Electrochemical Behavior and Discharge Performance of a Low-Alloyed Mg-Ag Alloy as Anode for Mg-Air Battery

doi:10.11900/0412.1961.2023.00332

Acta Metall Sin

2025, Vol. 61

Issue (6): 837-847 DOI: 10.11900/0412.1961.2023.00332

Research paper

Current Issue | Archive | Adv Search

Electrochemical Behavior and Discharge Performance of a Low-Alloyed Mg-Ag Alloy as Anode for Mg-Air Battery

HAO Xubang¹, CHENG Weili¹^,²(

), LI Jian², WANG Lifei¹, CUI Zeqin¹, YAN Guoqing³, ZHAI Kai³, YU Hui⁴

1 School of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2 Salt Lake Chemical Engineering Research Complex, Qinghai University, Xining 810016, China
3 Shanxi Regal Advanced Material Co. Ltd., Yuncheng 043800, China
4 School of Materials Science and Engineering, Hebei University of Technology, Tianjin 300132, China

Cite this article:

HAO Xubang, CHENG Weili, LI Jian, WANG Lifei, CUI Zeqin, YAN Guoqing, ZHAI Kai, YU Hui. Electrochemical Behavior and Discharge Performance of a Low-Alloyed Mg-Ag Alloy as Anode for Mg-Air Battery. Acta Metall Sin, 2025, 61(6): 837-847.

Download:

HTML

PDF(3945KB)
Export: BibTeX | EndNote (RIS)

Abstract

Primary Mg-air batteries have attracted considerable attention in the field of standby emergency energy storage in the wilderness because of their high theoretical voltage (3.1 V) and appreciable specific energy (6.8 kWh/kg). However, because of the severe self-corrosion and sluggish anodic kinetics of Mg anodes, the actual performance of Mg-air batteries is far from the theoretical limits. To synergistically enhance the discharge voltage and specific energy of Mg-air batteries, a low-alloyed Mg-1Ag (mass fraction, %) anode was developed, and its microstructure, electrochemical behavior, and discharge properties were evaluated. The results showed that the extruded alloy mainly consisted of equiaxed grains with an average grain size of (14.19 ± 2.27) μm. The anode studied exhibited a typical extrusion texture with a basal pole perpendicular to the transverse direction, and the texture intensity was 11.05. Additionally, the extruded alloy was shown to exhibit localized segregation of Ag. The Mg-air battery based on the Mg-1Ag alloy as the anode exhibited a stable discharge process. In addition, the cell voltage and specific energy reached 1.344 V and 1374.34 mWh/g at 10 mA/cm², respectively. The acceptable discharge performance of the anode was mainly due to the redeposition of metal Ag on the electrode surface, the multi-cracked discharge product film, and the non-basal-oriented grains with a high-volume fraction.

Key words: Mg-air battery Mg-Ag alloy microstructure discharge performance electrochemical behavior

Received: 10 August 2023

ZTFLH:

TG146.2

Fund: National Natural Science Foundation of China(52375370);Natural Science Foundation of Shanxi Province(202103021224049);Shanxi Zhejiang University New Materials and Chemical Research Institute Scientific Research Project(2022SX-TD025);Open Project of Salt Lake Chemical Engineering Research Complex, Qinghai University(2023-DXSSKF-Z02)

Corresponding Authors: CHENG Weili, professor, Tel: (0351)6010021, E-mail: chengweili7@126.com

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	HAO Xubang
	CHENG Weili
	LI Jian
	WANG Lifei
	CUI Zeqin
	YAN Guoqing
	ZHAI Kai
	YU Hui

URL:

https://www.ams.org.cn/EN/10.11900/0412.1961.2023.00332 OR https://www.ams.org.cn/EN/Y2025/V61/I6/837

Fig.1 Crystallographic orientation map (a), EBSD mapping of grains (b), and (0001) pole figures of extruded Mg-1Ag (Q1) alloy (c) (ED—extrusion direction, TD—transverse direction, f_{DRXed grains}—area fraction of dynamically recrystallized grains, f_Subgrains—area fraction of subgrains, f_{Deformed grains}—area fraction of deformed grains)

Fig.2 Grain size distributions of Q1 alloy (AGS—average grain size)

Fig.3 Low (a) and high (b) magnified SEM images and EDS element mappings of Mg (c) and Ag (d) of Q1 alloy

Fig.4 XRD spectrum of Q1 alloy

Table 1 EDS results of Q1 alloy in Fig.3b

Fig.5 Open circuit potentials (E_OCP) (a), anodic (b) and cathodic (c) branches of the polarization curves, and Nyquist diagram under open circuit potentials (d) of Q1 alloy and high purity magnesium (HP Mg) (E—potential; i—current density; Z' and Z"—real part and imaginary part of the impedance, respectively; SCE—saturated calomel electrode. Inset in Fig.5d is the zoom-in view of the box area)

