Discharge Performance and Electrochemical Behaviors of the Extruded Mg-2Bi-0.5Ca-0.5In Alloy as Anode for Mg-Air Battery
CHENG Weili1,2(), GU Xiongjie1, CHENG Shiming1, CHEN Yuhang1, YU Hui3, WANG Lifei1,2, WANG Hongxia1,2, LI Hang1
1.School of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China 2.Shanxi Key Laboratory of Advanced Magnesium-Based Materials, Taiyuan University of Technology, Taiyuan 030024, China 3.School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300132, China
Cite this article:
CHENG Weili, GU Xiongjie, CHENG Shiming, CHEN Yuhang, YU Hui, WANG Lifei, WANG Hongxia, LI Hang. Discharge Performance and Electrochemical Behaviors of the Extruded Mg-2Bi-0.5Ca-0.5In Alloy as Anode for Mg-Air Battery. Acta Metall Sin, 2021, 57(5): 623-631.
Mg-air batteries have excellent applicability in the fields of electrochemical energy storage and conversion due to their high theoretical voltage (3.09 V) and high specific energy density (6.8 kW·h/kg). Nevertheless, the high polarization and low Coulombic efficiency reduce the inherently outstanding discharge performance of the Mg anode. Alloying and plastic deformation have been utilized to overcome these drawbacks by developing novel anode materials with relatively enhanced performance. In this work, the effect of microstructural characteristics on the discharge performance and electrochemical behaviors of the extruded Mg-2Bi-0.5Ca-0.5In (mass fraction, %) alloy as an anode for Mg-air batteries have been systematically discussed. Results indicate that the extruded alloy primarily consists of complete dynamically recrystallized grains with an average grain size of (10.92 ± 0.23) μm. The texture component is mainly composed of nonbasal texture consisting of texture components of basal poles from the normal direction to extrusion direction by around 45o-60o. The alloy contains α-Mg, nanoscale Mg3Bi2 phases, and microscale Mg2Bi2Ca phases. Furthermore, the extruded alloy exhibits a stable discharge process and negative discharge potential of -1.628 V at 10 mA/cm2 in a half-cell test. Moreover, the Mg-air battery based on the extruded alloy as an anode exhibits a high cell voltage and power density. For instance, the cell voltage and peak power density reach up to 0.72 V and 86.4 mW/cm2 at 120 mA/cm2, respectively, which is significantly higher than commercially accepted AZ31 and AM50 anodes for Mg-air batteries. The outstanding discharge properties are primarily attributed to the re-deposition of metallic In at the electrode surface, the weakened texture intensity, the uniform microstructure and the loose and thin discharge products film.
Fund: National Natural Science Foundation of China(51704209);Natural Science Foundation of Shanxi Province(201801D121088);Shanxi Scholarship Council of China(2019-032);Science and Technology Major Project of Shanxi Province(20191102008)
About author: CHENG Weili, professor, Tel: (0351)6010021, E-mail: chengweili7@126.com
Fig.1 Crystallographic orientation map (a) and (0001) pole figure (b) of the extruded Mg-2Bi-0.5Ca-0.5In (BXI200) alloy (ED—extrusion direction, TD—transverse direction)
Fig.2 Grain size distributions of the extruded BXI200 alloy (AGS—average grain size)
Fig.3 Low (a) and high (b) magnified SEM images of the extruded BXI200 alloy
Point
Mg
Bi
Ca
A
63.4
36.6
0
B
44.5
42.1
13.4
Table 1 EDS results of the second phases for the extruded BXI200 alloy in Fig.3b
Fig.4 XRD spectrum of the extruded BXI200 alloy
Fig.5 Open circuit potential (Eocp) (a) and polarization curve (b) of the extruded BXI200 alloy (E—potential, i—current density)
Fig.6 Nyquist (a) and phase angle and frequency bode (b) diagrams of the extruded BXI200 alloy (Z'—the real part of impedance, Z''—the imaginary part of impedance, f—frequency)
Fig.7 Equivalent circuit diagram of the extruded BXI200 alloy (Rs—solution resistance, Rct—charge transfer resistance, CPE—constant phase element, L—inductor, RL—inductance resistance, RE—reference electrode, WE—working electrode)
Fig.8 Galvanostatic discharge curves (a), and cell voltages and power densities of Mg-air batteries (b) at different current densities of the extruded BXI200 alloy
Fig.9 Surface (a) and cross sectional (b) SEM images of the discharge products for the extruded BXI200 alloy after discharge at 120 mA/cm2 for 10 min
Fig.10 XPS analyses of discharge products for the extruded BXI200 alloy
Fig.11 Surface morphologies of the extruded BXI200 alloy without discharge products after discharge at 10 mA/cm2 (a, b) and 120 mA/cm2 (c, d) for 10 min (a, c) and 60 min (b, d) (Insets show the high magnified images)
1
Liu X, Xue J L. The role of Al2Gd cuboids in the discharge performance and electrochemical behaviors of AZ31-Gd anode for Mg-air batteries [J]. Energy, 2019, 189: 116314
2
