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

doi:10.1016/j.jmst.2020.04.057

Abstract

Abstract:

Mg-0.5Sn-0.5 Mn-0.5Ca (wt.%) alloys with different microstructures are designed through casting and extrusion with and without homogenization treatment prior to extrusion (HPE). The influence of HPE treatment on the microstructural characteristics and resultant discharge properties of Mg-Sn-Mn-Ca alloy in extruded condition as anode for Mg-air battery was investigated. HPE treatment exerts a prominent effect on the grain structure and orientation, distribution of the second phase particles as well as the dislocation density of the extruded alloy. The HPE alloy exhibits a distinctly high cell voltage together with specific energy compared with that of Non-HPE one. Intermittent discharge tests confirm that the HPE alloy possesses a more excellent discharge activity and more stable discharge process than the Non-HPE one. All results demonstrate that the HPE alloy is an attractive anode material for Mg-air battery with long-term storage and under intermittent discharge.

Key words: Mg-air battery, Homogenization prior to extrusion, Microstructure, Discharge property, Intermittent discharge

Xiong-jie Gu, Wei-li Cheng, Shi-ming Cheng, Yan-hui Liu, Zhi-feng Wang, Hui Yu, Ze-qin Cui, Li-fei Wang, Hong-xia Wang. 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: 77-89.

Figures/Tables 19

Fig. 1. Crystallographic orientation maps, (0001) pole figures, and grain size distributions of the investigated alloys: (a, b and c) Non-HPE alloy and (d, e and f) HPE alloy.

Fig. 2. SEM and TEM images of the investigated alloys: (a, b and c) Non-HPE alloy and (d, e and f) HPE alloy.

Fig. 3. (a) Open circuit potentials, (b) polarization curves and (c) anodic branches of the polarization curves for Non-HPE and HPE alloys.

Table 1 Electrochemical parameters evaluated from the polarization curves.

Specimen	E_OCP(V)	E_corr(V)	J_corr(μA/cm²)	β_a (mV)	β_c(mV)	R_p(Ω cm²)
Non-HPE	-1.620	-1.502	14.6	15.34	206.00	425.16
HPE	-1.641	-1.555	21.6	14.28	239.98	271.30

Fig. 4. EIS in Nyquist plots of the investigated alloys under different conditions at (a) OCPs and (b) the potentials of 100 mV more positive than OCPs and (c) equivalent circuit.

Table 2 Impedance parameters of the investigated alloys by fitting the EIS.

Potential	Specimen	R_s	R_ct	CPE		L	R_L
Potential	Specimen	Ω cm²	Ω cm²	Y/Ω^-1 cm² sⁿ	n_dl	H cm²	Ω cm²
OCP	Non-HPE	0.183	792.4	2.61 × 10^-5	0.91	2270	424
OCP	HPE	0.134	566.4	1.78 × 10^-5	0.92	1256	126
OCP +100 mV	Non-HPE	0.155	131.2	6.99 × 10^-6	0.84	564	70
OCP +100 mV	HPE	0.135	70.71	7.78 × 10^-6	0.89	329	28

Fig. 5. Discharge curves of the investigated alloys: (a) Non-HPE alloy and (b) HPE alloy.

Fig. 6. (a) Cell voltage and power density and (b) specific capacity and energy density for Non-HPE and HPE alloys.

Table 3 The anodic efficiencies for Non-HPE and HPE alloys.

Specimen	Anodic efficiency, η (%)
Specimen	2.5 mA cm^-2	5 mA cm^-2	10 mA cm^-2	20 mA cm^-2	40 mA cm^-2
Non-HPE	29.63	37.25	45.83	52.75	55.85
HPE	30.17	39.10	48.20	56.44	59.31

Fig. 7. Intermittent discharge curves at 2.5 mA cm-2 for Non-HPE and HPE alloys.

Fig. 8. Crystallographic orientation maps and (0001) pole figures of the basal planes for Non-HPE and HPE alloys: (a and b) Non-HPE alloy and (c and d) HPE alloy.

Fig. 9. The morphologies for the investigated alloys with discharge products after discharge for 1 h at (a and d) 2.5 mA cm-2 and (b, c, e and f) 20 mA cm-2: (a, b and c) Non-HPE alloy and (d, e and f) HPE alloy.

Fig. 10. XPS analysis of discharge products for Non-HPE and HPE alloys.

Fig. 11. The surface morphologies of the Non-HPE alloy discharged at different current densities for 10 h after removing the discharge products: (a, b and c) 2.5 mA cm-2, (d, e and f) 5 mA cm-2, (g, h and i) 10 mA cm-2 and (j, k and c) 20 mA cm-2.

Fig. 12. The surface morphologies of the HPE alloy discharged at different current densities for 10 h after removing the discharge products: (a, b and c) 2.5 mA cm-2, (d, e and f) 5 mA cm-2, (g, h and i) 10 mA cm-2 and (j, k and c) 20 mA cm-2.

Fig. 13. 3D morphologies of the Non-HPE and HPE alloys after discharge at 20 mA cm-2 for 10 h.

