Clarifying the roles of grain boundary and grain orientation on the corrosion and discharge processes of α-Mg based Mg-Li alloys for primary Mg-air batteries

doi:10.1016/j.jmst.2020.05.067

Abstract

Abstract:

The corrosion behavior at open circuit potential (OCP) and discharge properties under applied anodic currents of two α-Mg based Mg-Li alloys, i.e., LAZ131 and LAZ531, with different microstructural features for primary Mg-air batteries are investigated. The results show that the grain boundaries contribute equally to the corrosion and discharge processes, which are attacked preferentially than the grain interiors and accelerate the dissolution processes of α-Mg based Mg-Li alloys. The (10-10)/(11-20) orientated grains are attacked preferentially than the (0002) orientated grains on the corrosion and discharge process. The increased corrosion rate and improved discharge properties are attributed to the refinement of grain size, decreased content of (0002) orientated grains and increased content of (10-10)/(11-20) orientated grains. Of those, the LAZ531 alloy possesses high and steady discharge voltage at small discharge current density for long time, with the values of 1.4801 V at 2.5 mA cm^-2 and 1.3742 V at 10 mA cm^-2.

Key words: Grain boundary, Grain orientation, Corrosion behavior, Discharge property, Mg-air battery

Huabao Yang, Liang Wu, Bin Jiang, Wenjun Liu, Jiangfeng Song, Guangsheng Huang, Dingfei Zhang, Fusheng Pan. Clarifying the roles of grain boundary and grain orientation on the corrosion and discharge processes of α-Mg based Mg-Li alloys for primary Mg-air batteries[J]. J. Mater. Sci. Technol., 2021, 62: 128-138.

Figures/Tables 12

Table 1 Chemical compositions of LAZ131 and LAZ531 alloys (wt%).

Element	LAZ131	LAZ531
Li	0.99	5.10
Al	2.64	2.70
Zn	0.70	0.79
Mn	0.06	0.05
Fe	0.0028	0.0028
Cu	0.0006	0.0001
Si	0.0053	0.0051
Ni	<0.0001	<0.0001
Mg	Bal.	Bal.

Fig. 1. BSE images of LAZ131 (a) and LAZ531 (b) alloys; EDS result of the second phase particles (c) and XRD patterns (d) of the two alloys.

Fig. 2. Optical micrographs (a, c), corresponding grain size distributions (b, d), and (0002) pole figures (e, f) of LAZ131 (a, b, e) and LAZ531 (c, d, f) alloys.

Fig. 3. Hydrogen evolution curves (a), corrosion rates measured from hydrogen evolution and weight loss (b), potentiodynamic polarization curves (c), and Nyquist plots (d) for LAZ131 and LAZ531 alloys. The equivalent circuit used for fitting the EIS results (e).

Table 2 Parameters evaluated from the potentiodynamic polarization curves of LAZ131 and LAZ531 alloys.

Alloys	E_corr (V_SCE)	b_a (mV dec^-1)	i_corr (mA cm^-2)	P_i (mm y^-1)
LAZ131	-1.433	16.33	0.073 ± 0.002	1.67 ± 0.04
LAZ531	-1.480	15.52	0.132 ± 0.005	3.02 ± 0.11

Table 3 Parameters extracted from the EIS results.

Parameter	LAZ131	LAZ531
R_s (Ω cm²)	8.4	3.5
R_ct (Ω cm²)	2095	650
Y₁ (sⁿ Ω^-1 cm^-2)	1.25 × 10^-5	1.25 × 10^-5
n₁	0.92	0.93
R_f (Ω cm²)	1400	400
Y₂ (sⁿ Ω^-1 cm^-2)	1.19 × 10^-3	3.21 × 10^-3
n₂	0.83	0.89

Fig. 4. Galvanostatic discharge curves of Mg-air batteries based on LAZ131 and LAZ531 alloys at the current densities of 2.5 mA cm-2 for 10 h (a) and 10 mA cm-2 for 5 h (b).

Table 4 Average discharge voltages and anodic efficiencies of Mg-air batteries based on the two alloys during galvanostatic discharged at 2.5 mA cm-2 and 10 mA cm-2.

Alloys	Average discharge voltage (V)		Anodic efficiency (%)
Alloys	At 2.5 mA cm^-2	At 10 mA cm^-2	At 2.5 mA cm^-2	At 10 mA cm^-2
LAZ131	1.4589 ± 0.008	1.3037 ± 0.013	32.8 ± 0.7	44.3 ± 1.1
LAZ531	1.4801 ± 0.009	1.3742 ± 0.015	38.3 ± 0.8	48.7 ± 1.3

Fig. 5. Corrosion morphologies of LAZ131 (a, b) and LAZ531 (c, d) alloys after immersion in 3.5 wt% NaCl solution for 2 h (a, c) and 12 h (b, d).

Fig. 6. Grain boundaries morphologies of LAZ531I (a, b) and LAZ531II (c, d) samples.

Fig. 7. SE images of the surface morphologies for the two alloys discharged at 2.5 mA cm-2 for 10 h: (a, b) LAZ131 alloys; (c, d) LAZ531 alloys.

Fig. 8. SE images of the surface morphologies for the two alloys discharged at 10 mA cm-2 for 5 h: (a, b) LAZ131 alloys; (c, d) LAZ531 alloys.

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