Effects of Vanadium/Nickel Contents in Laves Phase-Related Body-Centered-Cubic Solid Solution Metal Hydride Alloys
Abstract
:1. Introduction
2. Experimental Section
3. Results and Discussion
3.1. Alloy Composition
Alloy | Ti | Zr | V | Cr | Mn | Co | Ni | Al | B/A | |
---|---|---|---|---|---|---|---|---|---|---|
P17 | Design | 15.6 | 2.1 | 44.0 | 11.2 | 6.9 | 1.4 | 18.5 | 0.3 | 4.65 |
ICP | 15.6 | 2 | 44.1 | 11.3 | 6.4 | 1.4 | 18.9 | 0.3 | 4.68 | |
P22 | Design | 15.6 | 2.1 | 40.0 | 11.2 | 6.9 | 1.4 | 22.5 | 0.3 | 4.65 |
ICP | 15.5 | 1.8 | 41.0 | 11.2 | 6.5 | 1.4 | 22.2 | 0.4 | 4.78 | |
P23 | Design | 15.6 | 2.1 | 38.0 | 11.2 | 6.9 | 1.4 | 24.5 | 0.3 | 4.65 |
ICP | 15.2 | 1.7 | 38.7 | 11.4 | 6.8 | 1.4 | 24.3 | 0.4 | 4.91 | |
P24 | Design | 15.6 | 2.1 | 36.0 | 11.2 | 6.9 | 1.4 | 26.5 | 0.3 | 4.65 |
ICP | 15.5 | 1.8 | 36.0 | 11.3 | 6.4 | 1.5 | 27.1 | 0.4 | 4.78 | |
P25 | Design | 15.6 | 2.1 | 34.0 | 11.2 | 6.9 | 1.4 | 28.5 | 0.3 | 4.65 |
ICP | 15.5 | 1.8 | 34.4 | 11.4 | 6.6 | 1.4 | 28.4 | 0.4 | 4.77 | |
P26 | Design | 15.6 | 2.1 | 32.0 | 11.2 | 6.9 | 1.4 | 30.5 | 0.3 | 4.65 |
ICP | 15.5 | 1.7 | 33.5 | 10.8 | 6.8 | 1.5 | 29.8 | 0.4 | 4.81 | |
P27 | Design | 15.6 | 2.1 | 30.0 | 11.2 | 6.9 | 1.4 | 32.5 | 0.3 | 4.65 |
ICP | 15.2 | 1.8 | 30.6 | 11.7 | 6.6 | 1.4 | 32.2 | 0.4 | 4.88 | |
P28 | Design | 15.6 | 2.1 | 28.0 | 11.2 | 6.9 | 1.4 | 34.5 | 0.3 | 4.65 |
ICP | 15.3 | 1.9 | 28.1 | 11.4 | 6.6 | 1.4 | 34.9 | 0.4 | 4.81 |
3.2. X-Ray Diffractometer Structure Analysis
Alloy | BCC | C14 | |||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
a (Å) | XS (Å) | Abundance (wt%) | a (Å) | c (Å) | c/a | Unit cell volume (Å3) | XS (Å) | Abundance (wt%) | |||
P17 | 2.977 | 171 | 52.8 | 4.912 | 8.010 | 1.631 | 167.3 | 215 | 13.2 | ||
P22 | 2.974 | 57 | 50.7 | 4.890 | 7.968 | 1.629 | 165.0 | 275 | 17.1 | ||
P23 | 2.973 | 86 | 57.5 | 4.878 | 7.936 | 1.627 | 163.5 | 311 | 19.4 | ||
P24 | 2.974 | 72 | 47.0 | 4.865 | 7.915 | 1.627 | 162.2 | 255 | 20.3 | ||
P25 | 2.954 | 86 | 61.2 | 4.858 | 7.895 | 1.625 | 161.4 | 287 | 22.1 | ||
P26 | 2.950 | 71 | 55.2 | 4.844 | 7.883 | 1.627 | 160.2 | 272 | 11.1 | ||
P27 | 2.948 | 68 | 47.8 | - | - | - | - | - | - | ||
P28 | 2.946 | 73 | 34.2 | - | - | - | - | - | - | ||
Alloy | C15 | TiNi | VNi | ||||||||
