Fast Hydrogen Sorption Kinetics in Mg-VCl3 Produced by Cryogenic Ball-Milling
Abstract
:1. Introduction
2. Materials and Methods
2.1. Mixtures Preparation
2.2. Hydriding and Dehydriding Reactions
2.3. Physicochemical Characterization of the Materials
3. Results
3.1. Hydriding and Dehydriding Reactions of Cryogenically Milled Mg-15wt.% VCl3
3.2. Hydriding and Dehydriding Reactions of Pure, Cryogenically Milled Mg and Mg-15wt.% VCl3-RT
3.3. Characterization of As-Milled, Hydrided, and Dehydrided Materials
4. Discussion
4.1. Remarks on Cryogenic Milling and Amount of Added VCl3
4.2. Other Reported Mg/MgH2-VCl3 Mixtures
4.3. Hydriding Activation Energy
4.4. Dehydriding Activation Energy
4.5. Reason for Improved Hydriding Kinetics
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Temperature [°C] | Time Interval [min] | k [s−1] |
---|---|---|
50 | 0–60 | 3.05 × 10−5 |
100 | 0–19 | 6.06 × 10−5 |
150 | 0–12 | 7.58 × 10−5 |
200 | 0–0.1 | 1.51 × 10−3 |
250 | 0–0.3 | 3.73 × 10−3 |
300 | 0–0.5 | 4.60 × 10−3 |
Previous Hydriding Temperature [°C] | k [s−1] of Dehydriding at 350 °C, 0.8 Bar |
---|---|
50 | 4.98 × 10−3 |
100 | 3.14 × 10−3 |
150 | 2.50 × 10−3 |
200 | 2.24 × 10−3 |
250 | 2.38 × 10−3 |
300 | 2.05 × 10−3 |
Material, Theoretical Hydrogen Content [wt.%], and Highlights of Preparation | Ref. | Hydrogen Uptake [wt.%] | Hydrogen Release [wt.%] | Peak Dehydriding Temperature [°C] and Conditions |
---|---|---|---|---|
Mg-5 wt.% VCl3 7.22 milled in hydrogen | [29] | 3.37 wt.% at 2.5 min 6.36 wt.% at 60 min 320 °C, 12 bar, isothermic. | 0.12 wt.% at 2.5 min 4.54 wt.% at 60 min 320 °C, 1 bar, isothermic. | Not reported |
Mg-15 wt.% VCl3 6.46 1 h cryomilling | This work | 5.19 wt.% at 2.5 min 5.6 wt.% at 60 min 300 °C, 26 bar, isothermic. | 0.95 wt.% at 2.5 min 5.34 wt.% at 20 min 350 °C, 0.8 bar, isothermic. | 314 °C, 1 °C/min, DSC |
1.26 wt.% at 2.5 min 5.3 wt.% at 60 min 320 °C, 12 bar, isothermic. | 0.03 wt.% at 2.5 min 5.07 wt.% at 60 min 320 °C, 1 bar, isothermic. | |||
MgH2-14 wt.% VCl3 6.53 1 h milling in argon | [25] | Not reported | Not reported | ~310 °C *, 5 °C/min, TPD |
MgH2-7 wt.% VCl3 7.06 1 h milling in argon | [25] | Not reported | Not reported | ~305 °C *, 5 °C/min, TPD |
278 °C, 5 °C/min, DSC | ||||
MgH2-5 wt.% VCl3 7.22 Planetary ball milling | [26] | ~7.0 wt.% * 100 °C, 20 bar, 60 min, isothermic | ~7.0 wt.% * TG-DSC No kinetics study | ~275 °C, 1 °C/min, TG-DSC |
MgH2-7 wt.%VCl3 7.06 Pre-milled in H2 at 2 bar for 24 h. Then milled for 20 min with the additive. | [30] | ~6.5 wt.% * 350 °C, 10 bar, 30 min Isothermic | ~6.2 wt.% * 350 °C, 0.1 bar (vacuum), 14 min Isothermic | ~375 °C DSC |
