Hydrogen Absorption into and Subsequent Diffusion Through Hydride-Forming Metals

  • Su-Il Pyun
  • Heon-Cheol Shin
  • Jong-Won Lee
  • Joo-Young Go
Chapter
Part of the Monographs in Electrochemistry book series (MOEC)

Abstract

In most theoretical and experimental investigations, it has been assumed that the rate-determining step (RDS) of hydrogen insertion (intercalation, ingress, cathodic charging/injection/introduction) into and desertion (deintercalation, egress, anodic extraction) from hydride-forming electrodes is hydrogen diffusion through the electrode. In practice, however, the rate of hydrogen insertion into and desertion from the electrode is simultaneously determined by the rates of two or more reaction steps, such as hydrogen ion transport through the electrolyte by diffusion and migration (ohmic potential drop), interfacial charge (electron) transfer (cathodic discharge of hydrogen ions), interfacial hydrogen transfer, and subsequent hydrogen diffusion through the electrode [1]. The RDS of the series-connected overall hydrogen insertion reaction is defined as the most strongly impeded/disturbed “slowest” step deviating far from its thermodynamic equilibrium state that represents the highest hydrogen overpotential and/or impedance pertaining to the step. In this respect, the mechanism of hydrogen insertion into and from a hydride-forming electrode has been extensively studied.

Keywords

Hydrogen Diffusion Hydrogen Evolution Reaction Transmission Line Model Subsequent Diffusion Entry Side 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

References

  1. 1.
    Lee SJ, Pyun SI, Yoon YG (2011) Pathways of diffusion mixed with subsequent reactions with examples of hydrogen extraction from hydride-forming electrode and oxygen reduction at gas diffusion electrode. J Solid State Electrochem 15:2437–2445CrossRefGoogle Scholar
  2. 2.
    Bolzan AE (1995) Phenomenological aspects related to the electrochemical behaviour of smooth palladium electrodes in alkaline solutions. J Electroanal Chem 380:127–138CrossRefGoogle Scholar
  3. 3.
    Deng B, Li Y, Wang R, Fang S (1999) Two reduction processes for hydrogen adsorption and absorption at MmNi5-type alloy electrodes (Mm: “Mischmetall”). Electrochim Acta 44:2853–2857CrossRefGoogle Scholar
  4. 4.
    Han JN, Lee JW, Seo M, Pyun SI (2001) Analysis of stresses generated during hydrogen transport through a Pd foil electrode under potential sweep conditions. J Electroanal Chem 506:1–10CrossRefGoogle Scholar
  5. 5.
    Gamboa SA, Sebastian PJ, Feng F, Geng M, Northwood DO (2002) Cyclic voltametry investigation of a metal hydride electrode for nickel metal hydride batteries. J Electrochem Soc 149:A137–A139CrossRefGoogle Scholar
  6. 6.
    Lim C, Pyun SI (1993) Theoretical approach to Faradaic admittance of hydrogen absorption reaction on metal membrane electrode. Electrochim Acta 38:2645–2652CrossRefGoogle Scholar
  7. 7.
    Lim C, Pyun SI (1994) Impedance analysis of hydrogen absorption reaction on Pd membrane electrode in 0.1 M LiOH solution under permeable boundary conditions. Electrochim Acta 39:363–373CrossRefGoogle Scholar
  8. 8.
    Zhang W, Sridhar Kumar MP, Srinivasan S, Ploehn HJ (1995) Ac impedance studies on metal hydride electrodes. J Electrochem Soc 142:2935–2943CrossRefGoogle Scholar
  9. 9.
    Yang TH, Pyun SI (1996) Hydrogen absorption into and diffusion in palladium: ac-impedance analysis under impermeable boundary conditions. Electrochim Acta 41:843–848CrossRefGoogle Scholar
  10. 10.
