Skip to main content

Advertisement

SpringerLink
Log in

The effects of anode additives towards suppressing dendrite growth and hydrogen gas evolution reaction in Zn-air secondary batteries

  • Original Paper
  • Published:
Ionics Aims and scope Submit manuscript

Abstract

In our continual effort to develop a cost effective rechargeable Zn-air batteries, herewith, we demonstrated Zn anodes comprising of (i) 30 wt.% Zn: 3 wt.% bismuth oxide: 10 wt.% potassium sulfide (ZBK), (ii) 30 wt.% Zn: 3 wt.% bismuth oxide: 5 wt.% lead (II) oxide (ZBP), and (iii) 30 wt.% Zn: 3 wt.% bismuth oxide: 10 wt.% potassium sulfide: 5 wt.% lead (II) oxide additives (ZBKP) in 6 M KOH aqueous solutions and 1.88 wt.% polyacrylic acid as the gelling agent. KOH gel constituted the remaining mass of the anode wt.%. Results were confirmed via cycle voltammetry (CV), Tafel, electrochemical impedance spectroscopy (EIS), etc., measurements. Among the various Zn anodes analyzed, ZBKP showed a superior cathodic peak of − 1.805 and 1.950 V vs. Hg/HgCl at 5th and 40th cycles during electrochemical cycle voltammetry. Tafel fitting on linear polarization test shows that ZBK exhibits the highest corrosion behavior followed by ZBP while ZBKP has the lowest corrosion behavior with an estimated corrosion inhibition efficiency of 36.06%. Furthermore, ZBKP displays the lowest dendrite growth, least corrosion rate, and superior capacity even at 60th cycles compared to ZBK and ZBP. In view of our finding, ZBKP has a higher positive electrode potential compare to ZBK and ZBP electrodes. Thus, ZBKP is the most suitable for aqueous battery due to its low minimal side effect. Field emission-scanning electron microscopy/energy dispersive x-ray spectroscopy (FE-SEM/EDS) images confirm that the various elemental additives were evenly deposited on the Zn anode surface. Ex situ spectroscopy and electrochemical performance studies also verified that the dendrite-free nature of improved Zn anode and the modified interfaces between electrolyte and Zn play vital roles towards advancing the energy storage performance. With all this indices and yard stick, the level of improvement we demonstrated in this current study is attractive for the design of an advanced secondary zinc-air batteries.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  1. Kamali SK, Tyagi VV, Rahim NA, Panwar NL, Mokhlis H (2013) Emergence of energy storage technologies as the solution for reliable operation of smart power systems: a review. Renew Sust Energ Rev 25:135–165

    Article  Google Scholar 

  2. Jorge OGP, Anthony JRR, Sofia PV, Vitor LM, Jordan M, Alistair B, Carol FG, David AW, Peter JH (2017) Aqueous batteries as grid scale energy storage solutions. Renew Sust Energ Rev 68:1174–1182

    Article  CAS  Google Scholar 

  3. Prakash KS, Balasundar P, Nagaraja S, Gopal PM, Kavimani V (2016) Mechanical and wear behaviour of Mg–SiC–Gr hybrid composites. J Magnesium Alloys 4(3):197–206

    Article  CAS  Google Scholar 

  4. 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):1604685–1604685

    Article  CAS  Google Scholar 

  5. Winsberg J, Janoschka T, Morgenstern S, Hagemann T, Muench S, Hauffman G, Gohy J-F, Hager MD, Schubert US (2016) Poly(TEMPO)zinc hybrid-flow battery: a novel, “Green,” high voltage, and safe energy storage system. Adv Mater 28:2238–2243

    Article  CAS  PubMed  Google Scholar 

  6. Fu J, Zhang J, Song X, Zarrin H, Tian X, Qiao J, Rasen L, Li K, Chen Z (2016) A flexible solid-state electrolyte for wide-scale integration of rechargeable zinc–air batteries. Energy Environ Sci 9:663–664

    Article  CAS  Google Scholar 

  7. Hwanga B, Ohb E, Kim K (2016) Observation of electrochemical reactions at Zn electrodes in Zn-air secondary batteries. Electrochim Acta 216:484–489