Table 2 Electrochemical parameters of Q1 alloy and HP Mg

Fig.6 Equivalent circuit diagram of the alloy (R_s—solution resistance; R_fand CPE_f—resistance and capacitance of the corrosion products generated on the surface, respectively; L and R_L—inductor and resistance, specifying the presence of desorption process of corrosion products; CPE_dl—capacitance of the electrical double layer at the interface; R_ct—charge transfer resistance; WE—working electrode; RE—reference electrode)

Table 3 Electrochemical parameters obtained from the fits of the experimental electrochemical impedance spectroscopy (EIS) data

Fig.7 Discharge curves of Q1 alloy and HP Mg at different current densities
(a) 2.5 mA/cm² (b) 5 mA/cm² (c) 10 mA/cm² (d) 20 mA/cm²

Fig.8 Discharge performance of Q1 alloy and HP Mg at different current densities
(a) anodic efficiency and cell voltage
(b) specific capacity and specific energy
(c) discharge performance statistics of anode materials for Mg-air batteries at 10 mA/cm² in recent years^{[1-3,5~8,11,20-26]}

Fig.9 Surface (a-h) and cross-sectional (i-l) SEM images for Q1 alloy after discharge in 3.5%NaCl solution at 2.5 mA/cm² (a, e, i), 5 mA/cm²(b, f, j), 10 mA/cm²(c, g, k), and 20 mA/cm²(d, h, l) for 10 h (Figs.9e-h show the local magnified morphologies corresponding to the boxes in Figs.9a-d, respectively)

Fig.10 XPS of the oxide films on the alloy surface after discharge at 2.5 and 20 mA/cm² in 3.5%NaCl solution for 10 h, including high-resolution Mg1s (a), Ag3d (b), Cl2p (c), and O1s (d) spectra

Fig.11 Surface SEM images of Q1 alloy discharged at different current densities for 10 min (a, f), 30 min (b, g), 1 h (c, h), 10 h (d, i) after removing the discharge products; and 3D morphologies of Q1 alloy discharged for 10 h after removing the discharge products (e, j) (Insets show the high magnified images)
(a-e) 2.5 mA/cm² (f-j) 20 mA/cm²

Fig.12 Crystallographic orientation maps for Q1 alloy (f_{Basal grains} and f_{Non-basal grains}—fractions of basal-oriented grains and non-basal-oriented grains, respectively; D, G, and H—areas similar to the dissolution morphologies indicated by the white dotted line in Fig.11a and red and green dotted lines in Fig.11f, respectively)
(a, e) basal-oriented (a) and non-basal-oriented (e) grains distributions
(b, f) grains that size distributions in the range of 0-14.19 μm (b) and more than 14.19 μm (f)
(c, g) basal-oriented grains that grain size distributions in the range of 0-14.19 μm (c) and more than 14.19 μm (g)
(d, h) non-basal-oriented grains that grain size distributions in the range of 0-14.19 μm (d) and more than 14.19 μm (h)