    Yang TH, Pyun SI (1996) An investigation of the hydrogen absorption reaction into and the hydrogen evolution reaction from a Pd foil electrode. J Electroanal Chem 414:127–133CrossRefGoogle Scholar
  11. 11.
    Yang TH, Pyun SI (1996) A study of the hydrogen absorption reaction into α- and β-LaNi5Hx porous electrodes by using electrochemical impedance spectroscopy. J Power Sources 62:175–178CrossRefGoogle Scholar
  12. 12.
    Wang C (1998) Kinetic behavior of metal hydride electrode by means of ac impedance. J Electrochem Soc 145:1801–1812CrossRefGoogle Scholar
  13. 13.
    Montella C (1999) Review and theoretical analysis of ac–av methods for the investigation of hydrogen insertion I. Diffusion formalism. J Electroanal Chem 462:73–87CrossRefGoogle Scholar
  14. 14.
    Montella C (2000) Review and theoretical analysis of ac–av methods for the investigation of hydrogen insertion: Part II. Entry side impedance, transfer function and transfer impedance formalism. J Electroanal Chem 480:150–165CrossRefGoogle Scholar
  15. 15.
    Montella C (2000) Review and theoretical analysis of ac–av methods for the investigation of hydrogen insertion: Part III. Comparison of entry side impedance, transfer function and transfer impedance methods. J Electroanal Chem 480:166–185CrossRefGoogle Scholar
  16. 16.
    Yuan X, Xu N (2002) Electrochemical and hydrogen transport kinetic performance of MINi3.75Co0.65Mn0.4Al0.2 (Ml denotes La-rich mischmetal being composed of La 61.11 wt %, Ce 27.16 wt %, Pr 3.09 wt %, and Nd 8.64 wt %) metal hydride electrodes at various temperatures. J Electrochem Soc 149:A407–A413CrossRefGoogle Scholar
  17. 17.
    Georén P, Hjelm AK, Lindbergh G, Lundqvist A (2003) An electrochemical impedance spectroscopy method applied to porous LiMn2O4 and metal hydride battery electrodes. J Electrochem Soc 150:A234–A241CrossRefGoogle Scholar
  18. 18.
    Haran BS, Popov BN, White RE (1998) Theoretical analysis of metal hydride electrodes- studies on equilibrium potential and exchange current density. J Electrochem Soc 145:4082–4090CrossRefGoogle Scholar
  19. 19.
    Feng F, Ping X, Zhou Z, Geng M, Han J, Northwood DO (1998) The relationship between equilibrium potential during discharge and hydrogen concentration in a metal hydride electrode. Int J Hydrogen Energy 23:599–602CrossRefGoogle Scholar
  20. 20.
    Conway BE, Wojtowicz J (1992) Time-scales of electrochemical desorption and sorption of H in relation to dimensions and geometries of host metal hydride electrodes. J Electroanal Chem 326:277–297CrossRefGoogle Scholar
  21. 21.
    Ura H, Nishina T, Uchida I (1995) Electrochemical measurements of single particles of Pd and LaNi5 with a microelectrode technique. J Electroanal Chem 396:169–173CrossRefGoogle Scholar
  22. 22.
    Nishina T, Ura H, Uchida I (1997) Determination of chemical diffusion coefficients in metal hydride particles with a microelectrode technique. J Electrochem Soc 144:1273–1277CrossRefGoogle Scholar
  23. 23.
    Kim HS, Nishizawa M, Uchida I (1999) Single particle electrochemistry for hydrogen storage alloys, MmNi3.55Co0.75Mn0.4Al0.3 (Mm: “Mischmetall”). Electrochim Acta 45:483–488CrossRefGoogle Scholar
  24. 24.
    Feng F, Han J, Geng M, Northwood DO (2000) Study of hydrogen transport in metal hydride electrodes using a novel electrochemical method. J Electroanal Chem 487:111–119CrossRefGoogle Scholar
  25. 25.
