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2020 | OriginalPaper | Buchkapitel

7. Diffusion in Ionic Solids

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Abstract

In charged particles systems or ionic solids, diffusion is always accompanied by charge transfer, thus leading to electrochemical phenomena depending on the nature of electrodes. We will learn how to describe mass/charge transport phenomena in terms of mobile charged components with actual charges and in terms of mobile structure elements with effective charges and the resulting electrical properties, ionic and electronic conductivities. There arises flux coupling to keep the local charge neutrality, which results in another type of chemical diffusivity called the Nernst-Planck type, in comparison with the Darken-type earlier in Chap. 4. The self-diffusivities are discussed on the basis of the equilibrium defect structure of a given system as well as the chemical or ambipolar diffusion in concentration gradients and nonstoichiometry re-equilibration kinetics in terms of the Nernst-Planck-type chemical diffusivity.

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Fußnoten
1
Typical changes are microstructural changes including grain growth and densification if polycrystalline and crystal shift or phase decomposition depending on the nature of the electrodes; see Yoo and Lee [1].
 
2
C. Wagner [3]. (For the English translation of the main part of this pioneering work, see Appendix II at the end of this book.)
 
3
Here, ionic defects are denoted in the Kröger-Vink system of notation, \( {\mathrm{S}}_{\mathrm{L}}^{\mathrm{C}} \), meaning the species “S” sitting on the site or locus “L” with an effective charge “C.” The effective charge of a point defect is defined as the actual charge of the species S less the actual charge that would be at the site L in perfect ionic crystal and represented by the corresponding number of dots (•) if positive, by primes (′) if negative, and by a cross (x) if neutral. For more detailed treatment, see Appendix I: “Defect Chemistry of Solid State Ionic Compounds.”
 
4
Equation (7.21) is only a limiting case in agreement with Kohlrausch’s law of independent migration of charge carriers. In reality, however, the charge carriers interfere with each other upon their transfer, and hence, the general flux equation should be written as
$$ {\mathrm{J}}_{\mathrm{k}}=-\sum \limits_{\mathrm{m}}{\mathrm{L}}_{\mathrm{k}\mathrm{m}}\nabla {\upeta}_{\mathrm{m}} $$
where m runs for all mobile charged components and the transport coefficients Lkm satisfy the Onsager reciprocity or
$$ {\mathrm{L}}_{\mathrm{km}}={\mathrm{L}}_{\mathrm{mk}}. $$
For a system with one type of mobile ionic carriers (k = i) and electrons (k = e), the experimental method to determine the three independent Onsager coefficients (Lii, Lie=Lei, Lee) is well established and experimentally practiced upon some mixed conductor systems. It is noted that the ion-electron interference coefficient Lie (=Lei) is by no means negligible depending on carrier concentrations, contrary to the conventional, Kohlrausch’s law of independent migration. The interested reader may refer to the reports:
1.
D.-K. Lee and H.-I. Yoo, “Electron-ion interference and Onsager reciprocity in mixed ionic-electronic transport in TiO2,” Phys. Rev. Lett., 97 (2006) 255901.
 
2.
T. Lee, H.-S. Kim and H.-I. Yoo, “From Onsager to mixed ionic electronic conductors,” Solid State Ion., 262 (2014) 2.
 
 
5
For a succinct treatment of defect chemistry, see Appendix I, “Defect Chemistry of Solid State Ionic Compounds,” at the end of this book.
 
6
For more detailed treatment, see Appendix I, Defect Chemistry of Solid State Ionic Compounds, at the end of this book.
 
7
The numerical solution is straightforward with a bit coding, but the Brouwer method allows us to quickly get analytical insights.
 
8
This is a special case of the general charge neutrality condition ∇i = 0. For an extensive detailed treatment, see Lee and Yoo [10].
 
9
For the analytic solutions, see Crank [11], and for experimental practices, see, e.g., Song and Yoo [12].
 
Literatur
2.
Zurück zum Zitat M. Faraday, Experimental Researches in Electricity Art (Taylor and Francis, London, 1839), p. 1339, quoted from K. Funke, Sci. Technol. Adv. Mater. 14, 043502 (2013) M. Faraday, Experimental Researches in Electricity Art (Taylor and Francis, London, 1839), p. 1339, quoted from K. Funke, Sci. Technol. Adv. Mater. 14, 043502 (2013)
3.
Zurück zum Zitat C. Wagner, Z. Phys. Chem. B21, 25 (1933) C. Wagner, Z. Phys. Chem. B21, 25 (1933)
4.
Zurück zum Zitat G. Brouwer, A general asymptotic solution of reaction equations common in solid-state chemistry. Philips Res. Rep. 9, 366–376 (1954) G. Brouwer, A general asymptotic solution of reaction equations common in solid-state chemistry. Philips Res. Rep. 9, 366–376 (1954)
5.
Zurück zum Zitat Y.-M. Chiang, D. Birnie III, W.D. Kingery, Physical Ceramics (John Wiley & Sons, Inc., New York, 1997), p. 202 Y.-M. Chiang, D. Birnie III, W.D. Kingery, Physical Ceramics (John Wiley & Sons, Inc., New York, 1997), p. 202
6.
Zurück zum Zitat D. Mapother, H.N. Crooks, R. Maurer, Self-diffusion of sodium in sodium chloride and sodium bromide. J. Chem. Phys. 18, 1231 (1950)CrossRef D. Mapother, H.N. Crooks, R. Maurer, Self-diffusion of sodium in sodium chloride and sodium bromide. J. Chem. Phys. 18, 1231 (1950)CrossRef
8.
Zurück zum Zitat H. Schmalzried, Solid State Reactions (Verlag Chemie, Weinheim, 1981), p. 175 H. Schmalzried, Solid State Reactions (Verlag Chemie, Weinheim, 1981), p. 175
9.
Zurück zum Zitat R. Dieckmann, H. Schmalzried, Ber. Bunsenges. Phys. Chem. 81, 344–347 (1977)CrossRef R. Dieckmann, H. Schmalzried, Ber. Bunsenges. Phys. Chem. 81, 344–347 (1977)CrossRef
10.
11.
Zurück zum Zitat J. Crank, The Mathematics of Diffusion, 2nd edn. (Clarendon Press, Oxford, 1975), p. 60 J. Crank, The Mathematics of Diffusion, 2nd edn. (Clarendon Press, Oxford, 1975), p. 60
12.
Metadaten
Titel
Diffusion in Ionic Solids
verfasst von
Han-Ill Yoo
Copyright-Jahr
2020
DOI
https://doi.org/10.1007/978-3-030-25950-1_7

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