Ionic Conductivities and Microstructures of CeO2:Y203 Solid Electrolytes

1998 ◽  
Vol 548 ◽  
Author(s):  
Chunyan Tian ◽  
Siu-Wai Chan
Keyword(s):  
Grain Boundary ◽  
Grain Boundaries ◽  
Solid Electrolytes ◽  
Dopant Concentration ◽  
Ionic Conductivities ◽  
Oxygen Depletion ◽  
Boundary Conductivity ◽  
Size Dependent ◽  
Impurity Segregation ◽  
Microanalytical Technique

ABSTRACTIonic conductivities of solid CeO2:Y203 electrolytes were systematically investigated as a function of dopant concentration and sintering temperatures. The highest lattice conductivity occurred at 6–8% dopant concentration, and maximum grain boundary conductivity was observed at 10% dopant concentration. The sintering temperature was found to have a significant effect on the conductivities of the pellets. The samples sintered at lower temperatures (T≤140°C) showed higher grain boundary conductivity than those sintered at 150°C; this was found to be related to size-dependent-impurity segregation and precipitation at grain boundaries. The grain boundary conductivities as related to the microstructure are discussed by adopting different grain boundary models. Solute segregation and oxygen depletion at grain boundaries, which have been suggested to be responsible for the grain boundary resistivities in these samples, were examined by a microanalytical technique for small-grain-size samples.

scholarly journals Towards Understanding the Different Influences of Grain Boundaries on Ion Transport in Sulfide and Oxide Solid Electrolytes

2019 ◽  
Author(s):  
James Dawson ◽  
Pieremanuele Canepa ◽  
Matthew Clarke ◽  
Theodosios Famprikis ◽  
Dibyajyoti Ghosh ◽  
...  
Keyword(s):  
Grain Boundary ◽  
Ion Transport ◽  
Grain Boundaries ◽  
Solid Electrolytes ◽  
Ionic Conductivities ◽  
Liquid Electrolyte ◽  
Boundary Resistance ◽  
Polycrystalline Materials ◽  
Solid State Batteries ◽  
And Performance

Solid electrolytes provide a route to the development of all-solid-state batteries that can potentially surpass the safety and performance of conventional liquid electrolyte-based devices. Sulfide solid electrolytes have received particular attention as a result of their high ionic conductivities. One of the main reasons for such high ionic conductivity is the apparently reduced grain boundary resistance of sulfide solid electrolytes compared to their oxide counterparts, but this is not fully established. Using two model electrolyte systems, Na3PS4 and Na3PO4, we apply a novel microscale simulation approach to analyze ionic transport in polycrystalline materials with various grain volumes. For Na3PO4, high grain boundary resistance is found, with the Na-ion conductivity decreasing with decreasing grain volume. For Na3PS4, the overall influence of grain boundaries is significantly reduced compared to the oxide. Detailed analysis reveals a minimal change in the local structures and Na-ion conduction mechanism between bulk and polycrystalline Na3PS4, whereas the change is far more substantial for Na3PO4, with evidence of over-coordination of Na ions at the grain boundaries. Our microscale approach helps to explain the fundamentally different influences of grain boundaries on ion transport in phosphate and thiophosphate solid electrolytes.

Towards Understanding the Different Influences of Grain Boundaries on Ion Transport in Sulfide and Oxide Solid Electrolytes

2019 ◽  
Author(s):  
James Dawson ◽  
Pieremanuele Canepa ◽  
Matthew Clarke ◽  
Theodosios Famprikis ◽  
Dibyajyoti Ghosh ◽  
...  
Keyword(s):  
Grain Boundary ◽  
Ion Transport ◽  
Grain Boundaries ◽  
Solid Electrolytes ◽  
Ionic Conductivities ◽  
Liquid Electrolyte ◽  
Boundary Resistance ◽  
Polycrystalline Materials ◽  
Solid State Batteries ◽  
And Performance