MgH2-5mol% VCl3 (i.e., 23.9 wt.% VCl3) 5.78 | [31] | wt.% not reported 270 and 320 °C, 100–150 bar In-situ SR-PXD | wt.% not reported 270 and 320 °C, dynamic vacuum In-situ SR-PXD | Not reported |
MgH2-10 wt.% NiCl2 2 h ball milled | [14] | ~6.1 wt.% * 350 °C, 20 bar, 5 min, isothermic | ~6.1 wt.% * 0.01 bar (vacuum), TPD | Not reported |
MgH2-4mol% TiCl3 (i.e., 19.6 wt.% TiCl3) 10 h milling in argon | [56,57] | ~5.1 wt.% * 300 °C, 20 bar, 1 min, isothermic | ~3.8 wt.% * 280 °C, 0.1 bar (vacuum), 25 min, isothermic | Not reported |
MgH2-5 wt.% NbCl5 milled in H2 at 2 bar for 24 h. | [58] | ~6.4 wt.% * 350 °C, 10 bar, 15 min, isothermic | ~6.4 wt.% * 350 °C, 0.1 bar (vacuum), 6 min, isothermic | ~375 °C DSC |
Material | Ea [kJ/mol H2] | Reference |
---|---|---|
Mg | 90 ± 10 | [60] |
95–130 | [61] | |
Mg-15wt.% VCl3 | 63.8 ± 5.6 | This work |
Material | Relevant Conditions of Materials Preparation | Ea [kJ/mol H2] | Reference |
---|---|---|---|
MgH2 | Not milled | 240 | [25] |
MgH2 | Commercial (not milled) | 195.3 ± 10 | [62] |
MgH2 | Not milled | 156 | [63] |
MgH2 | Particle size 45 µm | 160 ± 10 | [60,61] |
MgH2 | 2 h ball milled | 158.5 | [14] |
Mg-15wt.% VCl3 | Cryogenic ball milling (2.5–5 µm thickness) | 123.11 ± 0.61 | This work |
MgH2-5wt.% VCl3 | Planetary ball milling, 2 h, particle size < 10 µm | 122 ± 5 | [26] |
MgH2-10wt.% CoCl2 | 2 h ball milled | 121.3 | [14] |
MgH2-10wt.% NiCl2 | 2 h ball milled | 102.6 | [14] |
MgH2-7wt.% TiCl3 | 1 h milling in argon | 97 | [25] |
MgH2-5wt.% NbCl5 | 24 h reactive-milling in 2 bar H2 | 98 | [58] |
MgH2-7wt.% VCl3 | 1 h milling in argon | 96–97 | [25] |
MgH2-5 at.% V (9.2 wt.% V) | 20 h milling, particle size < 5 µm | 62 | [45] |
MgH2-7 wt.% VCl3 | Pre-milled in H2 at 2 bar for 24 h. Then milled for 20 min with the additive. | 47 | [30] |
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Suárez-Alcántara, K.; Flores-Jacobo, N.I.; Osorio-García, M.d.P.; Cabañas-Moreno, J.G. Fast Hydrogen Sorption Kinetics in Mg-VCl3 Produced by Cryogenic Ball-Milling. Materials 2023, 16, 2526. https://doi.org/10.3390/ma16062526
Suárez-Alcántara K, Flores-Jacobo NI, Osorio-García MdP, Cabañas-Moreno JG. Fast Hydrogen Sorption Kinetics in Mg-VCl3 Produced by Cryogenic Ball-Milling. Materials. 2023; 16(6):2526. https://doi.org/10.3390/ma16062526
Chicago/Turabian StyleSuárez-Alcántara, Karina, Nadia Isabel Flores-Jacobo, Mayara del Pilar Osorio-García, and José Gerardo Cabañas-Moreno. 2023. "Fast Hydrogen Sorption Kinetics in Mg-VCl3 Produced by Cryogenic Ball-Milling" Materials 16, no. 6: 2526. https://doi.org/10.3390/ma16062526