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pp 1–8 | Cite as

Effects of second phases in anode materials on discharge performance of Mg-air batteries

  • Yongfa Song
  • Jingling MaEmail author
  • Yaqiong Li
  • Guangxin WangEmail author
  • Conghui Qin
  • Heinz-Rolf Stock
Original Paper

Abstract

As-cast Mg-6Al and as-cast and hot-rolled Mg-6Al-1Ce alloys were used as anode materials in Mg-air batteries. Effects of second phases of anode materials on electrochemical properties and discharge behavior were investigated by backscattered electron (BSE), energy dispersive spectrometry (EDS), X-ray diffraction (XRD), and electrochemical test. Many β-(Mg17Al12) particles were found in as-cast Mg-6Al alloy. Deep corrosion pits were formed near these particles, which is not beneficial to improve discharge performance. The as-cast Mg-6Al-1Ce alloy forms larger γ-(Al4Ce) grains, which retard the shedding of corrosion products. The contact between electrolyte and metal anode is hindered, and corrosion product accumulation leads to a slowly decreasing voltage. With hot rolling, the γ phase breaks up into many fine and evenly distributed particles. In this way, corrosion products can easily peel off from the anode surface, leading to an improvement of anode discharge activity.

Keywords

Mg-air battery Second phase Hot rolling Discharge performance 

Notes

Funding information

This work was supported by the Chinese 02 Special Fund (Grand No. 2017ZX02408003), the Chinese 1000 Plan for High Level Foreign Experts (Grand No. WQ20154100278).

