Studies on Incorporation of Mg in Zr-Based AB2 Metal Hydride Alloys
Abstract
:1. Introduction
2. Experimental Setup
3. Results and Discussion
3.1. X-Ray Diffractometer Analysis
3.2. Scanning Electron Microscope/Energy Dispersive Spectroscopy Analysis
3.3. Pressure-Concentration-Temperature Analysis
3.4. Electrochemical Analysis
3.5. Magnetic Properties
3.6. Correlations
4. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
Abbreviations
MH | Metal hydride |
ICP-OES | Inductively coupled plasma-optical emission spectrometer |
XRD | X-ray diffractometer |
SEM | Scanning electron microscope |
EDS | Energy dispersive spectroscopy |
PCT | Pressure-concentration-temperature |
e/a | Average electron density |
ND | Non-detectable |
BEI | Back-scattering electron image |
DOD | Degree of disorder |
D | Diffusion constant |
Io | Surface exchange current |
Ms | Saturated magnetic susceptibility |
H1/2 | Magnetic field strength at one-half of the Ms value |
RT | Room temperature |
References
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Alloy | Source | Zr | Ti | V | Cr | Mn | Co | Ni | Mg | Sn | Al | e/a | B/A |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Mg0 | Design | 21.5 | 12.0 | 10.0 | 7.5 | 8.1 | 8.0 | 32.2 | 0.0 | 0.3 | 0.4 | 6.82 | 1.99 |
ICP | 21.5 | 12.0 | 10.0 | 7.5 | 8.1 | 8.0 | 32.2 | 0.0 | 0.4 | 0.3 | 6.82 | 1.99 | |
Mg1 | Design | 21.5 | 11.4 | 10.0 | 7.5 | 8.1 | 8.0 | 31.8 | 1.0 | 0.3 | 0.4 | 6.78 | 1.95 |
ICP | 21.0 | 11.3 | 10.0 | 7.5 | 8.3 | 8.1 | 32.2 | 0.6 | 0.3 | 0.7 | 6.82 | 2.04 | |
Mg2 | Design | 21.5 | 10.8 | 10.0 | 7.5 | 8.1 | 8.0 | 31.4 | 2.0 | 0.3 | 0.4 | 6.73 | 1.92 |
ICP | 22.5 | 10.9 | 9.9 | 7.2 | 8.2 | 8.0 | 31.8 | 0.8 | 0.3 | 0.4 | 6.78 | 1.92 | |
Mg3 | Design | 21.5 | 10.2 | 10.0 | 7.5 | 8.1 | 8.0 | 31.0 | 3.0 | 0.3 | 0.4 | 6.69 | 1.88 |
ICP | 21.5 | 10.5 | 10.3 | 7.3 | 8.4 | 8.4 | 32.0 | 0.7 | 0.3 | 0.6 | 6.82 | 2.06 | |
Mg4 | Design | 21.5 | 9.6 | 10.0 | 7.5 | 8.1 | 8.0 | 30.6 | 4.0 | 0.3 | 0.4 | 6.65 | 1.85 |
ICP | 21.0 | 9.6 | 9.8 | 6.9 | 8.3 | 8.2 | 34.7 | 0.6 | 0.3 | 0.6 | 6.96 | 2.21 | |
Mg5 | Design | 21.5 | 9.0 | 10.0 | 7.5 | 8.1 | 8.0 | 30.2 | 5.0 | 0.3 | 0.4 | 6.60 | 1.82 |
ICP | 20.5 | 8.6 | 9.6 | 7.0 | 8.0 | 7.9 | 36.7 | 0.8 | 0.3 | 0.6 | 7.05 | 2.34 |
Alloy | Mg0 | Mg1 | Mg2 | Mg3 | Mg4 | Mg5 |