Solid electrolytes provide a route to the development of all-solid-state batteries that can potentially surpass the safety and performance of conventional liquid electrolyte-based devices. Sulfide solid electrolytes have received particular attention as a result of their high ionic conductivities. One of the main reasons for such high ionic conductivity is the apparently reduced grain boundary resistance of sulfide solid electrolytes compared to their oxide counterparts, but this is not fully established. Using two model electrolyte systems, Na3PS4 and Na3PO4, we apply a novel microscale simulation approach to analyze ionic transport in polycrystalline materials with various grain volumes. For Na3PO4, high grain boundary resistance is found, with the Na-ion conductivity decreasing with decreasing grain volume. For Na3PS4, the overall influence of grain boundaries is significantly reduced compared to the oxide. Detailed analysis reveals a minimal change in the local structures and Na-ion conduction mechanism between bulk and polycrystalline Na3PS4, whereas the change is far more substantial for Na3PO4, with evidence of over-coordination of Na ions at the grain boundaries. Our microscale approach helps to explain the fundamentally different influences of grain boundaries on ion transport in phosphate and thiophosphate solid electrolytes.

Conductivity of Grains and Grain Boundaries in Polycrystalline Heteropoly Acid Salts

2005 ◽  
Vol 494 ◽  
pp. 101-106
Author(s):  
B. Škipina ◽  
T. Čajkovski ◽  
M. Davidović ◽  
D. Čajkovski ◽  
V. Likar-Smiljanić ◽  
...  
Keyword(s):  
Impedance Spectroscopy ◽  
Grain Boundary ◽  
Grain Boundaries ◽  
Heteropoly Acid ◽  
Tungstophosphoric Acid ◽  
Heteropoly Acids ◽  
Relaxation Phenomena ◽  
Frequency Range ◽  
Boundary Conductivity ◽  
Bivalent Ions

In our previous work we investigated the conductivity and dielectric relaxation phenomena in heteropoly acids and their salts. In this work, we have studied the conductivity of grains and grain boundaries in compressed powders of 12-tungstophosphoric acid (WPA) salts with univalent and bivalent ions. The method of impedance spectroscopy has been employed in the frequency range from 5 Hz to 500 kHz. We obtained grains and grain boundaries conductivities as well as corresponding activation energies. Grain conductivity in all investigated salts is always higher than the grain boundary conductivity.

Structural multiplicity in a tilt boundary in germanium

1988 ◽  
Vol 46 ◽  
pp. 592-593
Author(s):  
D.A. Smith ◽  
Z. Elgat ◽  
W. Krakow ◽  
A.A. Levi ◽  
C.B. Carter
Keyword(s):  
Grain Boundary ◽  
Grain Boundaries ◽  
Twin Boundary ◽  
Atomic Structure ◽  
Czochralski Method ◽  
Tilt Boundary ◽  
Considerable Progress ◽  
Related Structure ◽  
First Order ◽  
Impurity Segregation

There has been considerable progress made recently in understanding the atomic structure of grain boundaries in metals, semiconductors and ceramics. There is still, however, some dispute over whether a given grain boundary can exist with more than one non-symmetry-related structure. This has been shown experimentally to be the case in Ge for the first-order twin boundary lying parallel to the lateral {112} plane. In the present paper, it will be shown that a similar result holds for a more general grain boundary (actually Σ=137) lying close to the Σ=19 orientation; the Σ=19 boundary is formed by a rotation of 26.5° about a common <110> direction and lies along a common {31} plane. It is thus likely that a similar result will hold for other grain boundaries.Since it is essential to know that the different structures are not due to impurity segregation effects, bicrystals were grown from the melt with pre-oriented seeds using the Czochralski method following the approach of Bacmann as modified at Cornell by Skrotzki et al.