1	Zou Q, Le Q C, Chen X R, et al. The influence of Ga alloying on Mg-Al-Zn alloys as anode material for Mg-air primary batteries [J]. Electrochim. Acta, 2022, 401: 139372
2	Ma B J, Tan C, Ouyang L Z, et al. Microstructure and discharge performance of Mg-La alloys as the anodes for primary magnesium-air batteries [J]. J. Alloys Compd., 2022, 918: 165803
3	Bao J X, Sha J C, Li L H, et al. Electrochemical properties and discharge performance of Mg-3Sn-xCa alloy as a novel anode for Mg-air battery [J]. J. Alloys Compd., 2023, 934: 167849
4	Tong F L, Chen X Z, Teoh T E, et al. Mg-Sn alloys as anodes for magnesium-air batteries [J]. J. Electrochem. Soc., 2021, 168: 110531
5	Chen X R, Liao Q Y, Le Q C, et al. The influence of samarium (Sm) on the discharge and electrochemical behaviors of the magnesium alloy AZ80 as an anode for the Mg-air battery [J]. Electrochim. Acta, 2020, 348: 136315
6	Chen X R, Zou Q, Le Q C, et al. The quasicrystal of Mg-Zn-Y on discharge and electrochemical behaviors as the anode for Mg-air battery [J]. J. Power Sources, 2020, 451: 227807
7	Chen X R, Zou Q, Shi Z M, et al. The discharge performance of an as-extruded Mg-Zn-La-Ce anode for the primary Mg-air battery [J]. Electrochim. Acta, 2022, 404: 139763
8	Gong C W, Yan X, He X Z, et al. Influence of homogenization treatment on corrosion behavior and discharge performance of the Mg-2Zn-1Ca anodes for primary Mg-air batteries [J]. Mater. Chem. Phys., 2022, 280: 125802
9	Jiang P L, Li D P, Hou R Q, et al. A micro-alloyed Mg-Zn-Ge alloy as promising anode for primary Mg-air batteries [J]. J. Magnes. Alloy., doi: 10.1016/j.jma.2023.05.004
10	Jiang P L, Blawert C, Hou R Q, et al. Microstructural influence on corrosion behavior of MgZnGe alloy in NaCl solution [J]. J. Alloys Compd., 2019, 783: 179
11	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
12	Chen X R, Venezuela J, Shi Z M, et al. Tailoring the discharge performance of extruded Mg-Sm-Al anode for Mg-air battery applications via control of Al content [J]. Mater. Today Energy, 2023, 36: 101363
13	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
14	Xiao L R, Chen X F, Wei K, et al. Effect of dislocation configuration on Ag segregation in subgrain boundary of a Mg-Ag alloy [J]. Scr. Mater., 2021, 191: 219
15	Zerankeshi M M, Alizadeh R. Ag-incorporated biodegradable Mg alloys [J]. Materialia, 2022, 23: 101445
16	Shangguan F E, Cheng W L, Chen Y H, et al. Elucidating the dependence of electrochemical behavior and discharge performance on the grain structure of lean Mg-0.3Bi-0.3Ag-0.3In anodes in primary Mg-air battery [J]. J. Power Sources, 2023, 564: 232856
17	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 doi: 10.11900/0412.1961.2014.00652
	张忠明, 余凯, 任伟伟等. 正挤压态Mg-1Zn-1Ca合金的显微组织及其在SBF溶液中的腐蚀行为 [J]. 金属学报, 2015, 51: 985
18	Wang N G, Huang Y X, Liu J J, et al. AZ31 magnesium alloy with ultrafine grains as the anode for Mg-air battery [J]. Electrochim. Acta, 2021, 378: 138135
19	Wang L Q, Snihirova D, Deng M, et al. Insight into physical interpretation of high frequency time constant in electrochemical impedance spectra of Mg [J]. Corros. Sci., 2021, 187: 109501
20	Tong F L, Chen X Z, Wei S H, et al. Microstructure and battery performance of Mg-Zn-Sn alloys as anodes for magnesium-air battery [J]. J. Magnes. Alloy., 2021, 9: 1967
21	Gong C W, He X Z, Fang D Q, et al. Effect of second phases on discharge properties and corrosion behaviors of the Mg-Ca-Zn anodes for primary Mg-air batteries [J]. J. Alloys Compd., 2021, 861: 158493
22	Li S B, Li H, Zhao C C, et al. Effects of Ca addition on microstructure, electrochemical behavior and magnesium-air battery performance of Mg-2Zn-xCa alloys [J]. J. Electroanal. Chem., 2022, 904: 115944
23	Zhang Y W X, Fan L L, Guo Y Y, et al. Discharge performance of Mg-Y binary alloys as anodes for Mg-air batteries [J]. Electrochim. Acta, 2023, 460: 142594
24	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
25	Tong F L, Chen X Z, Wang Q, et al. Hypoeutectic Mg-Zn binary alloys as anode materials for magnesium-air batteries [J]. J. Alloys Compd., 2021, 857: 157579
26	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
27	Cheng W L, Gu X J, Cheng S M, et al. Discharge performance and electrochemical behaviors of the extruded Mg-2Bi-0.5Ca-0.5In alloy as anode for Mg-air battery [J]. Acta Metall. Sin., 2021, 57: 623
	程伟丽, 谷雄杰, 成世明等. 镁空气电池阳极用挤压态Mg-2Bi-0.5Ca-0.5In合金的放电性能和电化学行为 [J]. 金属学报, 2021, 57: 623 doi: 10.11900/0412.1961.2020.00272
28	Yang L, Shi Y Q, Shen L J, et al. Effect of Ag on cathodic activation and corrosion behaviour of Mg-Mn-Ag alloys [J]. Corros. Sci., 2021, 185: 109408
29	Liu X, Liu S Z, Xue J L. Discharge performance of the magnesium anodes with different phase constitutions for Mg-air batteries [J]. J. Power Sources, 2018, 396: 667
30	Gu X J, Cheng W L, Cheng S M, et al. Tailoring the microstructure and improving the discharge properties of dilute Mg-Sn-Mn-Ca alloy as anode for Mg-air battery through homogenization prior to extrusion [J]. J. Mater. Sci. Technol., 2021, 60: 77