Fig. 14. The surface morphologies of the investigated alloys without discharge products after discharge at 2.5 mA cm-2 for (a and d) 1 min and (b and e) 10 min; (c and f) Discharge at 20 mA cm-2 for 10 min: (a, b and c) Non-HPE alloy and (d, e and f) HPE alloy.

Fig. 15. Crystallographic orientation maps and (0001) pole figures of the investigated alloys: (a, b, e, f, i and c) Non-HPE alloy and (c, d, g, h, k and l) HPE alloy. (a-d) grain size distribution in the range of 0-5 μm, (e-h) grain size distribution in the range of 5-10 μm, (i-l) grain size distribution in the range of 10-15 μm, (m-p) grain size distribution in the range of more than 15 μm.

Fig. 16. Schematic illustration of the dissolution process of Mg matrix during discharge.

References 56

[1]	X. Liu, J. Xue, S. Liu, Mater. Design 160 (2018) 138-146.
[2]	M.A. Rahman, X. Wang, C. Wen, J. Electrochem. Soc. 160 (10) (2013) A1759-A1771.
[3]	T. Zhang, Z. Tao, J. Chen, Mater. Horiz. 1 (2) (2014) 196-206. DOI URL
[4]	T. Zheng, Y. Hu, Y. Zhang, S. Yang, F. Pan, Mater. Design 137 (2018) 245-255.
[5]	M. Yuasa, X. Huang, K. Suzuki, M. Mabuchi, Y. Chino, J. Power Sources 297 (2015) 449-456.
[6]	N. Wang, R. Wang, C. Peng, B. Peng, Y. Feng, C. Hu, Electrochim. Acta 149 (2014) 193-205. DOI URL
[7]	S. Shi, J. Gao, Y. Liu, Y. Zhao, Q. Wu, W. Ju, C. Ouyang, R. Xiao, Chin. Phys. B 25 (1) (2016), 018212.
[8]	X. Chen, S. Ning, Q. Le, H. Wang, Q. Zou, R. Guo, J. Hou, Y. Jia, A. Atrens, F. Yu, J. Mater. Sci. Technol. 38(2020) 47-55.
[9]	N. Wang, W. Li, Y. Huang, G. Wu, M. Hu, G. Li, Z. Shi, J. Power Sources 436 (2019). DOI URL PMID
[10]	H. Xiong, K. Yu, X. Yin, Y. Dai, Y. Yan, H. Zhu, J. Alloys. Compd. 708(2017) 652-661.
[11]	X. Liu, J. Xue, D. Zhang, J. Alloys. Compd. 790(2019) 822-828.
[12]	Y. Feng, W. Xiong, J. Zhang, R. Wang, N. Wang, J. Mater. Chem. A 4 (22) (2016) 8658-8668.
[13]	X. Li, H. Lu, S. Yuan, J. Bai, J. Wang, Y. Cao, Q. Hong, J. Electrochem. Soc. 164 (13) (2017) A3131-A3137.
[14]	Y. Feng, G. Lei, Y. He, R. Wang, X. Wang, Trans. Nonferrous Met. Soc. China 28 (11) (2018) 2274-2286.
[15]	Y. Wu, Int. J. Electrochem. Soc, (2018) 10325-10338.
[16]	N. Wang, R. Wang, Y. Feng, W. Xiong, J. Zhang, M. Deng, Corros. Sci. 112(2016) 13-24.
[17]	X. Liu, S. Liu, J. Xue, J. Power Sources 396 (2018) 667-674. DOI URL
[18]	G.-L. Song, R. Mishra, Z. Xu, Electrochem. commun. 12 (8) (2010) 1009-1012. DOI URL
[19]	M. Yuasa, X. Huang, K. Suzuki, M. Mabuchi, Y. Chino, Mater. Trans. 55 (8) (2014) 1202-1207.
[20]	Y. Wu, Z. Wang, Y. Liu, G. Li, S. Xie, H. Yu, H. Xiong, J. Mater. Eng. Perform. 28 (4) (2019) 2006-2016.
[21]	G. Huang, Y. Zhao, Y. Wang, H. Zhang, F. Pan, Mater. Lett. 113(2013) 46-49.
[22]	M. Deng, D. Höche, S.V. Lamaka, L. Wang, M.L. Zheludkevich, Corros. Sci. 153(2019) 225-235.
[23]	M. Deng, D. Höche, S.V. Lamaka, D. Snihirova, M.L. Zheludkevich, J. Power Sources 396 (2018) 109-118. DOI URL
[24]	N. Shrestha, K.S. Raja, V. Utgikar, J. Electrochem. Soc. 166 (14) (2019) A3139-A3153.
[25]	X. Liu, J. Xue, P. Zhang, Z. Wang, J. Power Sources 414 (2019) 174-182.