    Yuan X, Xu N (2001) Comparative study on electrochemical techniques for determination of hydrogen diffusion coefficients in metal hydride electrodes. J Appl Electrochem 31:1033–1039CrossRefGoogle Scholar
  26. 26.
    Kim HS, Itoh T, Nishizawa M, Mohamedi M, Umeda M, Uchida I (2002) Microvoltammetric study of electrochemical properties of a single spherical nickel hydroxide particle. Int J Hydrogen Energy 27:295–300CrossRefGoogle Scholar
  27. 27.
    Lee JW, Pyun SI (2005) Anomalous behaviour in diffusion impedance of intercalation electrodes. Z Metallkd 96:117–123Google Scholar
  28. 28.
    Lee JW, Pyun SI (2005) Anomalous behaviour of hydrogen extraction from hydride-forming metals and alloys under impermeable boundary conditions. Electrochim Acta 50:1777–1805CrossRefGoogle Scholar
  29. 29.
    Boes N, Züchner H (1976) Electrochemical methods for studying diffusion, permeation and solubility of hydrogen in metals. J Less-Common Met 49:223–240CrossRefGoogle Scholar
  30. 30.
    Subramanyan PK (1981) Electrochemical aspects of hydrogen in metals. In: Bockris JO’M, Conway BE, Yeager E, White RE (eds) Comprehensive treatise of electrochemistry, vol 4. Electrochemical materials science. Plenum, New York, p 411Google Scholar
  31. 31.
    Fullenwider MA (1983) Hydrogen entry and action in metals. Pergamon, New York, p 4Google Scholar
  32. 32.
    Pound BG (1993)  Chapter 2 Electrochemical techniques to study hydrogen ingress in metals. In: Bockris JO’M, Conway BE, Yeager E, White RE (eds) Modern aspects of electrochemistry, vol 25. Plenum, New York, p 63CrossRefGoogle Scholar
  33. 33.
    Devanathan MAV, Stachurski Z (1962) The absorption and diffusion of electrolytic hydrogen in palladium. Proc R Soc Lond A 270:90–102CrossRefGoogle Scholar
  34. 34.
    McBreen J, Nanis L, Beck W (1966) A method for determination of the permeation rate of hydrogen through metal membranes. J Electrochem Soc 113:1218–1222CrossRefGoogle Scholar
  35. 35.
    Nanis L, Govindan Namboodhiri TK (1972) Mathematics of the electrochemical extraction of hydrogen from iron. J Electrochem Soc 119:691–694CrossRefGoogle Scholar
  36. 36.
    Early JG (1978) Hydrogen diffusion in palladium by galvanostatic charging. Acta Metall 26:1215–1223CrossRefGoogle Scholar
  37. 37.
    Bockris JO’M, Genshaw MA, Fullenwider M (1970) The electro-permeation of hydrogen into metals. Electrochim Acta 15:47–60CrossRefGoogle Scholar
  38. 38.
    Kirchheim R, McLellan RB (1980) Electrochemical methods for measuring diffusivities of hydrogen in palladium and palladium alloys. J Electrochem Soc 127:2419–2425CrossRefGoogle Scholar
  39. 39.
    Pyun SI, Lee WJ, Yang TH (1997) Hydrogen diffusion through palladium-gold alloy coatings electrodeposited on palladium substrate under permeable boundary condition. Thin Solid Films 311:183–189CrossRefGoogle Scholar
  40. 40.
    Lee WJ, Pyun SI, Yang TH, Kim JD, Baek YH, Kim HG (1997) Hydrogen transport through Pd-Ni alloy electrodeposited on Pd substrate. J Solid State Electrochem 1:120–125CrossRefGoogle Scholar
  41. 41.
    Pyun SI (2007) Outlines of electrochemistry at materials. Chung-Moon-Gak Book Publishing, Seoul, pp 293, 330, 359, 610, 830, 835; Kim JS, Pyun SI (2011) Comparison of transmissive permeable and reflective impermeable interfaces between electrode and electrolyte. J Solid State Electrochem 15:2447–2452Google Scholar
  42. 42.