a (Å) | XS (Å) | Abundance (wt%) | a (Å) | XS (Å) | Abundance (wt%) | a (Å) | c (Å) | XS (Å) | Abundance (wt%) | ||
P17 | - | - | - | 2.993 | 170 | 34.0 | - | - | - | - | |
P22 | - | - | - | 2.962 | 175 | 32.4 | - | - | - | - | |
P23 | - | - | - | 2.959 | 273 | 23.0 | - | - | - | - | |
P24 | - | - | - | 2.958 | 204 | 32.6 | - | - | - | - | |
P25 | - | - | - | 2.899 | 105 | 8.9 | 9.009 | 4.686 | 184 | 7.7 | |
P26 | 6.859 | 637 | 15.1 | 2.905 | 228 | 4.5 | 9.010 | 4.692 | 219 | 14.1 | |
P27 | 6.860 | 405 | 26.6 | 2.912 | 127 | 13.0 | 9.017 | 4.644 | 250 | 12.6 | |
P28 | 6.858 | 347 | 24.7 | 2.912 | 115 | 25.5 | 9.012 | 4.642 | 344 | 15.7 |
3.3. Scanning Electron Microscope/Energy Dispersive Spectroscopy Microstructure Analysis
Location | Zr | Ti | V | Cr | Mn | Fe | Co | Ni | Al | B/A | e/a | Phase |
---|---|---|---|---|---|---|---|---|---|---|---|---|
Figure 4a-1 | 16.2 | 16.3 | 7.8 | 4.4 | 5.9 | 0.0 | 1.8 | 47.5 | 0.1 | 2.08 | 7.28 | C14 |
Figure 4a-2 | 4.7 | 36.4 | 7.8 | 0.8 | 3.6 | 0.0 | 2.0 | 44.4 | 0.3 | 1.04 | - | TiNi |
Figure 4a-3 | 6.2 | 48.5 | 11.7 | 1.2 | 2.3 | 0.0 | 1.8 | 28.3 | 0.1 | 0.51 | - | Ti2Ni |
Figure 4a-4 | 0.1 | 5.5 | 63.5 | 16.9 | 7.4 | 0.0 | 0.8 | 5.6 | 0.2 | - | - | BCC |
Figure 4b-1 | 14.3 | 17.3 | 9.4 | 0.6 | 4.8 | 0.0 | 0.8 | 52.5 | 0.3 | 2.16 | 7.44 | C14 |
Figure 4b-2 | 2.8 | 34.3 | 7.3 | 0.9 | 4.7 | 0.1 | 2.7 | 46.4 | 0.8 | 1.25 | - | TiNi |
Figure 4b-3 | 0.1 | 3.0 | 60.7 | 17.7 | 11.8 | 0.0 | 0.9 | 5.7 | 0.1 | - | - | BCC |
Figure 4b-4 | 87.2 | 3.0 | 3.1 | 0.5 | 0.8 | 0.1 | 0.4 | 4.8 | 0.1 | - | - | Zr |
Figure 4c-1 | 12.0 | 18.6 | 12.4 | 0.7 | 3.5 | 0.0 | 0.9 | 51.6 | 0.3 | 2.27 | 7.38 | C14 |
Figure 4c-2 | 2.4 | 34.5 | 8.4 | 1.0 | 3.7 | 0.0 | 2.3 | 47.2 | 0.5 | 1.21 | - | TiNi |
Figure 4c-3 | 0.1 | 4.5 | 58.1 | 18.2 | 8.6 | 0.0 | 1.1 | 9.3 | 0.1 | - | - | BCC |
Figure 4c-4 | 93.9 | 1.1 | 2.5 | 0.4 | 0.3 | 0.1 | 0.1 | 1.5 | 0.1 | - | - | Zr |
Figure 4d-1 | 10.6 | 17.9 | 16.5 | 2.5 | 4.7 | 0.0 | 1.4 | 46.2 | 0.2 | 2.51 | 7.20 | C14 |
Figure 4d-2 | 1.9 | 33.9 | 8.6 | 1.1 | 3.5 | 0.0 | 2.4 | 47.6 | 1.0 | 1.25 | - | TiNi |
Figure 4d-3 | 0.0 | 2.3 | 60.0 | 21.1 | 8.3 | 0.0 | 1.0 | 7.1 | 0.2 | - | - | BCC |
Figure 4d-4 | 94.7 | 0.7 | 1.8 | 0.4 | 0.1 | 0.0 | 0.2 | 1.9 | 0.2 | - | - | Zr |
Figure 4e-1 | 10.8 | 16.0 | 14.2 | 1.8 | 4.2 | 0.0 | 1.0 | 51.7 | 0.3 | 2.73 | 7.45 | C15 |