References

  1. 1.
    Bucur C, Gregory T, Oliver AG, Muldoon J (2015) Confession of a magnesium battery. J Phys Chem Lett:3578–3591Google Scholar
  2. 2.
    Mohtadi R, Mizuno F (2014) Magnesium batteries: current state of the art, issues and future perspectives. Beilstein Journal of Nanotechnology 5(1):1291–1311CrossRefGoogle Scholar
  3. 3.
    Li C-S, Sun Y, Gebert F, Chou S-L (2017) Current progress on rechargeable magnesium-air battery. Advanced Energy Materials 7(24):1700869CrossRefGoogle Scholar
  4. 4.
    Hahn R, Mainert J, Glaw F, Lang K-D (2015) Sea water magnesium fuel cell power supply. Journal of Power Sources 288:26–35CrossRefGoogle Scholar
  5. 5.
    Li Y, Ma J, Wang G, Reng F, Zhu Y, Song Y (2018) Investigation of sodium phosphate and sodium dodecylbenzenesulfonate as electrolyte additives for AZ91 magnesium-air battery. Journal of the Electrochemical Society 165(9):A1713–A1717CrossRefGoogle Scholar
  6. 6.
    Ma J, Wang G, Li Y, Li W, Ren F (2018) Influence of sodium silicate/sodium alginate additives on discharge performance of Mg-air battery based on AZ61 alloy. Journal of Materials Engineering and Performance 27(5):2247–2254CrossRefGoogle Scholar
  7. 7.
    Wang N, Wang R, Peng C, Peng B, Feng Y, Hu C (2014) Discharge behavior of Mg-Al-Pb and Mg-Al-Pb-In alloys as anodes for Mg-air battery. Electrochimica Acta 149:193–205CrossRefGoogle Scholar
  8. 8.
    Kim SH, Park JH, Kim HS, Kim JJ, Duck Kwon O (2014) Effect of Al and Sn on discharge behavior of Mg alloy as anode for Mg-air battery. Magnesium Technology:413–419Google Scholar
  9. 9.
    Ma Y, Li N, Li D, Zhang M, Huang X (2011) Performance of Mg-14Li-1Al-0.1Ce as anode for Mg-air battery. Journal of Power Sources 196(4):2346–2350CrossRefGoogle Scholar
  10. 10.
    Yuasa M, Huang X, Suzuki K, Mabuchi M, Chino Y (2015) Discharge properties of Mg-Al-Mn-Ca and Mg-Al-Mn alloys as anode materials for primary magnesium-air batteries. Journal of Power Sources 297:449–456CrossRefGoogle Scholar
  11. 11.
    Du J, Ding D, Zhang W, Xu Z, Gao Y, Chen G, You X, Chen R, Huang Y, Tang J (2018) Effect of Ce addition on the microstructure and properties of Al-Cu-Mn-Mg-Fe lithium battery shell alloy. Materials Characterization 142:252–260CrossRefGoogle Scholar
  12. 12.
    Denga M, Höche D, Lamaka SV, Snihirova D, Zheludkevich ML (2018) Mg-Ca binary alloys as anodes for primary Mg-air batteries. Journal of Power Sources 396:109–118CrossRefGoogle Scholar
  13. 13.
    Wanga N, Wang R, Feng Y, Xiong W, Zhang J, DengWang M (2016) Discharge and corrosion behaviour of Mg-Li-Al-Ce-Y-Zn alloy as the anode for Mg-air battery. Corrosion Science 112:13–24CrossRefGoogle Scholar
  14. 14.
    Xiong H, Zhu H, Luo J, Yu K, Shi C, Fang H, Zhang Y (2017) Effects of heat treatment on the discharge behavior of Mg-6wt.%Al-1wt.%Sn alloy as anode for magnesium-air batteries. Journal of Materials Engineering and Performance 26(6):2901–2911CrossRefGoogle Scholar
  15. 15.
    Liu X, Xue J, Zhang P, Wang Z (2019) Effects of the combinative Ca, Sm and La additions on the electrochemical behaviors and discharge performance of the as-extruded AZ91 anodes for Mg-air batteries. Journal of Power Sources. 414:174–182CrossRefGoogle Scholar
  16. 16.
    Xiong H, Yu K, Yin X, Dai Y, Yan Y, Zhu H (2017) Effects of microstructure on the electrochemical discharge behavior of Mg-6wt%Al-1wt%Sn alloy as anode for Mg-air primary battery. Journal of Alloys and Compounds 708:652–661CrossRefGoogle Scholar
  17. 17.
    Shi Y, Peng C, Feng Y, Wang R, Wang N (2017) Enhancement of discharge properties of an extruded Mg-Al-Pb anode for seawater-activated battery by lanthanum addition. Journal of Alloys and Compounds 721:392–404CrossRefGoogle Scholar
  18. 18.
    Shi Y, Peng C, Yan F, Wang R, Wang N (2017) Microstructure and electrochemical corrosion behavior of extruded Mg-Al-Pb-La alloy as anode for seawater-activated battery. Materials & Design 124:24–33CrossRefGoogle Scholar
  19. 19.
    Wang Y, Wei M, Gao J, Hu J, Wang YZ (2008) Corrosion process of pure magnesium in simulated body fluid. Materials Letters 62(14):2181–2184CrossRefGoogle Scholar
  20. 20.