Liu X, Guo Z C, Xue J L, et al. The role of Al2Ca and Al2(Sm, Ca, La) particles in the microstructures and electrochemical discharge performance of as-extruded Mg-3wt.%Al-1wt.%Zn-based alloys for primary Mg-air batteries [J]. Int. J. Energy Res., 2019, 43: 4569
3
Zheng T X, Hu Y B, Zhang Y X, et al. Composition optimization and electrochemical properties of Mg-Al-Sn-Mn alloy anode for Mg-air batteries [J]. Mater. Des., 2018, 137: 245
4
Rahman M, Wang X J, Wen C E. High energy density metal-air batteries: A review [J]. J. Electrochem. Soc., 2013, 160: A1759
5
Xiong H Q, Yu K, Yin X, et al. Effects of microstructure on the electrochemical discharge behavior of Mg-6wt%Al-1wt%Sn alloy as anode for Mg-air primary battery [J]. J. Alloys Compd., 2017, 708: 652
6
Feng Y, Xiong W H, Zhang J C, et al. Electrochemical discharge performance of the Mg-Al-Pb-Ce-Y alloy as the anode for Mg-air batteries [J]. J. Mater. Chem., 2016, 4A: 8658
7
Ma Y B, Li N, Li D Y, et al. Performance of Mg-14Li-1Al-0.1Ce as anode for Mg-air battery [J]. J. Power Sources, 2011, 196: 2346
8
Zeng R C, Cui L Y, Ke W. Biomedical magnesium alloys: Composition, microstructure and corrosion [J]. Acta Metall. Sin., 2018, 54: 1215
Zhang Z M, Yu K, Ren W W, et al. Microstructure of directly extruded Mg-1Zn-1Ca alloy and its corrosion behavior in SBF solution [J]. Acta Metall. Sin., 2015, 51: 985
Wang N G, Wang R C, Peng C Q, et al. Discharge behaviour of Mg-Al-Pb and Mg-Al-Pb-In alloys as anodes for Mg-air battery [J]. Electrochim. Acta, 2014, 149: 193
12
Gu X J, Cheng W L, Cheng S M, et al. Discharge behavior of Mg-Sn-Zn-Ag alloys with different Sn contents as anodes for Mg-air batteries [J]. J. Electrochem. Soc., 2020, 167: 020501
13
Liu X, Xue J L, Zhang P J, et al. 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 [J]. J. Power Sources, 2019, 414: 174
14
Wang N G, Wang R C, Peng C Q, et al. Effect of hot rolling and subsequent annealing on electrochemical discharge behavior of AP65 magnesium alloy as anode for seawater activated battery [J]. Corros. Sci., 2012, 64: 17
15
Feng Y, Lei G, He Y Q, et al. Discharge performance of Mg-Al-Pb-La anode for Mg-air battery [J]. Trans. Nonferrous Met. Soc. China, 2018, 28: 2274
16
Wang N G, Li W P, Huang Y X, et al. Wrought Mg-Al-Pb-RE alloy strips as the anodes for Mg-air batteries [J]. J. Power Sources, 2019, 436: 226855
17
Huang G S, Zhao Y C, Wang Y X, et al. Performance of Mg-air battery based on AZ31 alloy sheet with twins [J]. Mater. Lett., 2013, 113: 46
18
Yuasa M, Huang X S, Suzuki K, et al. Effects of microstructure on discharge behavior of AZ91 Alloy as anode for Mg-air battery [J]. Mater. Trans., 2014, 55: 1202
19
Liu X, Xue J L, Zhang D. Electrochemical behaviors and discharge performance of the as-extruded Mg-1.5 wt%Ca alloys as anode for Mg-air battery [J]. J. Alloys Compd., 2019, 790: 822
20
Deng M, Höche D, Lamaka S V, et al. Revealing the impact of second phase morphology on discharge properties of binary Mg-Ca anodes for primary Mg-air batteries [J]. Corros. Sci., 2019, 153: 225
21
Deng M, Höche D, Lamaka S V, et al. Mg-Ca binary alloys as anodes for primary Mg-air batteries [J]. J. Power Sources, 2018, 396: 109
22
Liu X, Xue J L, Liu S Z. Discharge and corrosion behaviors of the α-Mg and β-Li based Mg alloys for Mg-air batteries at different current densities [J]. Mater. Des., 2018, 160: 138
23
Wang N G, Wang R C, Feng Y, et al. Discharge and corrosion behaviour of Mg-Li-Al-Ce-Y-Zn alloy as the anode for Mg-air battery [J]. Corros. Sci., 2016, 112: 13
24
Cheng S M, Cheng W L, Gu X J, et al. Discharge properties of low-alloyed Mg-Bi-Ca alloys as anode materials for Mg-air batteries: Influence of Ca alloying [J]. J. Alloys Compd., 2020, 823: 153779
25
Flamini D O, Saidman S B. Electrochemical behaviour of Al-Zn-Ga and Al-In-Ga alloys in chloride media [J]. Mater. Chem. Phys., 2012, 136: 103
26
Park I J, Choi S R, Kim J G. Aluminum anode for aluminum-air battery—Part II: Influence of In addition on the electrochemical characteristics of Al-Zn alloy in alkaline solution [J]. J. Power Sources, 2017, 357: 47
27
Yuan S Q, Lu H M, Sun Z G, et al. Electrochemical performance of Mg-3Al modified with Ga, In and Sn as anodes for Mg-air battery [J]. J. Electrochem. Soc., 2016, 163: A1181
28
Gore P, Fajardo S, Birbilis N, et al. Anodic activation of Mg in the presence of In3+ ions in dilute sodium chloride solution [J]. Electrochim. Acta, 2019, 293: 199
29
Chai Y F, Jiang B, Song J F, et al. Improvement of mechanical properties and reduction of yield asymmetry of extruded Mg-Sn-Zn alloy through Ca addition [J]. J. Alloys Compd., 2019, 782: 1076
30
Yuasa M, Huang X S, Suzuki K, et al. Discharge properties of Mg-Al-Mn-Ca and Mg-Al-Mn alloys as anode materials for primary magnesium-air batteries [J]. J. Power Sources, 2015, 297: 449
31
Deng M, Wang L Q, Höche D, et al. Ca/In micro alloying as a novel strategy to simultaneously enhance power and energy density of primary Mg-air batteries from anode aspect [J]. J. Power Sources, 2020, 472: 228528