Figure 4e-2 | 8.5 | 17.7 | 18.2 | 2.5 | 5.0 | 0.0 | 1.5 | 46.2 | 0.3 | 2.81 | 7.22 | C14 |
Figure 4e-3 | 1.6 | 33.8 | 8.6 | 1.1 | 4.1 | 0.1 | 2.5 | 47.5 | 0.8 | 1.28 | - | TiNi |
Figure 4e-4 | 0.2 | 7.0 | 48.2 | 6.6 | 5.2 | 0.1 | 1.3 | 31.3 | 0.1 | 0.81 | - | VNi |
Figure 4e-5 | 0.0 | 2.4 | 58.7 | 21.8 | 8.5 | 0.0 | 1.0 | 7.4 | 0.1 | - | - | BCC |
Figure 4e-6 | 89.0 | 3.2 | 2.4 | 0.4 | 0.2 | 0.0 | 0.2 | 4.5 | 0.1 | - | - | Zr |
Figure 4e-7 | 4.7 | 69.5 | 7.8 | 1.3 | 1.6 | 0.0 | 0.6 | 14.1 | 0.3 | - | - | TiO2 |
Figure 4f-1 | 10.5 | 16.2 | 13.3 | 1.9 | 4.4 | 0.0 | 1.0 | 52.5 | 0.2 | 2.75 | 7.50 | C15 |
Figure 4f-2 | 8.9 | 17.3 | 15.7 | 2.5 | 5.1 | 0.0 | 1.4 | 48.8 | 0.2 | 2.81 | 7.35 | C14 |
Figure 4f-3 | 1.4 | 30.7 | 10.3 | 1.1 | 5.1 | 0.0 | 2.0 | 48.6 | 0.8 | 1.36 | - | TiNi |
Figure 4f-4 | 0.2 | 6.8 | 48.4 | 7.1 | 6.8 | 0.0 | 1.5 | 29.0 | 0.1 | 0.80 | - | VNi |
Figure 4f-5 | 0.0 | 2.1 | 58.3 | 21.6 | 8.7 | 0.0 | 1.1 | 8.0 | 0.1 | - | - | BCC |
Figure 4f-6 | 6.0 | 79.0 | 8.3 | 0.1 | 0.5 | 0.0 | 0.2 | 6.0 | 0.0 | - | - | TiO2 |
Figure 4g-1 | 10.4 | 16.5 | 11.9 | 2.1 | 5.2 | 0.1 | 1.2 | 52.4 | 0.3 | 2.72 | 7.53 | C15 |
Figure 4g-2 | 4.5 | 30.2 | 9.2 | 1.0 | 5.0 | 0.0 | 1.0 | 48.8 | 0.2 | 1.28 | - | TiNi |
Figure 4g-3 | 0.1 | 6.6 | 46.2 | 9.4 | 6.6 | 0.0 | 1.8 | 29.3 | 0.1 | 0.89 | - | VNi |
Figure 4g-4 | 0.0 | 1.8 | 55.4 | 25.3 | 8.6 | 0.0 | 1.1 | 7.6 | 0.1 | - | - | BCC |
Figure 4g-5 | 85.5 | 5.1 | 2.1 | 0.5 | 0.6 | 0.2 | 0.1 | 5.8 | 0.1 | - | - | Zr |
Figure 4g-6 | 3.5 | 82.8 | 7.6 | 0.1 | 0.6 | 0.0 | 0.1 | 5.2 | 0.1 | - | - | TiO2 |
Figure 4h-1 | 10.2 | 16.2 | 11.8 | 2.4 | 5.5 | 0.0 | 1.1 | 52.5 | 0.3 | 2.79 | 7.53 | C15 |
Figure 4h-2 | 1.3 | 30.1 | 9.1 | 1.0 | 6.3 | 0.0 | 2.3 | 49.0 | 0.9 | 1.47 | - | TiNi |
Figure 4h-3 | 0.1 | 6.6 | 43.5 | 11.6 | 6.8 | 0.2 | 1.8 | 29.2 | 0.2 | 0.99 | - | VNi |
Figure 4h-4 | 0.0 | 1.7 | 53.0 | 27.4 | 8.3 | 0.0 | 1.2 | 8.3 | 0.1 | - | - | BCC |
Figure 4h-5 | 86.1 | 3.9 | 2.2 | 0.4 | 0.7 | 0.0 | 0.2 | 6.2 | 0.2 | - | - | Zr |
Figure 4h-6 | 2.0 | 90.6 | 3.3 | 0.1 | 0.5 | 0.0 | 0.2 | 3.3 | 0.1 | - | - | TiO2 |
3.4. Gaseous Phase Study
Alloy No. | Desorption pressure @ 30 °C | Desorption pressure @ 60 °C | Maximum capacity @ 30 °C | Reversible capacity @ 30 °C | PCT hysteresis @ 30 °C | PCT hysteresis @ 60 °C | −ΔH | −ΔS |
