Superior electrochemical performance of La-Mg-Ni-based alloys with novel A2B7-A7B23 biphase superlattice structure

doi:10.1016/j.jmst.2020.10.081

Abstract

Abstract:

Nickel metal hydride (Ni-MH) rechargeable batteries hold an important position in the new-energy vehicle market owing to their key technology advantages. Their negative electrode materials—hydrogen storage alloys (HSAs) are always on the spotlight and are the key to compete with the burgeoning Li-ion batteries. Here, for the first time we report a series of biphase supperlattice HSAs with a (La,Mg)₂Ni₇ matrix phase and a novel (La,Mg)₇Ni₂₃ secondary phase. The biphase alloys show discharge capacities of 402-413 mAh g^-1 compared with 376-397 mAh g^-1 of the other multi- or single-phase alloys. These values are among the highest for superlattice HSAs. In addition, the alloy with 15.4 wt.% (La,Mg)₇Ni₂₃ phase exhibits good high rate dischargeability due to the proper compromise between the amount of crystal boundaries and equilibrium plateau voltage. The cycling stability of the biphase alloys is lower than that of the single-phase alloy but is till higher than the multiphase alloy. The novel superlattice biphase alloys with superior overall electrochemical properties are expected to inspire further design and development of HSAs as advanced electrode materials for power batteries.

Key words: Nickel metal hydride battery, Hydrogen storage alloy, A₇B₂₃-type phase, Electrochemical property, Effect mechanism

Jingjing Liu, Shuai Zhu, Xiangyu Chen, Jie Xu, Lu Zhang, Kai Yan, Wei Chen, Honghui Cheng, Shumin Han. Superior electrochemical performance of La-Mg-Ni-based alloys with novel A₂B₇-A₇B₂₃ biphase superlattice structure[J]. J. Mater. Sci. Technol., 2021, 80: 128-138.

Figures/Tables 11

Fig. 1. Preparation steps of nickel container (a)-(d), heat treatment equipment and procedures (e), Mg contents (f) and B/A ratios (g) of the alloy samples.

Fig. 2. XRD patterns in 2 Theta range of 20-90 degree (a) and 25-41 degree (b) of #M, #T, #B1-#B3 and #S alloys, superlattice crystal structure of (La,Mg)7Ni23 phase (c), phase abundance from Rietveld refinements (d) and back-scattered SEM image of #B1 alloy (e).

Table 1 Phase abundance, lattice parameters, and cell volumes of the alloy samples.

Samples	Phases	Phase abundance (wt.%)	a (Å)	c (Å)	V (Å³)
#M	LaMgNi₄	3.7	7.184	——	321.14
	3R-(La,Mg)Ni₃	32.9	5.041	24.306	534.81
	2H-(La,Mg)₂Ni₇	29.9	5.038	24.277	533.67
	3R-(La,Mg)₂Ni₇	17.3	5.039	36.416	800.59
	3R-(La,Mg)₅Ni₁₉	8.5	5.035	48.531	1065.57
	LaNi₅	7.7	5.038	3.988	87.65
#T	3R-(La,Mg)Ni₃	24.7	5.036	24.356	534.94
	2H-(La,Mg)₂Ni₇	57.7	5.038	24.298	534.02
	3R-(La,Mg)₂Ni₇	17.6	5.035	36.508	801.63
#B1	(La,Mg)₇Ni₂₃	44.3	5.040	40.578	892.52
	2H-(La,Mg)₂Ni₇	55.7	5.038	24.325	534.71
#B2	(La,Mg)₇Ni₂₃	25.6	5.037	40.540	890.83
	2H-(La,Mg)₂Ni₇	74.4	5.037	24.328	534.60
#B3	(La,Mg)₇Ni₂₃	15.4	5.038	40.587	892.00
	2H-(La,Mg)₂Ni₇	84.6	5.038	24.318	534.42
#S	2H-(La,Mg)₂Ni₇	100	5.038	24.296	533.96

Fig. 3. SAED pattern (a) and HR image (b) of #B1 alloy.

Fig. 4. Activation curves of the #M, #T, #B1-#B3 and #S alloy electrodes (a), XRD pattern of the #B1 alloy at full charge state (b), discharge curves of #B1-#B3 and #S alloy electrodes at the 4th cycle (c) and XRD pattern of the #B1 alloy at complete discharge state (d).

Table 2 Electrochemical properties of the alloy electrodes.

Samples	Activation cycle	C_max (mA g^-1)	S₁₀₀ (%)	HRD₁₅₀₀ (%)
#M	2	376	70.6	52.2
#T	2	397	80.5	49.2
#B1	2	402	79.1	47.5
#B2	2	408	82.0	48.8
#B3	2	413	81.0	52.7
#S	2	394	87.7	47.0

Fig. 5. Cycling stability curves of the #M, #T, #B1-#B3 and #S alloy electrodes (a), Tafel curves of #B1 and #S alloy electrodes (b) and surface morphologies of #B1 (c) and #S (d) alloy particles after 100 cycles.

Fig. 6. SEM images of #B1 (a1-a4) and #S (b1-b4) alloy particles, particle size distribution curves of #B1 and #S (c) after different cycles, and XRD patterns of #B1 and #S alloy powder after 20 cycles (d).

Fig. 7. HRD property of the #M, #T, #B1-#B3 and #S alloy electrodes at various discharge current densities (a), and XRD patterns of #B1 alloy powder at different discharge states (b).

Fig. 8. Linear polarization curves (a), EIS curves (b), anode polarization curves (c) and constant potential step curves (d) of #B1-#B3 and #S alloy electrodes.

Table 3 Kinetics parameters of #B1-#B3 and #S alloy electrodes.

Samples	R_ct (mΩ)	I₀ (mA g^-1)	I_L (mA g^-1)	D (10^-10 cm² s^-1)
#B1	258.9	282.8	2693	1.16
#B2	251.6	297.8	2871	1.21
#B3	241.0	317.4	3145	1.32
#S	262.1	278.3	2483	1.13

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Superior electrochemical performance of La-Mg-Ni-based alloys with novel A₂B₇-A₇B₂₃ biphase superlattice structure

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