Mixed ionic-electronic conducting (MIEC) ceramic-based membranes for oxygen separation

Solid-state batteries with desirable advantages, including high-energy density, wide temperature tolerance, and fewer safety-concerns, have been considered as a promising energy storage technology to replace organic liquid electrolyte-dominated Li-ion batteries. Solid-state electrolytes (SSEs) as the most critical component in solid-state batteries largely lead the future battery development. Among different types of solid-state electrolytes, garnet-type Li7La3Zr2O12 (LLZO) solid-state electrolytes have particularly high ionic conductivity (10-3 to 10-4 S/cm) and good chemical stability against Li metal, offering a great opportunity for solid-state Li-metal batteries. Since the discovery of garnet-type LLZO in 2007, there has been an increasing interest in the development of garnet-type solid-state electrolytes and all solid-state batteries. Garnet-type electrolyte has been considered one of the most promising and important solid-state electrolytes for batteries with potential benefits in energy density, electrochemical stability, high temperature stability, and safety. In this Review, we will survey recent development of garnet-type LLZO electrolytes with discussions of experimental studies and theoretical results in parallel, LLZO electrolyte synthesis strategies and modifications, stability of garnet solid electrolytes/electrodes, emerging nanostructure designs, degradation mechanisms and mitigations, and battery architectures and integrations. We will also provide a target-oriented research overview of garnet-type LLZO electrolyte and its application in various types of solid-state battery concepts (e.g., Li-ion, Li-S, and Li-air), and we will show opportunities and perspectives as guides for future development of solid electrolytes and solid-state batteries.

Garnet-Type Solid-State Electrolytes: Materials, Interfaces, and Batteries.

Critically selected values for the entropy (S°288.«), molar volume (VWw), and for the heat and Gibbs free energy of formation (AH 0 f,z98.i5 and AG°f.288.is) are given for 50 reference elements and 285 minerals and related substances. For 211 materials for which high-temperature heat-capacity or heat-content data are available AH°f,T , AG°f,T , S°T, logKf/r and (G°T H°298.i5/T) are tabulated at 100°K intervals for temperatures up to 2,000°K. For substances having solid-state phase changes or whose melting or boiling point is less than 2,000°K, we also have tabulated the properties listed above at the temperature of the phase change so that the heat or entropy changes associated with the transformation form an integral part of the high-temperature tables. INTRODUCTION The purpose of these tables is to present a critical summary of the available thermodynamic data for minerals and related substances in a convenient form for the use of earth scientists. To make the tables as useful as possible we have tried to include as much of the necessary auxiliary data as possible so that a single set of tables would suffice for most calculations, to insure internal consistency and to provide for the means of rapid revision and expansion as new data become available. This compilation is divided into two sections. In the first section we give values for the entropy (S°288.i 5 ), molar volume (V°298 . K ), the heat (enthalpy, AH°f.298.i 5 ) and Gibbs free energy (AG0 f,288. 15 ), and the logarithm of the equilibrium constant of formation (log Kf, 298.15) for the reference elements, minerals, a number of oxides, and other substances of geological interest. The data have been critically evaluated and uncertainties assigned to the 298.15°K properties. The sources of data are indicated numerically in the tables and listed in complete form following the tables. 2 THERMODYNAMIC PROPERTIES OF MINERALS The data are arranged in order of their conventional mineralogical groups. Within each group (for example the oxides) the listing is by alphabetical order of the chemical symbol of the principal cation. The tables in the second section contain values for the high-temperature thermodynamic properties, H°T H°ns.u, (G°T -H°298.iS )/T, S°T, AG°f,T, AH°,,T, and log Kf,T at 100°K intervals up to 2000°K. Heat-capacity data, as such, have been omitted from these tables in favor of the function H°T H 0 298.i 5 which is the quantity actually measured in most high-temperature experiments. Heat capacities, C P , derived from H°T H°298.i 5 data are at best only approximate and their use should be avoided when possible. Approximate values for C P are readily obtained from the first differences of the tabulated H° T H 0 298.i5 function. Thermodynamic properties of gases at high pressures have not been included in these tables. High pressure-high temperature functions of the geologically important gases H20 and C02 are given by Bain (1964), Hilsenrath and others (1955), and Robie (1966). These tables entirely supersede two earlier reports on the same subject matter by Robie (1959,1966)! ACKNOWLEDGMENTS Professor E. F. Westrum, Jr., University of Michigan, Professor 0. J. Kleppa, University of Chicago, and P. B. Barton, Jr., Priestley Toulmin, and D. R. Wones, U.S. Geological Survey, have kindly permitted us to use some of their unpublished data. We are particularly grateful to Keith Beardsley of the U.S. Geological Survey who wrote the computer routines for processing the 298.15°K tables and the bibliography. E-an Zen of the U.S. Geological Survey and Professor J. B. Thompson, Jr., of Harvard University offered many helpful suggestions for improving the clarity and usefulness of these tables. Computer facilities at the Massachusetts Institute of Technology were used initially to develop the program for compiling hightemperature thermodynamic functions. More recent revisions of the program and the present set of tables were prepared at the Harvard Computing Center, with computer costs supported by the Higgins Fund and the Committee on Experimental Geology and Geophysics of Harvard University. THERMODYNAMIC PROPERTIES OF MINERALS 3 PHYSICAL CONSTANTS AND ATOMIC WEIGHTS The symbols and constants adopted for this report are listed in table 1. Values for the physical constants used in the calculations were those recommended by the National Academy of ScienceNational Research Council (U.S. Natl. Bur. Standards Tech. News Bull., v. 47, p. 175-177, 1963). For convenience we also give values of the international atomic weights for 1963 (scale C12 = 12.0000) in alphabetical order by their chemical symbol in table 2. Elements for which no atomic weight is listed have no stable isotope. TABLE 1. Symbols and constants T Temperature in degrees Kelvin, (°K) gfw Gram formula weight H° -H° Enthalpy at temperature T relative to 298.15°K in cal gfw 1 , T S° Entropy at temperature T in cal deg-gfw" 1 G° -H° T SM.15 m Gibbs free energy function in cal deg-gfw" 1 A^f° Heat of formation from reference state in cal gfw" 1 AG° Gibbs free energy of formation from reference state in cal gfw"1 Kr Equilibrium constant of formation Cp Heat capacity at constant pressure in cal deg-gfw" 1 0 Superscript indicates the substance is in its standard state » TTO meit Heat of melting at one atmosphere in cal gfw" 1 AH° Heat of vaporization to ideal gas at one atmosphere at the "p normal boiling point in cal gfw" 1 V° Volume of one gram formula weight at one atmosphere and "* " 298.15°K in cm8 R Gas constant, 1.98717 ±.00030 cal deg-gfw 1 , 8.31469 joules deg-gfw" 1 cal Calorie, unit of energy, 4.1840 absolute joules, 41.2929 cm* atmosphere A Avogadro's number, (6.02252 ±. 00028) xlO23 formula ' units gfw1 P Pressure, either in atmosphere or bars atm Atmosphere, 1,013,260 dynes cm"* bar Bar, 1,000,000 dynes cm"2 log Common logarithm, base 10 In Natural logarithm, base e= 2.71828. . . THERMODYNAMIC PROPERTIES OF MINERALS TABLE 2. Atomic weights for 1963

