Browse > Article
http://dx.doi.org/10.5229/JKES.2009.12.1.001

Transport Behaviour of Electroactive Species in Ionic Compounds: A Focus on Li Diffusion through Transition Metal Oxide in Current Flowing Condition  

Lee, Sung-Jai (Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology)
Pyun, Su-Il (Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology)
Publication Information
Journal of the Korean Electrochemical Society / v.12, no.1, 2009 , pp. 1-10 More about this Journal
Abstract
This article reviewed transport behaviours of electroactive species in ionic compounds, focusing on chemical diffusion of Li through the transition metal oxide in a current flowing condition. For this purpose, a distinction has been first briefly made between migration and diffusion with respect to current, driving force and charge of electroactive species considered. Then, the equations for chemical diffusion are derived theoretically in open-circuit and current flowing conditions. Finally, the experimental methods such as ac impedance spectroscopy and current (potential) transient techniques are described in details for characterising chemical diffusion. In addition, the role of the thermodynamic enhancement factor in chemical diffusion is discussed.
Keywords
Chemical diffusion; Ionic compound; Chemical diffusivity; Current flowing condition; Thermodynamic enhancement factor;
Citations & Related Records
연도 인용수 순위
  • Reference
1 J. -S. Bae and S. -I. Pyun, 'Electrochemical lithium intercalation reaction of anodic vanadium oxide film', J. Alloys & Comp., 217, 52 (1995)   DOI   ScienceOn
2 Y. -M. Choi, S. -I. Pyun, J. -S. Bae, and S. -I. Moon, 'Effects of lithium content on the electrochemical lithium intercalation reaction into $LiNiO_{2}$ and $LiNiO_{2}$ electrodes', J. Power Sources, 56, 25 (1995)   DOI   ScienceOn
3 Y. -M. Choi and S. -I. Pyun, 'Determination of electrochemical active area of porous $Li_{1-\delta}CoO_{2}$ electrode using the GITT technique', Solid State Ionics, 109, 159 (1998)   DOI   ScienceOn
4 S. -W. Kim and S. -I. Pyun, 'Thermodynamic and kinetic approaches to lithium intercalation into a $Li_{1-\delta}Mn_{2}O_{4}$ electrode using Monte Carlo simulation', Electrochim. Acta, 46, 987 (2001)   DOI   ScienceOn
5 J. -S. Bae and S. -I. Pyun, 'Electrochemical lithium intercalation into and deintercalation from vanadium oxide electrode by using potentiostatic current transient technique', Solid State Ionics, 90, 251 (1996)   DOI   ScienceOn
6 S. -I. Pyun and Y. -M. Choi, 'Electrochemical lithium intercalation into and de-intercalation from porous $LiCoO_{2}$ electrode by using potentiostatic current transient technique', J. Power Sources, 68, 524 (1997)   DOI   ScienceOn
7 Y. -M. Choi, S. -I. Pyun, S. -I. Moon, and Y. -E. Hyung, 'A study of the electrochemical lithium intercalation behavior of porous $LiNiO_{2}$ electrodes by solid-state reaction and sol-gel methods', J. Power Sources, 72, 83 (1998)   DOI   ScienceOn
8 R. J. Chater, S. Carter, J. A. Kilner, and B. C. H. Steele, 'Development of a novel SIMS technique for oxygen self-diffusion and surface exchange coefficient measurements in oxides of high diffusivity', Solid State Ionics, 53-56, 859 (1992)   DOI   ScienceOn
9 S. -J. Lee, S. -I. Pyun, and H. -C. Shin, 'Chemical diffusion of electroactive species in ionic compounds: a focus on chemical equilibrium constraint', J. Solid State Electrochem., in press (2009)
10 T. -W. Tang, T. O. Regan, and B. Wu, 'Thomas-Fermi approximation for a two-dimensional electron gas at low temperatures', J. Appl. Phys., 95, 7990 (2004)   DOI   ScienceOn
11 D. N. Quang, L. Tuan, and N.T. Tien, 'Electron mobility in Gaussian heavily doped ZnO surface quantum wells', Phys. Rev. B, 77, 125326 (2008)   DOI   ScienceOn
12 Y.-M. Choi, S.-I. Pyun and S.-I. Moon, 'Effects of cation mixing on the electrochemical lithium intercalation reaction into porous $Li_{1-d}Ni_{1-y}Co_{y}O_{2}$ electrodes', Solid State Ionics, 89, 43 (1996)   DOI   ScienceOn
13 S. -I. Pyun, Y. -M. Choi, and I. -D. Jeng, 'Effect of the lithium content on electrochemical lithium intercalation into amorphous and crystalline powdered $Li_{1{\pm}\delta}Mn_{2}O_{4}$ electrodes prepared by sol-gel method', J. Power Sources, 68, 593 (1997)   DOI   ScienceOn
