The Thermodynamic Way of Assessing Reversible Metal Hydride Volume Expansion: Getting a Grip on Metal Hydride Formation Overpotential

Author(s):  
Roland Hermann Pawelke

<p>The relative volume change of reversible metal hydrides upon hydrogenation is determined by means of the van’t Hoff reaction entropy and STP ideal gas parameters. This method allows insight into the requirements to metal hydride formation, outlined by example of Ti-NaAlH<sub>4</sub>. This work presents a timeless perspective on the sorbent phase thermodynamics of reversible chemical hydrogen storage systems.</p>

2021 ◽  
Author(s):  
Roland Hermann Pawelke

<p>The relative volume change of reversible metal hydrides upon hydrogenation is determined by means of the van’t Hoff reaction entropy and STP ideal gas parameters. This method allows insight into the requirements to metal hydride formation, outlined by example of Ti-NaAlH<sub>4</sub>. This work presents a timeless perspective on the sorbent phase thermodynamics of reversible chemical hydrogen storage systems.</p>


2021 ◽  
Author(s):  
Roland Hermann Pawelke

<p>The relative volume expansion of reversible metal hydride crystals upon formation is determined by means of the van’t Hoff reaction entropy and STP ideal gas parameters, the development of this approach leads to a general method for calculating metal hydride single-crystal density. These results allow highlighting the pressure requirement to hydride phase formation, shown by the example of Ti-NaAlH<sub>4</sub>.</p>


2019 ◽  
Author(s):  
Roland Hermann Pawelke

<p>A practical way for assessing the relative volume change of reversible metal hydrides upon hydrogenation, based on the van’t Hoff reaction parameters, is outlined. Hitherto computational methods can provide that information only at a much higher level of complexity. By that method, the open issue of assessing the minimum pressure for complete [AlH<sub>4</sub>]-formation in Ti-doped NaAlH<sub>4</sub> is resolved and the nature of the additional reaction pathway in KH/Ti-co-doped NaAlH<sub>4</sub> elucidated. This work summarizes the essentials for the thermodynamic tailoring of metal hydrides in nine points and adds thus a central missing piece to the puzzle of understanding reversible chemical hydrogen storage in metal hydrides.</p>


2019 ◽  
Author(s):  
Roland Hermann Pawelke

<p>A practical way for assessing the relative volume change of reversible metal hydrides upon hydrogenation, based on the van’t Hoff reaction parameters, is outlined. Hitherto computational methods can provide that information only at a much higher level of complexity. By that method, the open issue of assessing the minimum pressure for complete [AlH<sub>4</sub>]-formation in Ti-doped NaAlH<sub>4</sub> is resolved and the nature of the additional reaction pathway in KH/Ti-co-doped NaAlH<sub>4</sub> elucidated. This work summarizes the essentials for the thermodynamic tailoring of metal hydrides in nine points and adds thus a central missing piece to the puzzle of understanding reversible chemical hydrogen storage in metal hydrides.</p>


Author(s):  
Michael Lee ◽  
Il-Seok Park ◽  
Sunwoo Kim ◽  
Kwang J. Kim

Pelletized Porous Metal Hydride (PMH) was investigated in order to assess its thermal capability for energy storage/transfer applications. Metal hydrides have been known as promising materials for hydrogen storage systems, heat storage systems, and thermal devices, thanks to their nearly reversible reaction characteristics during the hydrogen absorbing and desorbing processes. The conventional powder-type metal hydrides however have a relatively low thermal conductivity, which is responsible for low heat generation. In the present study three representative metal hydrides, LaNi5, Ca0.6Mm0.4Ni5, and LaNi4.75Al0.25, metal hydride powders were coated with thin copper and pressed at 3,000 psig with metal additives in order to improve the thermal conductivity. This pelletizing process does not require the use of an organic binder and additional processes such as sintering under high pressure. The pelletized PMH compacts employing the copper coating exhibit higher thermal conductivity compared to raw metal hydride powders. However, pelletizing may deteriorate the permeability of the PMH compacts, lowering mass transfer of hydrogen. Therefore, the permeability must be observed to verify whether it meets the required level for suitable applications. Measurements were performed by varying copper fractions and plotted against the upstream/downstream pressure differential. Darcy’s equation in conjunction with an ideal gas assumption was used to calculate the permeability of a rigid wall design. This investigation reveals that rising copper content is accompanied with decreases in permeability. Permeability values for most samples tested in this study were found to be larger than the desirable level, 5 × 10−15 m2. Additionally, the thermal performance of the LaNi5 PMH compacts was tested by calculating and comparing the heat generation of the PMH pellets and powders filled reactors during the hydrogen absorption process in water bath medium.


1985 ◽  
Vol 55 (12) ◽  
pp. 1089-1091 ◽  
Author(s):  
R.A. Butera ◽  
E. Franz ◽  
J.J. Joyce ◽  
J.H. Weaver

2016 ◽  
Vol 18 (16) ◽  
pp. 10688-10699 ◽  
Author(s):  
Stefan Hugenbruch ◽  
Hannah S. Shafaat ◽  
Tobias Krämer ◽  
Mario Ulises Delgado-Jaime ◽  
Katharina Weber ◽  
...  

Insight into the factors that favor metal–hydride interactions in NiFe-hydrogenase models is obtained through X-ray spectroscopic and quantum chemical studies.


2020 ◽  
Author(s):  
Roland Hermann Pawelke

Ti-doped NaAlH<sub>4</sub> requires at 125 °C for [AlH<sub>4</sub>] formation more than twice the equilibrium pressure; while it is straightforward to relate this conditional surplus in hydrogenation pressure respective chemical potential to kinetic hindrance, it appears strange that this matter has not been duly theoretically addressed in literature to this day. The interest in identifying such overpotentials is not of purely academic interest but touches a problem of very practical significance as the maximum applied pressure is an important threshold to metal hydride tank design. A theory-based tool would be a resource-efficient complement or even alternative to PCI measurements. This paper tracks the formation overpotential issue down to its root and outlines a simple yet accurate general method based on Arrhenius and van’t Hoff data. Rather unexpectedly, the result is also the final missing piece towards a comprehensive understanding of reversible chemical hydrogen storage with regard to attainable hydrogen storage capacity.


2020 ◽  
Author(s):  
Roland Hermann Pawelke

Ti-doped NaAlH<sub>4</sub> requires at 125 °C for [AlH<sub>4</sub>] formation more than twice the equilibrium pressure; while it is straightforward to relate this conditional surplus in hydrogenation pressure respective chemical potential to kinetic hindrance, it appears strange that this matter has not been duly theoretically addressed in literature to this day. The interest in identifying such overpotentials is not of purely academic interest but touches a problem of very practical significance as the maximum applied pressure is an important threshold to metal hydride tank design. A theory-based tool would be a resource-efficient complement or even alternative to PCI measurements. This paper tracks the formation overpotential issue down to its root and outlines a simple yet accurate general method based on Arrhenius and van’t Hoff data. Rather unexpectedly, the result is also the final missing piece towards a comprehensive understanding of reversible chemical hydrogen storage with regard to attainable hydrogen storage capacity.


2020 ◽  
Author(s):  
Roland Hermann Pawelke

Ti-doped NaAlH<sub>4</sub> requires at 125 °C for [AlH<sub>4</sub>] formation more than twice the equilibrium pressure; while it is straightforward to relate this conditional surplus in hydrogenation pressure respective chemical potential to kinetic hindrance, it appears strange that this matter has not been duly theoretically addressed in literature to this day. The interest in identifying such overpotentials is not of purely academic interest but touches a problem of very practical significance as the maximum applied pressure is an important threshold to metal hydride tank design. A theory-based tool would be a resource-efficient complement or even alternative to PCI measurements. This paper tracks the formation overpotential issue down to its root and outlines a simple yet accurate general method based on Arrhenius and van’t Hoff data. Rather unexpectedly, the result is also the final missing piece towards a comprehensive understanding of reversible chemical hydrogen storage with regard to attainable hydrogen storage capacity.


Sign in / Sign up

Export Citation Format

Share Document