C14 a (Å) | 4.9545 | 4.9566 | 4.9727 | 4.9593 | 4.9555 | 4.9473 |
C14 c (Å) | 8.0733 | 8.0781 | 8.1082 | 8.0846 | 8.0738 | 8.0586 |
C14 a/c | 0.6137 | 0.6136 | 0.6133 | 0.6134 | 0.6138 | 0.6139 |
C14 unit cell volume (Å3) | 171.63 | 171.87 | 173.64 | 172.20 | 171.71 | 170.82 |
C14 crystallite size (Å) | 685 | 518 | 400 | 385 | 398 | 373 |
C15 a (Å) | 6.9932 | 6.9894 | 7.0098 | 6.9926 | 6.9770 | 6.9628 |
TiNi a (Å) | 3.0667 | 3.0674 | 3.0914 | 3.0687 | 3.0590 | ND |
Mg-related cubic a (Å) | ND | 4.6553 | 4.6655 | 4.6670 | 4.6567 | 4.6711 |
Alloy | C14 Abundance (%) | C15 Abundance (%) | TiNi Abundance (%) | Cubic Abundance (%) |
---|---|---|---|---|
Mg0 | 93.7 | 5.2 | 1.2 | ND |
Mg1 | 81.8 | 15.9 | 2.0 | 0.3 |
Mg2 | 88.3 | 7.9 | 3.5 | 0.3 |
Mg3 | 72.0 | 25.1 | 2.4 | 0.5 |
Mg4 | 56.5 | 42.2 | 1.0 | 0.4 |
Mg5 | 36.9 | 62.6 | ND | 0.5 |
Area | Zr | Ti | V | Cr | Mn | Co | Ni | Mg | Sn | Al | e/a | B/A | Phase |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Mg1-1 | 20.4 | 10.5 | 11.1 | 8.6 | 8.8 | 8.7 | 31.0 | 0.2 | 0.2 | 0.5 | 6.83 | 2.22 | C14 |
Mg1-2 | 21.0 | 12.2 | 6.9 | 4.2 | 6.2 | 6.1 | 41.9 | 0.1 | 0.8 | 0.6 | 7.15 | 2.00 | C15 |
Mg1-3 | 16.9 | 23.4 | 2.4 | 1.3 | 3.1 | 5.9 | 45.2 | 0.3 | 1.1 | 0.4 | 7.14 | 1.33 | TiNi |
Mg1-4 | 9.9 | 8.4 | 4.6 | 2.7 | 3.6 | 3.6 | 20.0 | 46.6 | 0.4 | 0.2 | 4.65 | 0.54 | Mg-cubic |
Mg1-5 | 27.5 | 12.1 | 2.2 | 1.0 | 2.5 | 3.2 | 42.0 | 0.3 | 8.9 | 0.3 | 6.79 | 1.05 | ZrNi |
Mg2-1 | 21.9 | 9.9 | 11.9 | 8.0 | 9.1 | 8.7 | 29.4 | 0.3 | 0.2 | 0.6 | 6.74 | 2.12 | C14 |
Mg2-2 | 22.8 | 11.6 | 6.7 | 3.7 | 6.4 | 6.2 | 40.9 | 0.4 | 0.8 | 0.5 | 7.08 | 1.87 | C15 |
Mg2-3 | 20.7 | 21.4 | 1.4 | 0.5 | 2.3 | 6.0 | 45.5 | 1.2 | 0.5 | 0.5 | 7.09 | 1.24 | TiNi |
Mg2-4 | 12.9 | 5.7 | 2.0 | 1.0 | 2.0 | 2.3 | 16.1 | 57.2 | 0.7 | 0.0 | 4.03 | 0.32 | Mg-cubic |
Mg2-5 | 29.0 | 11.7 | 1.8 | 0.9 | 2.5 | 3.4 | 41.5 | 0.9 | 7.7 | 0.5 | 6.74 | 1.03 | ZrNi |
Mg3-1 | 20.6 | 9.8 | 11.9 | 7.4 | 9.3 | 9.1 | 31.0 | 0.3 | 0.2 | 0.4 | 6.85 | 2.26 | C14 |
Mg3-2 | 20.4 | 12.2 | 7.2 | 3.2 | 6.5 | 6.3 | 42.5 | 0.5 | 0.7 | 0.5 | 7.18 | 2.02 | C15 |
Mg3-3 | 15.6 | 25.7 | 1.7 | 0.4 | 2.6 | 5.8 | 45.6 | 1.3 | 0.8 | 0.6 | 7.10 | 1.26 | TiNi |
Mg3-4 | 9.2 | 2.7 | 0.4 | 0.2 | 0.5 | 0.6 | 4.2 | 82.1 | 0.1 | 0.0 | 2.66 | 0.06 | Mg-cubic |
