In-depth structural understanding of zinc oxide addition to alkaline electrolytes to protect aluminum against corrosion and gassing


Several approaches have been tried to reduce Al corrosion in primary and secondary alkaline batteries. The most successful to date has been the addition of ZnO to the electrolyte, which results in the spontaneous deposition of a protective metallic Zn film on the Al surface. However, there is a limited understanding in the literature of the structure of this Zn film and how that structure (i) influences the protection of Al, and (ii) is influenced by the electrolyte composition. This work aims to develop a fundamental understanding of the protection mechanism against Al corrosion when zincate is added to KOH electrolytes. This was accomplished through morphological studies of the resulting Zn film using SEM, XRD, N2 adsorption, and measurements of H2 gas evolution as well as electrochemical characterization during discharge. It was found that adding saturated ZnO to KOH electrolytes provides the most protective Zn film with good adherence and high density, which can lower the Al corrosion rate by 2 orders of magnitude. Moreover, configurations with a capacity near the Al theoretical capacity were achieved.

Graphic abstract

This is a preview of subscription content, log in to check access.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7


  1. 1.

    Reddy TB (2002) Linden handbook of batteries. McGraw-Hill, New York

    Google Scholar 

  2. 2.

    Chen B, Leung DY, Xuan J, Wang H (2015) A high performance dual electrolyte aluminium–air cell. Energy Procedia 75:1983–1989

    CAS  Article  Google Scholar 

  3. 3.

    Tang Y, Lu L, Roesky HW, Wang L, Huang B (2004) The effect of zinc on the aluminum anode of the aluminum–air battery. J Power Sources 138(1–2):313–318

    CAS  Article  Google Scholar 

  4. 4.

    Zaromb S (1962) The use and behavior of aluminum anodes in alkaline primary batteries. J Electrochem Soc 109(12):1125–1130

    CAS  Article  Google Scholar 

  5. 5.

    Li Q, Bjerrum NJ (2002) Aluminum as anode for energy storage and conversion: a review. J Power Sources 110(1):1–10

    CAS  Article  Google Scholar 

  6. 6.

    Moden JR, Perkons G (1979) Aluminum anode alloy for primary high power density alkaline fuel cells and batteries. Google Patents

  7. 7.

    Sarangapani K, Balaramachandran V, Kapali V, Iyer SV, Potdar M, Rajagopalan K (1984) Aluminium as anode in primary alkaline batteries. Influence of additives on the corrosion and anodic behaviour of 2S aluminium in alkaline citrate solution. J Appl Electrochem 14(4):475–480

    CAS  Article  Google Scholar 

  8. 8.

    Brown GM, Paranthaman MP, Dai S, Sun X-G, Liu H (2018) High energy density aluminum battery. Google Patents

  9. 9.

    Huang J, Yang Z, Wang R, Zhang Z, Feng Z, Xie X (2015) Zn–Al layered double oxides as high-performance anode materials for zinc-based secondary battery. J Mater Chem A 3(14):7429–7436

    CAS  Article  Google Scholar 

  10. 10.

    Yang H, Yang Z, Wen X, Liu L (2017) The in situ growth of zinc–aluminum layered double hydroxides on graphene and its application as anode active materials for Zn–Ni secondary battery. Electrochim Acta 252:507–515

    CAS  Article  Google Scholar 

  11. 11.

    Dai J, Li SF, Xiao TD, Wang DM, Reisner DE (2000) Structural stability of aluminum stabilized alpha nickel hydroxide as a positive electrode material for alkaline secondary batteries. J Power Sources 89(1):40–45

    CAS  Article  Google Scholar 

  12. 12.

    Fan L, Lu H (2015) The effect of grain size on aluminum anodes for Al–air batteries in alkaline electrolytes. J Power Sources 284:409–415

    CAS  Article  Google Scholar 

  13. 13.

    Wen X, Yang Z, Xie X, Feng Z, Huang J (2015) The effects of element Cu on the electrochemical performances of zinc–aluminum-hydrotalcites in Zinc/Nickel secondary battery. Electrochim Acta 180:451–459

    CAS  Article  Google Scholar 

  14. 14.

    Zhou M, Sammells AF (2017) Molten alkali metal-aluminum secondary battery. Google Patents

  15. 15.

    Laurent C, Scenini F, Monetta T, Bellucci F, Curioni M (2017) The contribution of hydrogen evolution processes during corrosion of aluminium and aluminium alloys investigated by potentiodynamic polarisation coupled with real-time hydrogen measurement. npj Mater Degrad 1(1):6

    Article  CAS  Google Scholar 

  16. 16.

    Curioni M, Scenini F (2015) The mechanism of hydrogen evolution during anodic polarization of aluminium. Electrochim Acta 180:712–721

    CAS  Article  Google Scholar 

  17. 17.