    Harrington DA, Conway BE (1987) Ac impedance of Faradaic reactions involving electrosorbed intermediates – I. Kinetic theory. Electrochim Acta 32:1703–1712CrossRefGoogle Scholar
  43. 43.
    Raistrick ID (1990) Impedance studies of porous electrodes. Electrochim Acta 35:1579–1586CrossRefGoogle Scholar
  44. 44.
    Bisquert J, Garcia-Belmonte G, Bueno P, Longo E, Bulhoes LOS (1998) Impedance of constant phase element (CPE)-blocked diffusion in film electrodes. J Electroanal Chem 452:229–234CrossRefGoogle Scholar
  45. 45.
    Bisquert J (2000) Influence of the boundaries in the impedance of porous film electrodes. Phys Chem Chem Phys 2:4185–4192CrossRefGoogle Scholar
  46. 46.
    Bisquert J, Compte A (2001) Theory of the electrochemical impedance of anomalous diffusion. J Electroanal Chem 499:112–120CrossRefGoogle Scholar
  47. 47.
    Jamnik J, Maier J (2001) Generalised equivalent circuits for mass and charge transport: chemical capacitance and its implications. Phys Chem Chem Phys 3:1668–1678CrossRefGoogle Scholar
  48. 48.
    Bisquert J (2002) Analysis of the kinetics of ion intercalation: ion trapping approach to solid-state relaxation processes. Electrochim Acta 47:2435–2449CrossRefGoogle Scholar
  49. 49.
    Bisquert J, Vikhrenko VS (2002) Analysis of the kinetics of ion intercalation. Two state model describing the coupling of solid state ion diffusion and ion binding processes. Electrochim Acta 47:3977–3988CrossRefGoogle Scholar
  50. 50.
    Bisquert J, Garcia-Belmonte G, Pitarch A (2003) An explanation of anomalous diffusion patterns observed in electroactive materials by impedance methods. A European J ChemPhysChem 4:287–292CrossRefGoogle Scholar
  51. 51.
    Boukamp BA (2004) Electrochemical impedance spectroscopy in solid state ionics: recent advances. Solid State Ionics 169:65–73CrossRefGoogle Scholar
  52. 52.
    Barsoukov E, Macdonald JR (2005) Impedance spectroscopy. Wiley, New York, pp 16, 54CrossRefGoogle Scholar
  53. 53.
    Crank J (1975) The mathematics of diffusion. Clarendon, Oxford, p 11Google Scholar
  54. 54.
    Kim JS, Pyun SI (2008) Theoretical and experimental approaches to oxygen reduction at porous composite electrodes for fuel cells by analyses of ac-impedance spectra and potentiostatic current transients. Isr J Chem 48:277–286CrossRefGoogle Scholar
  55. 55.
    Ho C, Raistrick ID, Huggins RA (1980) Application of a-c techniques to the study of lithium diffusion in tungsten trioxide thin films. J Electrochem Soc 127:343–350CrossRefGoogle Scholar
  56. 56.
    Jacobsen T, West K (1995) Diffusion impedance in planar, cylindrical and spherical symmetry. Electrochim Acta 40:255–262CrossRefGoogle Scholar
  57. 57.
    Ding S, Petuskey WT (1998) Solutions to Fick’s second law of diffusion with a sinusoidal excitation. Solid State Ionics 109:101–110CrossRefGoogle Scholar
  58. 58.
    Pitarch A, Garcia-Belmonte G, Mora-Sero I, Bisquert J (2004) Electrochemical impedance spectra for the complete equivalent circuit of diffusion and reaction under steady-state recombination current. Phys Chem Chem Phys 6:2983–2988CrossRefGoogle Scholar
  59. 59.
    Bockris JO’M, McBreen J, Nanis L (1965) The hydrogen evolution kinetics and hydrogen entry into α-iron. J Electrochem Soc 112:1025–1031CrossRefGoogle Scholar
  60. 60.