Mg3-5 | 30.7 | 9.4 | 1.0 | 0.6 | 1.9 | 2.2 | 41.1 | 1.1 | 11.7 | 0.4 | 6.63 | 0.89 | ZrNi |
Mg3-6 | 95.2 | 1.8 | 0.3 | 0.2 | 0.4 | 0.3 | 1.7 | 0.1 | 0.0 | 0.0 | 4.13 | 0.03 | Zr |
Mg3-7 | 78.1 | 5.4 | 2.4 | 1.3 | 1.9 | 2.0 | 8.4 | 0.2 | 0.2 | 0.0 | 4.70 | 0.19 | ZrO2 |
Mg4-1 | 22.4 | 7.1 | 12.1 | 12.3 | 10.1 | 9.9 | 25.4 | 0.3 | 0.1 | 0.3 | 6.68 | 2.36 | C14 |
Mg4-2 | 19.3 | 12.6 | 7.9 | 3.9 | 6.7 | 6.6 | 41.7 | 0.3 | 0.5 | 0.5 | 7.18 | 2.11 | C15 |
Mg4-3 | 13.8 | 26.8 | 2.0 | 0.6 | 3.0 | 5.8 | 45.8 | 0.7 | 1 | 0.5 | 7.14 | 1.31 | TiNi |
Mg4-4 | 7.1 | 8.9 | 2.0 | 0.9 | 2.1 | 2.6 | 19.6 | 56.0 | 0.6 | 0.1 | 4.28 | 0.39 | Mg-cubic |
Mg4-5 | 26.6 | 11.5 | 2.7 | 1.1 | 3.1 | 2.8 | 42.8 | 0.6 | 8.4 | 0.4 | 6.83 | 1.12 | ZrNi |
Mg4-6 | 95.1 | 1.6 | 0.3 | 0.2 | 0.3 | 0.3 | 1.9 | 0.2 | 0.0 | 0.0 | 4.14 | 0.03 | Zr |
Mg5-1 | 21.8 | 6.3 | 11.1 | 11.9 | 9.4 | 9.8 | 28.8 | 0.3 | 0.1 | 0.4 | 6.84 | 2.52 | C14 |
Mg5-2 | 17.6 | 11.7 | 8.6 | 4.0 | 7.2 | 6.4 | 42.8 | 0.7 | 0.4 | 0.6 | 7.25 | 2.33 | C15 |
Mg5-3 | 8.4 | 28.8 | 3.3 | 0.8 | 3.9 | 6.1 | 45.4 | 1.0 | 1.2 | 1.0 | 7.16 | 1.41 | TiNi |
Mg5-4 | 12.9 | 8.0 | 3.0 | 1.0 | 2.4 | 2.2 | 24.4 | 45.4 | 0.6 | 0.2 | 4.79 | 0.51 | Mg-cubic |
Mg5-5 | 25.4 | 13.0 | 1.8 | 0.7 | 2.1 | 2.1 | 44.5 | 0.3 | 9.9 | 0.3 | 6.87 | 1.06 | ZrNi |
Mg5-6 | 83.6 | 4.8 | 1.0 | 0.7 | 0.8 | 0.7 | 7.8 | 0.2 | 0.5 | 0.0 | 4.55 | 0.13 | Zr |
Alloy | Mg0 | Mg1 | Mg2 | Mg3 | Mg4 | Mg5 |
Maximum capacity @ 30 °C (wt%) | 1.45 | 1.42 | 1.54 | 1.41 | 1.25 | 0.89 |
Reversible capacity @ 30 °C (wt%) | 1.32 | 1.32 | 1.33 | 1.30 | 1.16 | 0.87 |
Desorption pressure @ 0.75 wt%, 30 °C (MPa) | 0.078 | 0.096 | 0.026 | 0.102 | 0.246 | 1.203 |
SF @ 30 °C | 0.60 | 0.54 | 0.55 | 0.51 | 0.38 | 0.18 |
PCT hysteresis @ 0.75 wt%, 30 °C | 0.04 | 0.05 | 0.10 | 0.01 | 0.06 | 0.02 |
−ΔHh (kJ·mol−1) | 32.0 | 32.2 | 36.2 | 35.2 | 31.2 | - |
−ΔSh (J·mol−1·K−1) | 104 | 106 | 108 | 116 | 110 | - |
Alloy | Mg0 | Mg1 | Mg2 | Mg3 | Mg4 | Mg5 |
10th cycle capacity @ 50 mA·g−1 (mAh·g−1) | 346 | 327 | 360 | 339 | 311 | 221 |
10th cycle capacity @ 4 mA·g−1 (mAh·g−1) | 366 | 362 | 377 | 351 | 320 | 225 |
HRD @ 10th cycle | 0.94 | 0.96 | 0.96 | 0.97 | 0.97 | 0.98 |
Number of activation cycles to reach 90% HRD | 8 | 3 | 4 | 4 | 3 | 2 |
Diffusion coefficient D (10−10 cm2·s−1) | 2.5 | 1.3 | 1.2 | 1.8 | 2.8 | 2.9 |