    Article  CAS  Google Scholar 

  8. Park DJ, Aremu EO, Ryu KS (2018) Bismuth oxide as an excellent anode additive for inhibiting dendrite formation in zinc-air secondary batteries. Appl Surf Sci 456:507–514

    Article  CAS  Google Scholar 

  9. Zhang J, Xu R, Yu B, He Y, Li Y, Qin Z (2017) Study on the properties of Pb–Co3O4–PbO2composite inert anodes prepared by vacuum hot pressing technique. RSC Adv 7:49166–49168

    Article  CAS  Google Scholar 

  10. Manohar AK, Yang C, Malkhandi S, Prakash GKS, Narayanan SR (2013) Recent advances in inexpensive aqueous batteries for large scale electrical energy storage. J Electrochem Soc 160(11):A2078–A2084

    Article  CAS  Google Scholar 

  11. Tingting W, Zhanhong Y, Bin Y, Ruijuan W, Jianhang H (2014) The electrochemical performances of Zn-Sn-Alhydrotalcites in Zn-Ni secondary cells. J Power Source 257:174–180

    Article  CAS  Google Scholar 

  12. Zhong XC, Yu XY, Jiang LX, Li F, Li J, Li YX (2013) Electrochemical behavior of Pb–Ag–Nd alloy during pulse current polarization in KOH solution. Hydrometallurgy 131:144–157

    Google Scholar 

  13. Qinmin P, Zijia W, Jia L, Geping Y, Min G (2009) PbO@C core–shell nanocomposites as an anode material of lithium-ion batteries. Electrochem Commun 11:917–920

    Article  CAS  Google Scholar 

  14. Sivaram H, Selvakumar D, Alsalme A, Alswieleh A, Jayavel R (2018) Enhanced performance of PbO nanoparticles and PbO-CdO and PbO-ZnO nanocomposites for supercapacitor application. J Alloys Compd 731:55–63

    Article  CAS  Google Scholar 

  15. Miomir GP, Aleksandar D (1997) On the use of platinized and activated titanium anodes in some electrodeposition processes. J Solid State Electrochem 1:208–214

    Article  Google Scholar 

  16. Wenjing X, Hao S, Yuzhen S, Guanglou J, Bing H, Jian W (2018) Performance of PbO2 on the basis of porous graphite/Pb conductive substrates for hybrid supercapacitors. Micro Nano Lett 13:122–126

    Article  CAS  Google Scholar 

  17. Clancy M, Bettles CJ, Stuart A, Birbilis N (2013) The influence of alloying elements on the electrochemistry of lead anodes for electrowinning of metals: a review. Hydrometallurgy 131:144–157

    Article  CAS  Google Scholar 

  18. Cachet C, Rerolle C, Wiart R (1996) Kinetics of Pb and Pb-Ag anodes for zinc electrowinning-ii. oxygen evolution at high polarization. Electrochim Acta 41:83–90

    Article  CAS  Google Scholar 

  19. Mirza A, Burr M, Ellis T, Evans D, Kakengela D, Webb L, Gagnon J, Leclercq C, Johnson A (2016) Corrosion of lead anodes in base metals electrowinning. J Southern Afr Inst Min Technol 116:533–537

    Article  CAS  Google Scholar 

  20. Zhao Z, Chuncheng Z, Zihui L, Ying Y, Yuxin Z, Yu S (2014) All-solid-state Al air batteries with polymer alkaline gel electrolyte. J Power Sources 251:470–475

    Article  CAS  Google Scholar 

  21. Martos M, Morales J, Sa’nchez L (2003) Lead-based systems as suitable anode materials for Li-ion batteries. Electrochim Acta 48:615–621

    Article  CAS  Google Scholar 

  22. Jiangfeng N, Haibo W, Yaohui Q, Lijun G (2013) PbO2 electrodeposited on graphite for hybrid supercapacitor applications. Phys Scr 87:045802

    Article  CAS  Google Scholar 

  23. Torabi M, Razavi SH (2011) Electrochemical evaluation of Pbo nanoparticles as anode for Lithium ion batteries. IJE Trans B Appl 24:348–351

    Google Scholar 

  24. Manohar AK, Yang C, Narayanan SR (2015) The role of sulfide additives in achieving long cycle life rechargeable iron electrodes in alkaline batteries. J Electrochem Soc 162(9):A1864–A1872