    Wang HZ, Leung DYC, Leung MKH, Ni M (2009) A review on hydrogen production using aluminum and aluminum alloys. Renew Sustain Energy Rev 13(4):845–853

    CAS  Article  Google Scholar 

  18. 18.

    Soler L, Candela AM, Macanás J, Muñoz M, Casado J (2009) In situ generation of hydrogen from water by aluminum corrosion in solutions of sodium aluminate. J Power Sources 192(1):21–26

    CAS  Article  Google Scholar 

  19. 19.

    Wang D, Gao L, Zhang D, Yang D, Wang H, Lin T (2016) Experimental and theoretical investigation on corrosion inhibition of AA5052 aluminium alloy by l-cysteine in alkaline solution. Mater Chem Phys 169(Supplement C):142–151

    CAS  Article  Google Scholar 

  20. 20.

    Macdonald DD, Real S, Urquidi-Macdonald M (1988) Development of alloy anodes for aluminium/air batteries: final report

  21. 21.

    Macdonald DD, Lee KH, Moccari A, Harrington D (1988) Evaluation of alloy anodes for aluminum–air batteries: corrosion studies. Corrosion 44(9):652–657

    CAS  Article  Google Scholar 

  22. 22.

    Real S, Urquidi-Macdonald M, Macdonald DD (1988) Evaluation of alloy anodes for aluminum–air batteries: II. Delineation of anodic and cathodic partial reactions. J Electrochem Soc 135(7):1633–1636

    CAS  Article  Google Scholar 

  23. 23.

    Macdonald DD, Real S, Smedley SI, Urquidi-Macdonald M (1988) Evaluation of alloy anodes for aluminum–air batteries: IV. Electrochemical impedance analysis of pure aluminum in at 25 °C. J Electrochem Soc 135(10):2410–2414

    CAS  Article  Google Scholar 

  24. 24.

    Gale JD, Rohl AL, Watling HR, Parkinson GM (1998) Theoretical investigation of the nature of aluminum-containing species present in alkaline solution. J Phys Chem B 102(50):10372–10382

    CAS  Article  Google Scholar 

  25. 25.

    Paramasivam M, Jayachandran M, Venkatakrishna Iyer S (2003) Influence of alloying additives on the performance of commercial grade aluminium as galvanic anode in alkaline zincate solution for use in primary alkaline batteries. J Appl Electrochem 33(3):303–309

    CAS  Article  Google Scholar 

  26. 26.

    El Abedin SZ, Saleh A (2004) Characterization of some aluminium alloys for application as anodes in alkaline batteries. J Appl Electrochem 34(3):331–335

    Article  Google Scholar 

  27. 27.

    Macdonald DD, Real S, Urquidi-Macdonald M (1988) Evaluation of alloy anodes for aluminum–air batteries: III. Mechanisms of activation, passivation, and hydrogen evolution. J Electrochem Soc 135(10):2397–2409

    CAS  Article  Google Scholar 

  28. 28.

    Soler L, Macanás J, Muñoz M, Casado J (2007) Aluminum and aluminum alloys as sources of hydrogen for fuel cell applications. J Power Sources 169(1):144–149

    CAS  Article  Google Scholar 

  29. 29.

    Macdonald DD, English C (1990) Development of anodes for aluminium/air batteries—solution phase inhibition of corrosion. J Appl Electrochem 20(3):405–417

    CAS  Article  Google Scholar 

  30. 30.

    Xhanari K, Finšgar M (2016) Organic corrosion inhibitors for aluminum and its alloys in chloride and alkaline solutions: a review. Arab J Chem.

    Article  Google Scholar 

  31. 31.

    Abdel-Gaber AM, Khamis E, Abo-ElDahab H, Adeel S (2008) Inhibition of aluminium corrosion in alkaline solutions using natural compound. Mater Chem Phys 109(2–3):297–305

    CAS  Article  Google Scholar 

  32. 32.

    Abdel-Gaber AM, Khamis E, Abo-Eldahab H, Adeel S (2010) Novel package for inhibition of aluminium corrosion in alkaline solutions. Mater Chem Phys 124(1):773–779

    CAS  Article  Google Scholar 

  33. 33.

    Verma C, Singh P, Bahadur I, Ebenso EE, Quraishi MA (2015) Electrochemical, thermodynamic, surface and theoretical investigation of 2-aminobenzene-1,3-dicarbonitriles as green corrosion inhibitor for aluminum in 0.5 M NaOH. J Mol Liq 209(Supplement C):767–778

    CAS  Article  Google Scholar 

  34. 34.

    Moon S-M, Pyun S-I (1999) The formation and dissolution of anodic oxide films on pure aluminium in alkaline solution. Electrochim Acta 44(14):2445–2454

    CAS  Article  Google Scholar 

  35. 35.

    Wang XY, Wang JM, Shao HB, Zhang JQ, Cao CN (2005) Influences of zinc oxide and an organic additive on the electrochemical behavior of pure aluminum in an alkaline solution. J Appl Electrochem 35(2):213–216

    CAS  Article  Google Scholar 

  36. 36.

