Mechanochemical reactions and hydrogen storage capacities in MBH4–SiS2 systems (M=Li or Na)

Dolotko, Oleksandr; Gupta, Shalabh; Kobayashi, Takeshi; McDonald, Eric; Hlova, Ihor; Majzoub, Eric; Balema, Viktor P.; Pruski, Marek; Pecharsky, Vitalij K.

doi:10.1016/j.ijhydene.2019.01.211

Title: Mechanochemical reactions and hydrogen storage capacities in MBH₄–SiS₂ systems (M=Li or Na)

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Abstract

The hydrogen storage properties, and phase compositions of mechanochemically prepared mixtures of xMBH₄-SiS₂ (x = 2–8), where M = Li or Na, were investigated using gas sorption analysis, powder X-ray diffraction, and infrared and solid-state NMR spectroscopic methods. The 2LiBH₄:1SiS₂ system forms an amorphous product that releases ca. 4.3 wt % of H₂ below 385 °C with a T_onset of 88 °C without detectable diborane emission. The dehydrogenated sample reversibly absorbs 1.5 wt % of H₂ at 385 °C under 160 bar pressure. The H₂ release from materials with varying LiBH₄:SiS₂ ratios peaks at 8.2 wt % for the 6LiBH₄:1SiS₂ composition, with a reversible hydrogen storage capacity of 2.4 wt %. The H₂ desorption capacities of the Li-containing systems surpass those of Na-containing systems. Solid-state NMR studies indicate that products of mechanochemical reactions in the LiBH₄SiS₂ system consist of one-dimensional chains of edge-sharing SiS_4/2 tetrahedra in which the non-bridging S-ends are terminated with Li⁺, which are further coordinated to the [BH₄]^– anions. Here, a variety of possible polymorphs in the Li—Si—S-(BH₄) composition space have been identified using first principles and thermodynamic modeling that supports the likelihood of formation of such novel complexes.

Authors:

Dolotko, Oleksandr ^[1];

^[1];

^[1]; McDonald, Eric ^[1]; Hlova, Ihor ^[1]; Majzoub, Eric ^[2]; Balema, Viktor P. ^[1]; Pruski, Marek ^[1];

^[1]

Ames Lab. and Iowa State Univ., Ames, IA (United States)
Univ. of Missouri, St. Louis, MO (United States)

Publication Date:: Sat Feb 16 00:00:00 EST 2019

Research Org.:: Ames Lab., Ames, IA (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:: 1506106

Alternate Identifier(s):: OSTI ID: 1636468

Report Number(s):: IS-J-9923
Journal ID: ISSN 0360-3199

Grant/Contract Number:: AC02-07CH11358; EE-0007047

Resource Type:: Accepted Manuscript

Journal Name:: International Journal of Hydrogen Energy

Additional Journal Information:: Journal Volume: 44; Journal Issue: 14; Journal ID: ISSN 0360-3199

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 08 HYDROGEN; Mechanochemistry; Hydrogen storage; Solid-state NMR

Citation Formats


                    Dolotko, Oleksandr, Gupta, Shalabh, Kobayashi, Takeshi, McDonald, Eric, Hlova, Ihor, Majzoub, Eric, Balema, Viktor P., Pruski, Marek, and Pecharsky, Vitalij K. Mechanochemical reactions and hydrogen storage capacities in MBH4–SiS2 systems (M=Li or Na).  United States: N. p., 2019. 
Web.  doi:10.1016/j.ijhydene.2019.01.211.

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                    Dolotko, Oleksandr, Gupta, Shalabh, Kobayashi, Takeshi, McDonald, Eric, Hlova, Ihor, Majzoub, Eric, Balema, Viktor P., Pruski, Marek, & Pecharsky, Vitalij K. Mechanochemical reactions and hydrogen storage capacities in MBH4–SiS2 systems (M=Li or Na).  United States.  https://doi.org/10.1016/j.ijhydene.2019.01.211

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                    Dolotko, Oleksandr, Gupta, Shalabh, Kobayashi, Takeshi, McDonald, Eric, Hlova, Ihor, Majzoub, Eric, Balema, Viktor P., Pruski, Marek, and Pecharsky, Vitalij K. Sat .  
"Mechanochemical reactions and hydrogen storage capacities in MBH4–SiS2 systems (M=Li or Na)".  United States.  https://doi.org/10.1016/j.ijhydene.2019.01.211.  https://www.osti.gov/servlets/purl/1506106.

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@article{osti_1506106,

  title        = {Mechanochemical reactions and hydrogen storage capacities in MBH4–SiS2 systems (M=Li or Na)},

  author       = {Dolotko, Oleksandr and Gupta, Shalabh and Kobayashi, Takeshi and McDonald, Eric and Hlova, Ihor and Majzoub, Eric and Balema, Viktor P. and Pruski, Marek and Pecharsky, Vitalij K.},

  abstractNote = {The hydrogen storage properties, and phase compositions of mechanochemically prepared mixtures of xMBH4-SiS2 (x = 2–8), where M = Li or Na, were investigated using gas sorption analysis, powder X-ray diffraction, and infrared and solid-state NMR spectroscopic methods. The 2LiBH4:1SiS2 system forms an amorphous product that releases ca. 4.3 wt % of H2 below 385 °C with a Tonset of 88 °C without detectable diborane emission. The dehydrogenated sample reversibly absorbs 1.5 wt % of H2 at 385 °C under 160 bar pressure. The H2 release from materials with varying LiBH4:SiS2 ratios peaks at 8.2 wt % for the 6LiBH4:1SiS2 composition, with a reversible hydrogen storage capacity of 2.4 wt %. The H2 desorption capacities of the Li-containing systems surpass those of Na-containing systems. Solid-state NMR studies indicate that products of mechanochemical reactions in the LiBH4SiS2 system consist of one-dimensional chains of edge-sharing SiS4/2 tetrahedra in which the non-bridging S-ends are terminated with Li+, which are further coordinated to the [BH4]– anions. Here, a variety of possible polymorphs in the Li—Si—S-(BH4) composition space have been identified using first principles and thermodynamic modeling that supports the likelihood of formation of such novel complexes.},

  doi          = {10.1016/j.ijhydene.2019.01.211},

  journal      = {International Journal of Hydrogen Energy},

  number       = 14,

  volume       = 44,

  place        = {United States},

  year         = {Sat Feb 16 00:00:00 EST 2019},

  month        = {Sat Feb 16 00:00:00 EST 2019}

}

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Title: Mechanochemical reactions and hydrogen storage capacities in MBH4–SiS2 systems (M=Li or Na)

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Title: Mechanochemical reactions and hydrogen storage capacities in MBH₄–SiS₂ systems (M=Li or Na)