found:

Limit I: At very small grain sizes and reasonably small cation lattice diffusivities the creep rate will be controlled by the slower-moving ion in the grain-boundary regions (i.e. Coble creep).

Limit II: For intermediate grain sizes and cation lattice diffusivities the creep rate will be controlled by cation lattice diffusion when anion transport is significantly faster near grain boundaries than in the lattice (i.e. Nabarro-Herring creep).

Limit III: For an appropriate combination of large grain size and high cation lattice diffusivity the creep rate will be controlled by anion boundary diffusion (i.e. Coble creep).

Well-defined examples of limits I and II have been observed in the creep of Fe-doped polycrystalline MgO, and tentative evidence exists for limit III. Most results of studies of creep in polycrystalline Al2O3 (doped and undoped) fall within limit II, with some overlap with limit III.

The model developed in the present work explains much of the data in the literature in which creep rates correspond to cation lattice mobilities. It is concluded that in the creep of polycrystalline ionic solids anion transport near grain boundaries is rapid and can, in some circumstances, be rate-controlling. It should also be possible to apply this model to sintering and thermal-grooving data for such systems, particularly for Al2O3, in which cation lattice diffusion is frequently observed to be rate-controlling.32

Mass Transport in the Diffusional Creep of Ionic Solids

The sodium ion resistivity of lithia-stabilized polycrystalline β”-alumina was measured as a function of temperature for fine-grained and coarse-grained specimens with a chemical composition of 8.80 Na20-0.75 Li2O-90.45 A12O3 (wt%). A model is presented which explains the dependence of sodium ion resistivity on grain size. Using the model the activation energy was determined for the transport of sodium ions across a grain boundary in this form of sodium β”-alumina.

Ronald S. Gordon

Papers

Calculation of Stresses and Strains in Four-Point Bending Creep Tests

Review of Oxygen Activities and Phase Boundaries in Wustite as Determined by Electromotive-Force and Gravimetric Methods

Creep of polycrystalline alumina, pure and doped with transition metal impurities

Mass Transport in the Diffusional Creep of Ionic Solids

Resistivity‐Microstructure Relations in Lithia‐Stabilized Polycrystalline β”‐Alumina