    Kim CD, Wilde BE (1971) The kinetics of hydrogen absorption into iron during cathodic hydrogen evolution. J Electrochem Soc 118:202–206CrossRefGoogle Scholar
  61. 61.
    Iyer RN, Pickering HW, Zamanzadeh M (1989) Analysis of hydrogen evolution and entry into metals for the discharge-recombination process. J Electrochem Soc 136:2463–2470CrossRefGoogle Scholar
  62. 62.
    Bockris JO’M (1954) Chapter 4 Electrode kinetics. In: Bockris JO’M (ed) Modern aspects of electrochemistry, vol 1. Butterworths Scientific Publications, London, p 180Google Scholar
  63. 63.
    Enyo M, Maoka T (1980) The overpotential components on the palladium hydrogen electrode. J Electroanal Chem 108:277–292CrossRefGoogle Scholar
  64. 64.
    Cabanel R, Barral G, Diard JP, Le Gorrec B, Montella C (1993) Determination of the diffusion-coefficient of an inserted species by impedance spectroscopy- application to the H/HXNb2O5 system. J Appl Electrochem 23:93–97CrossRefGoogle Scholar
  65. 65.
    Armstrong RD, Henderson M (1972) Impedance plane display of a reaction with an adsorbed intermediate. J Electroanal Chem 39:81–90CrossRefGoogle Scholar
  66. 66.
    Bagotskaya IA (1962) Effect of the solution composition on the diffusion rate of electrolytic hydrogen through metallic diaphragms. I. Diffusion of hydrogen through iron diaphragms. Zhur Fiz Khim 36:2667–2673Google Scholar
  67. 67.
    Frumkin AN (1963)  Chapter 5 Hydrogen overvoltage and adsorption phenomena part II. In: Delahay P (ed) Advances in electrochemistry and electrochemical engineering, vol 3. Interscience, New York, p 375Google Scholar
  68. 68.
    Franceschetti DR, Macdonald JR, Buck RP (1991) Interpretation of finite-length-Warburg-type impedances in supported and unsupported electrochemical cells with kinetically reversible electrodes. J Electrochem Soc 138:1368–1371CrossRefGoogle Scholar
  69. 69.
    Breger V, Gileadi E (1971) Adsorption and absorption of hydrogen in palladium. Electrochim Acta 16:177–190CrossRefGoogle Scholar
  70. 70.
    Lee JW, Pyun SI, Filipeck S (2003) The kinetics of hydrogen transport through amorphous Pd82–yNiySi18alloys (y = 0 − 32) by analysis of anodic current transient. Electrochim Acta 48:1603–1611CrossRefGoogle Scholar
  71. 71.
    Han JN, Pyun SI, Yang TH (1997) Roles of thiourea as an inhibitor in hydrogen absorption into palladium electrode. J Electrochem Soc 144:4266–4272CrossRefGoogle Scholar
  72. 72.
    Lasia A (2002)  Chapter 1 Application of electrochemical impedance spectroscopy to hydrogen adsorption, evolution and absorption into metals. In: Conway BE, White RE (eds) Modern aspects of electrochemistry, vol 35. Kluwer/Plenum, New York, p 1CrossRefGoogle Scholar
  73. 73.
    Reichman B, Bard AJ, Laser D (1980) A digital simulation model for electrochromic processes at WO3 electrodes. J Electrochem Soc 127:647–654CrossRefGoogle Scholar
  74. 74.
    Yayama H, Kuroki K, Hirakawa K, Tomokiyo A (1984) Electrode resistance of metal hydride in alkaline aqueous solution. Jpn J Appl Phys 23:1619–1623CrossRefGoogle Scholar
  75. 75.
    Brug GJ, van der Eeden ALG, Sluyters-Rehbach M, Sluyters JH (1984) The analysis of electrode impedances complicated by the presence of a constant phase element. J Electroanal Chem 176:275–295CrossRefGoogle Scholar
  76. 76.