14 J. -S. Kim, S. -I. Pyun, J. -W. Lee, and R. -H. Song, 'Kinetics of oxygen reduction on porous mixed conducting $(La_{0.85}Sr_{0.15})_{0.9}$$MnO_{3}$ electrode by ac-impedance analysis', J. Solid State Electrochem., 11, 117 (2007)   DOI   ScienceOn
15 S. -I. Pyun and J. -S. Bae, 'Electrochemical lithium intercalation into vanadium pentoxide xerogel film electrode', J. Power Sources, 68, 669 (1997)   DOI   ScienceOn
16 H. -C. Shin and S. -I. Pyun, 'Investigation of lithium transport through lithium cobalt dioxide thin film sputter-deposited by analysis of cyclic voltammogram', Electrochim. Acta, 46, 2477 (2001)   DOI   ScienceOn
17 P. -W. Li, L. Schaefer, and M. K. Chyu, 'Multiple transport processes in solid oxide fuel cells' in Transport phenomena in fuel cells, 1-42, ed. B. Sunden and M. Faghri, WIT Press, Boston (2005)
18 J. -S. Kim, and S. -I. Pyun, 'Effects of secondary phase and thickness on mixed controlled oxygen reduction at dense composite electrode', J. Electrochem. Soc., 155, B8 (2008)   DOI
19 J. -S. Kim, S. -I. Pyun, H. -C. Shin, and S. -J. L. Kang, 'Oxygen reduction kinetics at dense $(La_{0.85}Sr_{0.15})_{0.9}$$MnO_{3}$ -YSZ composite electrodes investigated using potentiostatic current transient method', J. Electrochem. Soc., 155, B762 (2008)   DOI   ScienceOn
20 J. -S. Kim and S. -I. Pyun, 'Kinetics of oxygen reduction at composite electrodes with controlled three-phase boundaries by patterning YSZ column', Electrochim. Acta, 54, 952 (2009)   DOI   ScienceOn
21 J. -S. Kim, S. -I. Pyun, and H. -C. Shin, 'Kinetics of cathodic reaction at porous composite electrode under mixed control of migration and oxygen-exchange', J. Electrochem. Soc., submitted for publication (2009)
22 A. J. Bard and L. R. Faulkner, 'Electrochemical methods', 28-35, John Wiley & Sons, New York (1980)
23 A. Kumar, D. Rajdev, and D.L. Douglass, 'Effect of oxide defect structure on the electrical properties of $ZrO_{2}$', J. Amer. Ceram. Soc., 55, 439 (1972)   DOI
24 S. -I. Pyun and Y. -E. Ihm, 'Electrical conduction of partially stabilized zirconia $Zr_{0.94}Ca_{0.06}O_{1.94}$ as a function of temperature and oxygen partial pressure', J. Mat. Sci., 17, 2577 (1982)   DOI
25 T. Z. Fahidy and S. Mohanta, 'Mass transport in electrochemical systems' in Advances in transport processes, 84-92, ed. A.S. Mujumdar and R.A. Mashelkar, John Wiley & Sons, New York (1980)
26 W. Weppner, 'Electrode Performance', in Solid State Electrochemistry, 199-228, ed. P.G. Bruce, Cambridge Univ. Press, Cambridge (1995)
27 S. -I. Pyun, 'What Do We Understand by Chemical and Component Diffusivities of Cation in Mixed Conductor? - Basic Concepts and Electrochemical Techniques to Their Determination at Cathode Materials of Secondary Lithium Battery', J. Corr. Sci. of Korea, 28, 1 (1999)
28 F. A. Kroeger, 'The Chemistry of Imperfect Crystals', 794-813, North-Holland Publishing Company, Amsterdam (1964)
29 S. R. De Groot and P. Mazur, 'Non-Equilibrium Thermodynamics', 238-273, North-Holland Publishing Company, Amsterdam (1969)
30 H. Schmalzried, 'Solid State Reactions', in Monographs in Modern Chemistry, 59-91, ed. H.F. Ebel, Verlag Chemie, Weinheim (1981)
31 H. Schmalzried, 'Chemical Kinetics of Solids', 95-107, VCH Verlagsgesellschaft mbH, Weinheim (1995)
32 W. Van. Gool, 'Principles of defect chemistry of crystalline solids', 13-25, Academic Press, New York (1966)
33 S. Machlup and L. Onsager, 'Fluctuations and Irreversible Processes. II. Systems with Kinetic Energy', Phys. Rev., 91, 1512 (1953)   DOI
34 G. Balducci, J. Kaspar, P. Fornasiero, M. Graziani, M. S. Islam, and J. D. Gale, 'Computer simulation studies of bulk reduction and oxygen migration in $CeO_{2}-ZrO_{2}$ solid solutions', J. Phys. Chem. B, 101, 1705 (1997)   DOI   ScienceOn
35 M. Kilo, R. A. Jackson, and G. Borchardt, 'Computer modelling of ion migration in zirconia', Phil. Mag., 83, 3309 (2003)   DOI   ScienceOn
36 L. Onsager and S. Machlup, 'Fluctuations and Irreversible Processes', Phys. Rev., 91, 1505 (1953)   DOI