    Soliman HN (2011) Influence of 8-hydroxyquinoline addition on the corrosion behavior of commercial Al and Al-HO411 alloys in NaOH aqueous media. Corros Sci 53(9):2994–3006

    CAS  Article  Google Scholar 

  37. 37.

    Robertson SG, Ritchie IM, Druskovich DM (1995) A kinetic and electrochemical study of the zincate immersion process for aluminium. J Appl Electrochem 25(7):659–666

    CAS  Article  Google Scholar 

  38. 38.

    Paramasivam M, Suresh G, Muthuramalingam B, Iyer SV, Kapali V (1991) Different commercial grades of aluminum as galvanic anodes in alkaline zincate solutions. J Appl Electrochem 21(5):452–456

    CAS  Article  Google Scholar 

  39. 39.

    Lee S-K, Lee J-H, Kim Y-H (2007) Nucleation and growth of zinc particles on an aluminum substrate in a zincate process. J Electron Mater 36(11):1442–1447

    CAS  Article  Google Scholar 

  40. 40.

    Rashvand Avei M, Jafarian M, Moghanni Bavil Olyaei H, Gobal F, Hosseini SM, Mahjani MG (2013) Study of the alloying additives and alkaline zincate solution effects on the commercial aluminum as galvanic anode for use in alkaline batteries. Mater Chem Phys 143(1):133–142

    CAS  Article  Google Scholar 

  41. 41.

    Strohmeier BR, Evans WT, Schrall DM (1993) Preparation and surface characterization of zincated aluminum memory-disc substrates. J Mater Sci 28(6):1563–1572

    CAS  Article  Google Scholar 

  42. 42.

    Khan E, Oduoza CF, Pearson T (2007) Surface characterization of zincated aluminium and selected alloys at the early stage of the autocatalytic electroless nickel immersion process. J Appl Electrochem 37(11):1375–1381

    CAS  Article  Google Scholar 

  43. 43.

    Paramasivam M, Iyer SV, Kapali V (1994) Effect of zincate conversion coating on corrosion and anodic behaviour of commercial aluminium in alkaline media. Br Corros J 29(3):207–209

    CAS  Article  Google Scholar 

  44. 44.

    Wang XY, Wang JM, Wang QL, Shao HB, Zhang JQ (2011) The effects of polyethylene glycol (PEG) as an electrolyte additive on the corrosion behavior and electrochemical performances of pure aluminum in an alkaline zincate solution. Mater Corros 62(12):1149–1152

    CAS  Article  Google Scholar 

  45. 45.

    Fu J, Cano ZP, Park MG, Yu A, Fowler M, Chen Z (2017) Electrically rechargeable zinc–air batteries: progress, challenges, and perspectives. Adv Mater 29(7):1604685

    Article  CAS  Google Scholar 

  46. 46.

    Sharma RA (1986) Physico-chemical properties of calcium zincate. J Electrochem Soc 133(11):2215–2219

    CAS  Article  Google Scholar 

  47. 47.

    Floro J et al (2001) The dynamic competition between stress generation and relaxation mechanisms during coalescence of Volmer–Weber thin films. J Appl Phys 89(9):4886–4897

    CAS  Article  Google Scholar 

  48. 48.

    Koch R (1994) The intrinsic stress of polycrystalline and epitaxial thin metal films. J Phys Condens Matter 6(45):9519

    CAS  Article  Google Scholar 

  49. 49.

    Budevski E, Staikov G, Lorenz W, Keusler K (1997) Electrochemical phase formation and growth. Angewandte Chemie-German Edition 109(12):1418

    Google Scholar 

  50. 50.

    Wang R, Kirk D, Zhang G (2006) Effects of deposition conditions on the morphology of zinc deposits from alkaline zincate solutions. J Electrochem Soc 153(5):C357–C364

    CAS  Article  Google Scholar 

  51. 51.

    Faegh E et al (2018) Understanding the dynamics of primary Zn–MnO2 alkaline battery gassing with operando visualization and pressure cells. J Electrochem Soc 165(11):A2528–A2535

    CAS  Article  Google Scholar 

  52. 52.

    Chu D, Savinell RF (1991) Experimental data on aluminum dissolution in KOH electrolytes. Electrochim Acta 36(10):1631–1638

    CAS  Article  Google Scholar 

Download references

Author information



Corresponding author

Correspondence to William E. Mustain.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 928 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Faegh, E., Shrestha, S., Zhao, X. et al. In-depth structural understanding of zinc oxide addition to alkaline electrolytes to protect aluminum against corrosion and gassing. J Appl Electrochem 49, 895–907 (2019).

Download citation


  • Alkaline battery
  • Aluminum
  • Corrosion
  • Zinc
  • Zinc oxide
  • Capacity