    Macdonald JR, Schoonman J, Lehner AP (1982) Applicability and power of complex nonlinear least squares for the analysis of impedance and admittance data. J Electroanal Chem 131:77–95CrossRefGoogle Scholar
  77. 77.
    Bae JS, Pyun SI (1994) An ac impedance study of LiI–Al2O3 composite solid electrolyte. J Mater Sci Lett 13:573–576CrossRefGoogle Scholar
  78. 78.
    Bai L, Harrington DA, Conway BE (1987) Behavior of overpotential-deposited species in Faradaic reactions – II. ac Impedance measurements on H2 evolution kinetics at activated and unactivated Pt cathodes. Electrochim Acta 32:1713–1731CrossRefGoogle Scholar
  79. 79.
    Ekdunge P, Jüttner K, Kreysa G, Kessler T, Ebert M, Lorenz WJ (1991) Electrochemical impedance study on the kinetics of hydrogen evolution at amorphous metals in alkaline solution. J Electrochem Soc 138:2660–2668CrossRefGoogle Scholar
  80. 80.
    Lee SK, Pyun SI, Lee SJ, Jung KN (2007) Mechanism transition of mixed diffusion and charge transfer-controlled to diffusion-controlled oxygen reduction at Pt-dispersed carbon electrode by Pt-loading, nafion content and temperature. Electrochim Acta, 53: 740–751.CrossRefGoogle Scholar
  81. 81.
    Lee SJ, Pyun SI (2010) Kinetics of mixed-controlled oxygen reduction at nafion-impregnated Pt-alloy-dispersed carbon electrode by analysis of cathodic current transients. J Solid State Electrochem 14:775–786.CrossRefGoogle Scholar
  82. 82.
    Lasia A (2006) On the mechanism of the hydrogen absorption reaction. J Electroanal Chem 593:159–166.CrossRefGoogle Scholar
  83. 83.
    Birry L, Lasia A (2006) Effect of crystal violet on the kinetics of H sorption into Pd. Electrochim Acta 51: 3356–3364.CrossRefGoogle Scholar
  84. 84.
    Pyun SI (2007) The fundamentals of corrosion of metals and their application into practice. Chung-Moon-Gak Book Publishing, Seoul, p 566Google Scholar
  85. 85.
    Lee SJ, Pyun SI, Lee JW (2005) Investigation of hydrogen transport through Mm (Ni3.6Co0.7Mn0.4Al0.3)1.12 (Mm denotes a “Mischmetall”) and Zr0.65Ti0.35Ni1.2V0.4Mn0.4 hydride electrodes by analysis of anodic current transient. Electrochim Acta 50:1121–1130CrossRefGoogle Scholar
  86. 86.
    Pourbaix M (1974) Chapter 4 Establishment and interpretation of potential-pH equilibrium diagrams on Pd. In: Franklin JA (translated from the French) Atlas of electrochemical equilibria in aqueous solutions, 2nd edn. National Association of Corrosion Engineers, Houston, p 358Google Scholar
  87. 87.
    Bucur RV (1985) The influence of experimental conditions upon the measurements of hydrogen diffusion in palladium by electrochemical methods. Z Phys Chem NF 146:217–229CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2012

Authors and Affiliations

  • Su-Il Pyun
    • 1
  • Heon-Cheol Shin
    • 2
  • Jong-Won Lee
    • 3
  • Joo-Young Go
    • 4
  1. 1.Dept. Materials Science & Eng. Korea Adv. Inst. of Science and Techn.Jeju National UniversityDaejeonRepublic of Korea
  2. 2.School of Materials Science & Eng.Pusan National Univ.Busan, Geumjeong-guRepublic of Korea
  3. 3.Fuel Cell Research CenterKorea Inst. of Energy ResearchDaejonRepublic of Korea
  4. 4.SB LiMotive Co., LtdGyeonggi-doRepublic of Korea

Personalised recommendations