[1]

Download

[1]	LI Dayu, YAO Zhihao, ZHAO Jie, DONG Jianxin, GUO Jing, ZHAO Yu. Evolution of Microstructure and Mechanical Properties of FGH4720Li P/M Superalloy Under Near-Service Conditions[J]. 金属学报, 2025, 61(6): 826-836.
[2]	LIU Ziru, GUO Qianying, ZHANG Hongyu, LIU Yongchang. Effects of V on the Microstructure Evolution and Hardness Enhancement of Ti₂AlNb Alloy[J]. 金属学报, 2025, 61(6): 848-856.
[3]	ZHOU Renyuan, ZHU Lihui. Formation of γ′-Denuded Zone and Its Effect on the Mechanical Properties of Inconel 740H Welded Joint After Creep at Different Temperatures[J]. 金属学报, 2025, 61(5): 744-756.
[4]	LEI Yunlong, YANG Kang, XIN Yue, JIANG Zitao, TONG Baohong, ZHANG Shihong. Microstructure Evolution of Mechanically-Alloying and Its Subsequently-Annealed AlCrCu_0.5Mo_0.5Ni High-Entropy Alloy[J]. 金属学报, 2025, 61(5): 731-743.
[5]	YANG Minghui, LI Xingwu, SUN Chonghao, RUAN Ying. Microstructure and Mechanical Properties of Monel K-500 Alloy in Synergetic Modulation of Directional Solidification and Thermal Processing[J]. 金属学报, 2025, 61(4): 561-571.
[6]	WANG Sheng, ZHU Yancheng, PAN Hucheng, LI Jingren, ZENG Zhihao, QIN Gaowu. Effect of Yb Content on Microstructure and Mechanical Property of Mg-Gd-Y-Zn-Zr Alloy[J]. 金属学报, 2025, 61(3): 499-508.
[7]	JIANG Bin, ZHANG Ang, SONG Jiangfeng, LI Tian, YOU Guoqiang, ZHENG Jiang, PAN Fusheng. Defect Control of Magnesium Alloy Gigacastings[J]. 金属学报, 2025, 61(3): 383-396.
[8]	HUANG Ke, LI Xinzhi, FANG Xuewei, LU Bingheng. State-of-the-Art Progress and Outlook in Wire Arc Additive Manufacturing of Magnesium Alloys[J]. 金属学报, 2025, 61(3): 397-419.
[9]	HAN Qifei, DI Xinglong, GUO Yueling, YE Shuijun, ZHENG Yuanxuan, LIU Changmeng. Microstructure and Mechanical Properties of Mg/Mg Bimetals Fabricated by Wire Arc Additive Manufacturing[J]. 金属学报, 2025, 61(2): 211-225.
[10]	WANG Qitao, LI Yanfen, ZHANG Jiarong, LI Yaozhi, FU Haiyang, LI Xinle, YAN Wei, SHAN Yiyin. Low Cycle Fatigue Behavior of 9Cr-ODS Steel as a Fusion Blanket Structural Material at Room Temperature[J]. 金属学报, 2025, 61(2): 323-335.
[11]	DAI Jincai, MIN Xiaohua, XIN Shewei, LIU Fengjin. Effect of Interstitial Element O on Cryogenic Mechanical Properties in β-Type Ti-15Mo Alloy[J]. 金属学报, 2025, 61(2): 243-252.
[12]	ZHOU Shengyu, HU Minghao, LI Chong, DING Haimin, GUO Qianying, LIU Yongchang. *Creep Behavior of a Ni-Based Superalloy with Strengthening of γ' and γ''* Phases**[J]. 金属学报, 2025, 61(2): 226-234.
[13]	GUO Xingxing, SHUAI Meirong, CHU Zhibing, LI Yugui, XIE Guangming. Microstructure Evolution Near Interface and the Element Diffusion Dynamics of the Composite Stainless Steel Rebar[J]. 金属学报, 2025, 61(2): 336-348.
[14]	ZHU Man, ZHANG Cheng, XU Junfeng, JIAN Zengyun, XI Zengzhe. Microstructure, Mechanical Properties, and High-Temperature Oxidation Behaviors of the CrNbTiVAl _x Refractory High-Entropy Alloys[J]. 金属学报, 2025, 61(1): 88-98.
[15]	YU Dong, MA Weilong, WANG Yali, WANG Jincheng. Phase Field Modeling of Microstructure Evolution During Solidification and Subsequent Solid-State Phase Transformation of Au-Pt Alloys[J]. 金属学报, 2025, 61(1): 109-116.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed