Differential Scanning Calorimetry (DSC) and Synchrotron X-ray Diffraction Study of Unmilled and Milled LiBH4: A Partial Release of Hydrogen at Moderate Temperatures
Abstract
:1. Introduction
2. Experimental Method
- Wide temperature range: upon heating from 100 to 500 K, with 60 K per hour rate;
- Fine temperature sampling: upon heating from 368 to 398 K, followed by cooling in the same temperature range with a rate of 10 K per hour; the same heating/cooling cycle was then repeated on the same sample spot, but with a rate of 100 K per hour.
- Under 2 bar of H2: first upon heating from 297 to 400 K with a rate of 40 K per hour and then on cooling from 400K to 350 K with a rate of 100 K per hour;
- Under 40 bar of H2: upon heating from 350 to 395 K, with a rate of 20 K per hour.
3. Results and Discussion
3.1. Structural Characterization
3.2. Phases Transformations in Unmilled LiBH4
First heating | First cooling | Second heating | ||||
DSC atmosphere | First endotherm | Exotherm | Phase transition | Phase transition | Exotherm | Phase transition |
Argon | -- | 368.3 | 390.6 | 380.4 | -- | 390.3 |
2 bar Hydrogen | 320.6 | 367.7 | 388.1 | 381.0 | 368.9 | 387.6 |
3.3. Investigation of the Exotherm
3.3.1. Effect of PDSC Atmosphere
3.3.2. Effect of Settling Time
3.3.3. Effect of Exposure to Dry Air
First heating | First cooling | Second heating | ||||
Sample | First endotherm | Exotherm | Phase transition | Phase transition | Exotherm | Phase transition |
Before air exposure | 319.6 | 362.6 | 385.9 | 378.8 | 364.4 | 386.1 |
After two days air exposure | 320.8 | 365.0 | 389.4 | 378.6 | -- | 389.1 |
3.4. Effect of Milling
3.4.1. PDSC Curves
3.4.1.1. PDSC Performed under Argon Atmosphere
3.4.1.2. PDSC Performed under Hydrogen Atmosphere (2 and 20 bar)
3.4.2. Activation Energy of the Exothermic Peak
Sample/Atmosphere | argon | 2 bar hydrogen |
---|---|---|
Unmilled | 79 ± 6 | 102 ± 2 |
Milled | 95 ± 8 | 100 ± 12 |
3.5. In-situ Synchrotron X-ray Diffraction Study
3.5.1. Temperature Variation of Lattice Parameters: Effect of Milling
3.5.2. Temperature Variation of Lattice Parameters: Effect of Hydrogen Atmosphere and of a Hydrostatic Pressure
4. Conclusion
Acknowledgements
References
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Lang, J.; Gerhauser, A.; Filinchuk, Y.; Klassen, T.; Huot, J. Differential Scanning Calorimetry (DSC) and Synchrotron X-ray Diffraction Study of Unmilled and Milled LiBH4: A Partial Release of Hydrogen at Moderate Temperatures. Crystals 2012, 2, 1-21. https://doi.org/10.3390/cryst2010001
Lang J, Gerhauser A, Filinchuk Y, Klassen T, Huot J. Differential Scanning Calorimetry (DSC) and Synchrotron X-ray Diffraction Study of Unmilled and Milled LiBH4: A Partial Release of Hydrogen at Moderate Temperatures. Crystals. 2012; 2(1):1-21. https://doi.org/10.3390/cryst2010001
Chicago/Turabian StyleLang, J., A. Gerhauser, Y. Filinchuk, T. Klassen, and J. Huot. 2012. "Differential Scanning Calorimetry (DSC) and Synchrotron X-ray Diffraction Study of Unmilled and Milled LiBH4: A Partial Release of Hydrogen at Moderate Temperatures" Crystals 2, no. 1: 1-21. https://doi.org/10.3390/cryst2010001