An atom probe field ion microscope analysis of grain boundary chemistry in boron and carbon doped NiAl

1992 ◽  
Vol 50 (2) ◽  
pp. 1220-1221
Author(s):  
Raman Jayaram ◽  
M.K Miller
Keyword(s):  
Grain Boundary ◽  
Enrichment Factor ◽  
Grain Boundaries ◽  
Atom Probe ◽  
Probe Field ◽  
Carbon Doped ◽  
Boron Segregation ◽  
Microanalytical Technique ◽  
Microalloying Elements ◽  
Boundary Chemistry

The low temperature brittleness of nickel aluminides has been a serious impediment to their technological applications. A commonly employed technique to ductilize these materials involves the addition of suitable microalloying elements and correlating grain boundary chemistry with fracture mode. In the well documented case of Ni3Al, boron segregation to grain boundaries is accompanied by suppression of intergranular fracture and a significant increase in ductility. The high resolution microanalytical technique of atom probe field ion microscopy (APFIM) has been used in this study to analyze grain boundaries in order to characterize similar attempts to ductilize NiAl. APFIM specimens were prepared from tensile specimens of stoichiometric NiAl doped with either 0.04 or 0.12 at. % boron or 0.1 at % carbon, respectively. A field ion image of a grain boundary in a B-doped NiAl specimen is shown in Fig. 1. The brightly-imaging spots decorating the boundary were determined by atom probe analysis to be boron atoms. The boron enrichment factor at the boundary depends on the assumed thickness of the segregation as shown in Fig. 2 with an enrichment factor of ∼850 times for a monolayer coverage (i.e. 0.2 nm).

STEM Investigation of Segregation and Local Structure at Grain Boundary in Tetragonal Zirconia

1997 ◽  
Vol 3 (S2) ◽  
pp. 549-550
Author(s):  
H. Gu ◽  
F. Wakai
Keyword(s):  
Grain Boundary ◽  
Grain Boundaries ◽  
Solid Electrolytes ◽  
Tetragonal Zirconia ◽  
Boundary Structure ◽  
Contrast Imaging ◽  
Amorphous Films ◽  
Grain Boundary Structure ◽  
Z Contrast ◽  
Segregation Of Impurities

Y or Ca stabilized tetragonal ZrO2 (TZP) exhibits superplasticity at high temperature, and can also be used as solid electrolytes. Those properties are dictated by structure and chemistry of grain boundaries, which can be controlled by segregation of impurities or additives. The grain boundaries were found either covered by amorphous films or free of the film. Co-segragation of additives and stabilizers has also been observed. To fully understand the correlation between segregation and grain boundary structure, a dedicated STEM (VG HB601) capable of EDX/EELS analysis and phase/Z-contrast imaging is employed to study 3Y-TZP doped with 0.3 and 0.9 mol% SiO2.Although Y-L lines arc dominated by overlapping Zr-L lines in EDX, Y excess at grain boundaries can still be measured by “spatial difference” which removes Zr signal with a spectrum from the bulk. The co-segregation of Si and Y is also observed (Fig. 1) at many boundaries. Their average excesses arc 5±2 nm−2and 25±10 run−2 respectively, close to 1 monolayer each of SiO2 and Y2O3.

Interfaces Part II: Mechanical and High-Temperature Behavior

MRS Bulletin ◽  
1990 ◽  
Vol 15 (10) ◽  
pp. 23-25 ◽  
Author(s):  
Dieter Wolf ◽  
Sidney Yip
Keyword(s):  
High Temperature ◽  
Grain Boundary ◽  
Grain Boundaries ◽  
Fracture Behavior ◽  
Boundary Energy ◽  
Temperature Behavior ◽  
Boundary Structure ◽  
Elastic Response ◽  
High Temperature Behavior ◽  
Impurity Segregation

This is the second of two issues of the MRS BULLETIN on interface materials and is entirely devoted to their mechanical and high-temperature behavior. Mechanical properties provide a rich area for investigating the effect of the local inhomogeneities near the interfaces, and their effect on the interrelation between the structure and chemistry on one hand, and the elastic and fracture behavior on the other.Based on much experimental work on grain-boundary fracture it seems that, with the exception of “beneficial” segregants, the embrittlement potential of most impurities is governed by their propensity for segregation to the grain boundaries, which in turn is strongly influenced by the energies of the pure boundaries. To investigate the role of the grain-boundary structure in its fracture behavior, one must therefore consider the correlations between (1) the structure (i.e., the five macroscopic degrees of freedom) and the energy of pure grain boundaries, (2) impurity segregation and the grain boundary energy, (3) structure, impurity segregation and elastic response at the interface, and finally (4) the correlation between embrittlement and segregation. In addition, the mobility of dislocations near a crack tip also plays an important role. Unfortunately, relatively little knowledge has been accumulated on most of these complex interrelations even though their unraveling is widely recognized as the ultimate goal.