Exchange current Io (mA·g−1) | 22.5 | 31.6 | 35.8 | 34.7 | 27.4 | 25.9 |
Ms (emu·g−1) | 0.0372 | 0.0388 | 0.0148 | 0.0598 | 0.0730 | 0.0563 |
H1/2 (kOe) | 0.111 | 0.261 | 0.260 | 0.290 | 0.140 | 0.118 |
Alloy | R @ −40 °C (Ω·g) | C @ −40 °C (Farad·g−1) | R @ RT (Ω·g) | C @ RT (Farad·g−1) |
---|---|---|---|---|
Mg0 | 29 | 0.24 | 0.32 | 0.34 |
Mg1 | 38 | 0.23 | 0.52 | 0.45 |
Mg2 | 130 | 0.22 | 0.56 | 0.39 |
Mg3 | 118 | 0.21 | 0.70 | 0.38 |
Mg4 | 90 | 0.21 | 0.92 | 0.30 |
Mg5 | 148 | 0.15 | 1.44 | 0.23 |
Property | Ni Content | Ti Content | C14 Abundance | TiNi Abundance | B/A | e/a |
B/A | 0.92 | 0.79 | 0.94 | 0.72 | 1.00 | 0.96 |
C14 unit cell volume | 0.51 | 0.19 | 0.40 | 0.91 | 0.63 | 0.57 |
C14 crystallite size | 0.17 | 0.61 | 0.42 | 0.00 | 0.20 | 0.16 |
C14 abundance | 0.88 | 0.95 | 1.00 | 0.49 | 0.94 | 0.90 |
Maximum capacity | 0.94 | 0.76 | 0.88 | 0.71 | 0.93 | 0.94 |
Reversible capacity | 0.95 | 0.80 | 0.87 | 0.62 | 0.87 | 0.92 |
Plateau pressure | 0.84 | 0.68 | 0.75 | 0.57 | 0.76 | 0.80 |
Low rate capacity | 0.93 | 0.79 | 0.88 | 0.64 | 0.90 | 0.91 |
HRD | 0.45 | 0.85 | 0.76 | 0.08 | 0.55 | 0.46 |
D | 0.61 | 0.31 | 0.43 | 0.80 | 0.59 | 0.66 |
Io | 0.25 | 0.01 | 0.05 | 0.70 | 0.19 | 0.26 |
R @ −40 °C | 0.21 | 0.57 | 0.37 | 0.00 | 0.16 | 0.18 |
C @ −40 °C | 0.76 | 0.86 | 0.84 | 0.33 | 0.72 | 0.72 |
Ms | 0.34 | 0.36 | 0.49 | 0.41 | 0.56 | 0.43 |
H1/2 | 0.44 | 0.09 | 0.15 | 0.69 | 0.30 | 0.43 |
© 2016 by the authors; licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons by Attribution (CC-BY) license (http://creativecommons.org/licenses/by/4.0/).
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Chang, S.; Young, K.-h.; Ouchi, T.; Meng, T.; Nei, J.; Wu, X. Studies on Incorporation of Mg in Zr-Based AB2 Metal Hydride Alloys. Batteries 2016, 2, 11. https://doi.org/10.3390/batteries2020011
Chang S, Young K-h, Ouchi T, Meng T, Nei J, Wu X. Studies on Incorporation of Mg in Zr-Based AB2 Metal Hydride Alloys. Batteries. 2016; 2(2):11. https://doi.org/10.3390/batteries2020011
Chicago/Turabian StyleChang, Shiuan, Kwo-hsiung Young, Taiehi Ouchi, Tiejun Meng, Jean Nei, and Xin Wu. 2016. "Studies on Incorporation of Mg in Zr-Based AB2 Metal Hydride Alloys" Batteries 2, no. 2: 11. https://doi.org/10.3390/batteries2020011