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Thermodynamic properties of minerals and related substances at 298.15 K (25.0 C) and one atmosphere (1.013 bars) pressure and at higher temperatures

Thermodynamics of formation of simple spinels

The phase diagram for the system ZrO/sub 2/--Y/sub 2/O/sub 3/ was redetermined. The extent of the fluorite-type ZrO/sub 2/--Y/sub 2/O/sub 3/ solid solution field was determined with a high-temperature x-ray furnace, precise lattice parameter measurements, and a hydrothermal technique. Long range ordering occurred at 40 mol% Y/sub 2/O/sub 3/ and the corresponding ordered phase was Zr/sub 3/Y/sub 4/O/sub 12/. The compound has rhombohedral symmetry (space group R3), is isostructural with UY/sub 6/O/sub 12/, and decomposes above 1250 +- 50/sup 0/C. The results indicate that the eutectoid may occur at a temperature <400/sup 0/C at a composition between 20 and 30 mol% Y/sub 2/O/sub 3/. Determination of the liquidus line indicated a eutectic at 83 +- 1 mol% Y/sub 2/O/sub 3/ and a peritectic at 76 +- 1 mol% Y/sub 2/O/sub 3/.

Phase Equilibria and Ordering in the System ZrO2‐Y2O3

Electromotive force measurements on galvanic cells involving solid electrolytes have been made in order to obtain the standard molar free energy of formation of , , , , , , and several phases of the system Ag‐Te at elevated temperatures.

Measurements on Galvanic Cells Involving Solid Electrolytes

The use of electromotive force measurements on galvanic cells for the determination of standard molar free energies of formation of halides, oxides, sulfides, and other compounds at elevated temperatures is surveyed. New potentialities and inherent limitations are shown. Formulas for the estimate of errors resulting from electronic conduction and from transference of the components of electrolytes between different activity levels are derived.

https://iopscience.iop.org/article/10.1149/1.2428567/pdf

Kalevi Kiukkola

Papers

Measurements on Galvanic Cells Involving Solid Electrolytes

Galvanic Cells for the Determination of the Standard Molar Free Energy of Formation of Metal Halides, Oxides, and Sulfides at Elevated Temperatures