[26]	H. Xiong, L. Li, Y. Zhang, K. Yu, H. Fang, Y. Dai, H. Dai, J. Electrochem. Soc. 164 (7) (2017) A1745-A1754.
[27]	S. Yuan, H. Lu, Z. Sun, L. Fan, X. Zhu, W. Zhang, J. Electrochem. Soc. 163 (7) (2016) A1181-A1187. DOI URL
[28]	Y. Ma, N. Li, D. Li, M. Zhang, X. Huang, J. Power Sources 196 (4) (2011) 2346-2350.
[29]	X. Liu, J. Xue, Energy 189 (2019), 116314.
[30]	X. Liu, Z. Guo, J. Xue, P. Zhang, Int. J. Energ. Res. 43(2019) 4569-4579. DOI URL
[31]	M. Hao, W. Cheng, L. Wang, E. Mostaed, L. Bian, H. Wang, X. Niu, Mat. Sci. Eng. A 748 (2019) 418-427.
[32]	X. Gu, W. Cheng, S. Cheng, H. Yu, Z. Wang, H. Wang, L. Wang, J. Electrochem. Soc. 167(2020) 20501. DOI URL
[33]	D. Cao, L. Wu, G. Wang, Y. Lv, J. Power Sources 183 (2) (2008) 799-804. DOI URL
[34]	S. Cheng, W. Cheng, X. Gu, H. Yu, Z. Wang, H. Wang, L. Wang, J. Alloys. Compd. 823(2020), 153779.
[35]	N. Wang, R. Wang, C. Peng, Y. Feng, Corros. Sci. 81(2014) 85-95.
[36]	J.-G. Jung, S.H. Park, H. Yu, Y.M. Kim, Y.-K. Lee, B.S. You, Scripta Mater 93 (2014) 8-11.
[37]	W. Cheng, L. Tian, H. Wang, L. Bian, H. Yu, Mat. Sci. Eng. A 687 (2017) 148-154. DOI URL
[38]	L. Zhong, Y. Wang, H. Luo, X. Cui, Y. Zhang, B. Dou, J. Peng, J. Alloys. Compd. 780(2019) 783-791. DOI URL
[39]	X.Q. Zeng, D.H. Li, J. Dong, C. Lu, W.J. Ding, J. Alloys. Compd. 456 (1-2) (2008) 419-424.
[40]	M.C. Lin, C.Y. Tsai, J.Y. Uan, Corros. Sci. 51 (10) (2009) 2463-2472. DOI URL
[41]	H. Miao, H. Huang, Y. Shi, H. Zhang, J. Pei, G. Yuan, Corros. Sci. 122(2017) 90-99. DOI URL
[42]	Y. Chai, B. Jiang, J. Song, Q. Wang, H. Gao, B. Liu, G. Huang, D. Zhang, F. Pan, J. Alloys. Compd. 782(2019) 1076-1086.
[43]	D. Chen, Y.-p. Ren, Y. Guo, W.-l. Pei, H.-d. Zhao, G.-w. Qin, Trans. Nonferrous Met. Soc. China 20 (7) (2010) 1321-1325.
[44]	W. Cheng, Y. Bai, L. Wang, H. Wang, L. Bian, H. Yu, Materials 10 (7) (2017). URL PMID
[45]	C. Fang, Z. Wen, X. Liu, H. Hao, G. Chen, X. Zhang, Mat. Sci. Eng. A 684 (2017) 229-232.
[46]	T. Zhang, Y. Shao, G. Meng, Z. Cui, F. Wang, Corros. Sci. 53 (5) (2011) 1960-1968. DOI URL
[47]	Y. Liu, W. Cheng, Y. Zhao, X. Niu, H. Wang, L. Wang, J. Alloys. Compd. 815(2020), 152414. DOI URL
[48]	H. Jia, X. Feng, Y. Yang, J. Mater. Sci. Technol. 34 (7) (2018) 1229-1235. DOI URL
[49]	S.-M. Baek, J.S. Kang, J.C. Kim, B. Kim, H.-J. Shin, S.S. Park, Corros. Sci. 141(2018) 203-210. DOI URL
[50]	L. Hou, Z. Li, H. Zhao, Y. Pan, S. Pavlinich, X. Liu, X. Li, Y. Zheng, L. Li, J. Mater. Sci. Technol. 32 (9) (2016) 874-882.
[51]	Q. Luo, Y. Guo, B. Liu, Y. Feng, J. Zhang, Q. Li, K. Chou, J. Mater. Sci. Technol. 44(2020) 171-190. DOI URL
[52]	N. Wang, R. Wang, C. Peng, Y. Feng, B. Chen, Corros. Sci. 64(2012) 17-27.
[53]	D. Song, A. Ma, J. Jiang, P. Lin, D. Yang, J. Fan, Corros. Sci. 52 (2) (2010) 481-490. DOI URL
[54]	J. Wu, R. Wang, Y. Feng, C. Peng, J. Alloys. Compd. 765(2018) 736-746. DOI URL
[55]	Y. Luo, Y. Deng, L. Guan, L. Ye, X. Guo, A. Luo, Corros. Sci. 164(2020), 108338. DOI URL
[56]	K.D. Ralston, N. Birbilis, C.H.J. Davies, Scripta. Mater. 63 (12) (2010) 1201-1204. DOI URL