    Wu Y, Wang Z, Liu Y, Li G, Xie S, Yu H, Xiong H (2019) AZ61 and AZ61-La alloys as anodes for Mg-air battery. Journal of Materials Engineering and Performance 28(4):2006–2016CrossRefGoogle Scholar
  21. 21.
    Song G, Atrens A, Wu X, Zhang B (1998) Corrosion behaviour of AZ21, AZ501 and AZ91 in sodium chloride. Corrosion Science 40(10):1769–1791CrossRefGoogle Scholar
  22. 22.
    Liu X, Xue J, Liu S (2018) Discharge and corrosion behaviors of the α-Mg and β-Li based Mg alloys for Mg-air batteries at different current densities. Materials and Design. 160:138–146CrossRefGoogle Scholar
  23. 23.
    Li CQ, Xu D, Chen X-B, Wang BJ, Wu RZ, Han EH, Birbilis N (2018) Composition and microstructure dependent corrosion behaviour of Mg-Li alloys. Electrochimica Acta 260:55–64CrossRefGoogle Scholar
  24. 24.
    Zhu H, Liu H, Fang H, Dai Y, Li L, Xu X, Yan Y, Yu K (2018) Electrochemical performance of Mg-Al-Zn and Mg-Al-Zn-Ce alloys as anodes for Mg-air battery. International Journal of Electrochemical Science 13:11180–11192CrossRefGoogle Scholar
  25. 25.
    Lv Y, Tang D, Cao D, Wang G, Zhangm M, Feng J (2015) The effect of NaF on the electrochemical behavior of the Mg-11Li-3.5Al-1Zn-1Sn-1Ce-0.1Mn electrode in NaCl solution. RSC Advances 5(58):46423–46429CrossRefGoogle Scholar
  26. 26.
    Cheng P, Chen Y-G, Ding W-C (2017) Improving corrosion resistance of hot extruded Mg-Sn-Al-Ce magnesium alloy by rapid solidification. Materials Science Forum 904:80–84CrossRefGoogle Scholar
  27. 27.
    Yang J, Yi D, Deng S, Wang B, Liu G (2008) Effect of trace Ce on the microstructure and corrosion resistance of AZ91 magnesium alloy. Journal of Materials Science and Engineering. 28:205–209Google Scholar
  28. 28.
    Li J, Zhang B, Wei Q, Wang N, Hou B (2017) Electrochemical behavior of Mg-Al-Zn-In alloy as anode materials in 3.5 wt.% NaCl solution. Electrochimica Acta 238:156–167CrossRefGoogle Scholar
  29. 29.
    Li J, Wan K, Jiang Q, Sun H, Yantao Li 1, Baorong Hou, Liwei Zhu, Min Liu (2016) Corrosion and discharge behaviors of Mg-Al-Zn and Mg-Al-Zn-In alloys as anode material. Metals 6(3):65CrossRefGoogle Scholar
  30. 30.
    Liu X, Liu S, Xue J (2018) Discharge performance of the magnesium anodes with different phase constitutions for Mg-air batteries. Journal of Power Sources. 396:667–674CrossRefGoogle Scholar
  31. 31.
    Wang N, Mu Y, Li Q, Shi Z (2017) Discharge and corrosion behaviour of AP65 magnesium anode plates with different rolling reductions. RSC Advances 7(84):53226–53235CrossRefGoogle Scholar
  32. 32.
    Wang N, Mu Y, Xiong W, Zhang J, Li Q, Shi Z (2018) Effect of crystallographic orientation on the discharge and corrosion behaviour of AP65 magnesium alloy anodes. Corrosion Science 144:107–126CrossRefGoogle Scholar
  33. 33.
    Wen L, Yu K, Fang H-j, Xiong H-q, Yin X, Zhu H-l, Ma J-j, Jiang D-y (2016) Electrochemical behavior of Mg-Al-Pb alloy in 3.5% NaCl solution. Journal of Central South University 23(10):2475–2482CrossRefGoogle Scholar
  34. 34.
    Li J, Jiang Q, Sun H, Li Y (2016) Effect of heat treatment on corrosion behavior of AZ63 magnesium alloy in 3.5wt.% sodium chloride solution. Corrosion Science 111:288–301CrossRefGoogle Scholar
  35. 35.
    Liu C, Yang H, Wan P, Wang K, Tan L, Yang K (2014) Study on biodegradation of the second phase Mg17Al12 in Mg-Al-Zn alloys: in vitro experiment and thermodynamic calculation. Materials Science and Engineering: C 35:1–7CrossRefGoogle Scholar
  36. 36.
    Cao D, Wu L, Wang G, Lv Y (2008) Electrochemical oxidation behavior of Mg-Li-Al-Ce-Zn and Mg-Li-Al-Ce-Zn-Mn in sodium chloride solution. Journal of Power Sources 183(2):799–804CrossRefGoogle Scholar
  37. 37.
    Feng Y, Wang R-c, Peng C-q, Tang H-p, Liu H-y (2011) Influence of Mg5Ga2 compound on microstructures and electrochemical properties of Mg-5%Hg-22%Ga alloy. Progress in Natural Science: Materials International 21(1):73–79CrossRefGoogle Scholar
  38. 38.
    Hong TT, Sun YH, Jepson WP (2002) Study on corrosion inhibitor in large pipelines under multiphase flow using EIS. Corrosion Science 44(1):101–112CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Research Center for High Purity Materials, School of Materials Science and EngineeringHenan University of Science and TechnologyLuoyangChina

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