---|---|---|---|---|---|---|---|---|
(MPa) | (MPa) | (wt%) | (wt%) | (kJ·mol−1) | (J·mol−1·K−1) | |||
P17 | 0.17 | 0.53 | 1.68 | 1.01 | 1.06 | 1.10 | 30.9 | 107 |
P22 | 0.21 | 0.60 | 1.53 | 1.24 | 1.14 | 1.13 | 29.9 | 105 |
P23 | 0.22 | 0.79 | 1.45 | 1.25 | 1.20 | 1.06 | 35.3 | 123 |
P24 | 0.32 | 1.07 | 1.38 | 1.20 | 1.10 | 0.86 | 34.2 | 122 |
P25 | 0.45 | 1.42 | 1.33 | 1.16 | 0.77 | 0.82 | 32.1 | 119 |
P26 | 0.43 | 1.36 | 1.14 | 0.93 | 0.79 | 0.84 | 32.4 | 119 |
P27 | 1.06 | 3.20 | 0.85 | 0.75 | 0.79 | 0.46 | 31.0 | 122 |
P28 | 1.90 | - | 0.63 | 0.51 | 0.76 | - | - | - |
3.5. Electrochemical Measurement
Alloy No. | 4th cycle capacity @ 50 mA·g−1 | 4th cycle capacity @ 4 mA·g−1 | HRD200 | Activation cycle to reach maximum capacity | Diffusion coefficient, D @RT | Exchange current Io @RT | Ms | H1/2 | Open circuit voltage |
---|---|---|---|---|---|---|---|---|---|
(mAh·g−1) | (mAh·g−1) | (10−10·cm2·s−1) | (mA·g−1) | (emu·g−1) | (kOe) | (V) | |||
P17 | 382.7 | 400.7 | 0.815 | 6 | 1.69 | 36.5 | 0.39 | 0.11 | 1.302 |
P22 | 360.4 | 371.0 | 0.873 | 5 | 1.67 | 25.2 | 1.40 | 0.11 | 1.306 |
P23 | 342.6 | 348.8 | 0.920 | 5 | 2.95 | 25.5 | 0.62 | 0.11 | 1.326 |
P24 | 308.1 | 314.1 | 0.939 | 6 | 2.85 | 20.0 | 0.92 | 0.10 | 1.330 |
P25 | 253.9 | 259.2 | 0.965 | 5 | 1.58 | 18.9 | 1.03 | 0.10 | 1.312 |
P26 | 201.6 | 207.7 | 0.913 | 5 | 1.22 | 12.8 | 1.81 | 0.11 | 1.288 |
P27 | 100.1 | 105.6 | - | 6 | 1.39 | 12.3 | 1.42 | 0.14 | 1.264 |
P28 | 68.0 | 72.4 | - | 6 | 1.46 | 16.3 | 1.40 | 0.12 | 1.332 |
4. Conclusions
Acknowledgments
Conflicts of Interest
References
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Young, K.-h.; Wong, D.F.; Nei, J. Effects of Vanadium/Nickel Contents in Laves Phase-Related Body-Centered-Cubic Solid Solution Metal Hydride Alloys. Batteries 2015, 1, 34-53. https://doi.org/10.3390/batteries1010034
Young K-h, Wong DF, Nei J. Effects of Vanadium/Nickel Contents in Laves Phase-Related Body-Centered-Cubic Solid Solution Metal Hydride Alloys. Batteries. 2015; 1(1):34-53. https://doi.org/10.3390/batteries1010034
Chicago/Turabian StyleYoung, Kwo-hsiung, Diana F. Wong, and Jean Nei. 2015. "Effects of Vanadium/Nickel Contents in Laves Phase-Related Body-Centered-Cubic Solid Solution Metal Hydride Alloys" Batteries 1, no. 1: 34-53. https://doi.org/10.3390/batteries1010034