Dopant-concentration dependence of grain-boundary conductivity in ceria: A space-charge analysis

2009 ◽  
Vol 19 (27) ◽  
pp. 4837 ◽  
Author(s):  
Hugo J. Avila-Paredes ◽  
Kwanghoon Choi ◽  
Chien-Ting Chen ◽  
Sangtae Kim
Keyword(s):  
Grain Boundary ◽  
Space Charge ◽  
Concentration Dependence ◽  
Dopant Concentration ◽  
Boundary Conductivity ◽  
Charge Analysis

Nanostructure, Nanochemistry and Grain Boundary Conductivity of Yttria-Doped Zirconia

2005 ◽  
Vol 106 ◽  
pp. 83-86
Author(s):  
A. Rizea ◽  
Jean Marc Raulot ◽  
C. Petot ◽  
Georgette Petot-Ervas ◽  
Gianguido Baldinozzi
Keyword(s):  
Grain Boundary ◽  
Beneficial Effect ◽  
Grain Boundaries ◽  
Strong Interaction ◽  
Glassy Phase ◽  
Yttria Stabilized Zirconia ◽  
Stabilized Zirconia ◽  
Boundary Conductivity ◽  
Comprehensive Study

This work was directed at a comprehensive study of the role of the nanostructure and nanochemistry on the transport properties of yttria-stabilized zirconia. Alumina additions lead to a decrease of sgb when the samples have clean grain boundaries, while sgb goes through a maximum in samples having glassy grain boundaries. The differences were attributed to the strong interaction between Al2O3 and SiO2 impurities leading to a glassy phase depletion at the grain-boundaries, due to a change in wettability. Moreover, XPS analyses show that Si and Y segregate near these interfaces according to a kinetic demixing process, explaining why a faster cooling rate after sintering has a beneficial effect on sgb.

Intergranular Fatigue Cracking Enhanced by Impurity Segregation

2007 ◽  
Vol 539-543 ◽  
pp. 2137-2142 ◽  
Author(s):  
Claire Daniel ◽  
Frédéric Christien ◽  
René Le Gall
Keyword(s):  
Electron Microscopy ◽  
Scanning Electron Microscopy ◽  
Grain Boundary ◽  
Grain Boundaries ◽  
Fatigue Cracking ◽  
Cold Drawing ◽  
High Concentration ◽  
Impurity Segregation ◽  
High Level ◽  
Scanning Electron

It was previously reported that fatigue life of some alloys can be dramatically reduced if the grain boundaries contain a high level of impurity segregation before fatigue tests. In this paper the susceptibility of single phase brass samples (90Cu10Zn) to this form of damage is studied. After cold drawing of as cast brass bars, fatigue samples were heat treated at 800°C during 30min to promote recrystallization and impurity segregation at grain boundary. The samples were then tested under high frequency bending fatigue test at 200°C. After cracking, fracture surfaces were studied using both scanning electron microscopy (SEM) and electron probe microanalysis (EPMA). The SEM micrographs showed that the fractures were mostly intergranular. Chemical composition of intergranular cracks surface were analyzed using EPMA at low accelerating voltage. A high concentration of sulfur was found on most of grain boundary facets. The internal stress in alloys after fatigue was qualitatively estimated using electron backscattering diffraction in scanning electron microscopy. A high level of local misorientation was found near most grain boundaries. The mechanism of intergranular cracks formation during fatigue is discussed taking into account both the segregation of sulfur at grain boundaries and accumulation of plastic strain at grain boundaries

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