    Article  CAS  Google Scholar 

  25. Xingwen Y, Arumugam M (2017) A voltage-enhanced, low-cost aqueous iron−air battery enabled with a mediator-ion solid electrolyte. ACS Energy Lett 2:1050–1055

    Article  CAS  Google Scholar 

  26. Jorge O, Gil P, Peter JH (2015) The effect of electrolyte additives on the performance of iron based anodes for NiFe cells. J Electrochem Soc 162:A2036–A2043

    Article  CAS  Google Scholar 

  27. Long W, Yang Z, Fan X, Yang B, Zhao Z, Jing J (2013) The effect of carbon on the electrochemical performances of ZnO in Ni-Zn secondary batteries. Electrochim Acta 105:40–46

    Article  CAS  Google Scholar 

  28. Hosseini S, Woranunt L, Han SJ, Arpornwichanop A, Yonezawa T, Kheawhom S (2018) Discharge performance of zinc-air flow batteries under the efects of sodium dodecyl sulfate and pluronic F-127. Sci Rep 8:14909

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. Chotipanich J, Arpornwichanop A, Yonezawa T, Kheawhom S (2018) Electronic and ionic conductivities enhancement of zinc anode for flexible printed zinc-air battery. Eng J 22(2):47–57

    Article  Google Scholar 

  30. Turney DE, Gallaway JW, Yadav GG, Ramirez R, Nyce M, Banerjee S, Chen-Wiegart YK, Wang J, D’Ambrose MJ, Kolhekar S, Huang J, Wei X (2017) Rechargeable zinc alkaline anodes for long cycle energy storage. Chem Mater 29:4819–4832

    Article  CAS  Google Scholar 

  31. Xiao TX, Li WH, Bao HH, Yang Y, Gu ZY, Xing LW (2019) Dendrite-free lithium anode enables the lithium/graphite dual on battery with much improved cyclic stability. ACS Appl Energy Mater 2:201–206

    Article  CAS  Google Scholar 

  32. Sun KEK, Hoang TKA, Doan TNL, Yu Y, Zhu X, Tian Y, Chen P (2017) Suppression of dendrite formation and corrosion on zinc anode of secondary aqueous batteries. ACS Appl Mater Interfaces 9:9681–9687

    Article  CAS  PubMed  Google Scholar 

  33. Duan H, Yin YX, Shi Y, Wang PF, Zhang XD, Yang CP, Shi JL, Wen R, Guo YG, Wan LJ (2018) Dendrite-free Li-metal battery enabled by a thin asymmetric solid electrolyte with engineered layers. J Am Chem Soc 140:82–85

    Article  CAS  PubMed  Google Scholar 

  34. Yu X, Manthiram A (2017) Long life, high voltage acidic Zn–air batteries. ACS Energy Lett 2:1050–1055

    Article  CAS  Google Scholar 

  35. Zeng DQ, Yang ZH, Wang SW (2011) Preparation and electrochemical performance of In-doped ZnO as anode material for Ni–Zn secondary cells. Electrochim Acta 56:4075–4080

    Article  CAS  Google Scholar 

Download references

Funding

This study was supported by a National Research Foundation of Korea (NRF) grant funded by the Korean Government (MEST) (No. 2012–M1A2A2).

Author information

Authors and Affiliations

  1. Department of Chemistry, University of Ulsan, Doowang-dong, Nam-gu, Ulsan, 44776, South Korea

    Emmanuel Olugbemisola Aremu, Da-Jeong Park & Kwang-Sun Ryu

Authors
  1. Emmanuel Olugbemisola Aremu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Da-Jeong Park
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kwang-Sun Ryu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Kwang-Sun Ryu.

Ethics declarations

Conflict of interest

The authors declare that they have no conflicts of interest.

Additional information

Publisher’s note

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Aremu, E.O., Park, DJ. & Ryu, KS. The effects of anode additives towards suppressing dendrite growth and hydrogen gas evolution reaction in Zn-air secondary batteries. Ionics 25, 4197–4207 (2019). https://doi.org/10.1007/s11581-019-02973-y

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11581-019-02973-y

Keywords

Search

Navigation