Rerouting Pathways of Solid-State Ammonia Borane Energy Release

Biswas, Prithwish; Ghildiyal, Pankaj; Kwon, Hyuna; Wang, Xizheng; Alibay, Zaira; Xu, Feiyu; Wang, Yujie; Wong, Bryan M.; Zachariah, Michael R.

doi:10.1021/acs.jpcc.1c08985

Cited by 11 publications

(23 citation statements)

References 66 publications

(91 reference statements)

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“…Details about the mass spectrometer can be found in several of our previous publications. 3,48,49 For this measurement, a thin Pt wire (∼75 μm) is used as the sample holder, on which thin layers of solid nanopowder samples are coated by drop-casting through micropipets. During the measurement, the Pt wire is resistively heated to ∼1500 K by applying a voltage pulse of width ∼3 ms, which leads to an average heating rate of ∼10 5 K/s.…”

Section: Methodsmentioning

confidence: 99%

In-Situ Thermochemical Shock-Induced Stress at the Metal/Oxide Interface Enhances Reactivity of Aluminum Nanoparticles

Biswas

Ghildiyal

et al. 2022

ACS Appl. Mater. Interfaces

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Although aluminum (Al) nanoparticles have been widely explored as fuels in energetic applications, researchers are still exploring approaches for tuning their energy release profile via microstructural alteration. In this study, we show that a nanocomposite (∼70 nm) of a metal ammine complex, such as tetraamine copper nitrate (Cu(NH 3 ) 4 (NO 3 ) 2 /TACN), coated Al nanoparticles containing only 10 wt. % TACN, demonstrates a ∼200 K lower reaction initiation temperature coupled with an order of magnitude enhancement in the reaction rate. Through time/temperature-resolved mass spectrometry and ignition onset measurements at high heating rates, we show that the ignition occurs due to a condensed phase reaction between Al and copper oxide (CuO) crystallized on TACN decomposition. TEM and XRD analyses on the nanoparticles at an intermediate stage show that the rapid heat release from TACN decomposition in-situ enhances the strain on the Al core with induction of nonuniformities in the thickness of its AlO x shell. The thinner region of the nonuniform shell enables rapid mass transfer of Al ions to the crystallized CuO, enabling their condensed phase ignition. Hence, the thermochemical shock from TACN coating induces stresses at the Al/AlO x interface, which effectively switches the usual gas phase O 2 diffusion-limited ignition process of Al nanoparticles to become condensed phase Al ion transfer controlled, thereby enhancing their reactivity.

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Section: Methodsmentioning

confidence: 99%

In-Situ Thermochemical Shock-Induced Stress at the Metal/Oxide Interface Enhances Reactivity of Aluminum Nanoparticles

Biswas

Ghildiyal

et al. 2022

ACS Appl. Mater. Interfaces

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“…NaBH4 [49,74,216,236,241], Mg(BH4)2 [42,55,61,70,105,126,132,151,159,207,216,220,224,236,242,243], Ca(BH4)2 [116,216,236,243] and (TM)(BH4)x [150,216], ammonia-borane NH3.BH3 [36,38,63,64,75,85,86,88,90,139,[140][141][142][143][144]153,154,156,162,171,175,197,213,[244]…”

Section: Tm-hydridesmentioning

confidence: 99%

Recent Development in Nanoconfined Hydrides for Energy Storage

Comănescu

2022

IJMS

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Hydrogen is the ultimate vector for a carbon-free, sustainable green-energy. While being the most promising candidate to serve this purpose, hydrogen inherits a series of characteristics making it particularly difficult to handle, store, transport and use in a safe manner. The researchers’ attention has thus shifted to storing hydrogen in its more manageable forms: the light metal hydrides and related derivatives (ammonia-borane, tetrahydridoborates/borohydrides, tetrahydridoaluminates/alanates or reactive hydride composites). Even then, the thermodynamic and kinetic behavior faces either too high energy barriers or sluggish kinetics (or both), and an efficient tool to overcome these issues is through nanoconfinement. Nanoconfined energy storage materials are the current state-of-the-art approach regarding hydrogen storage field, and the current review aims to summarize the most recent progress in this intriguing field. The latest reviews concerning H2 production and storage are discussed, and the shift from bulk to nanomaterials is described in the context of physical and chemical aspects of nanoconfinement effects in the obtained nanocomposites. The types of hosts used for hydrogen materials are divided in classes of substances, the mean of hydride inclusion in said hosts and the classes of hydrogen storage materials are presented with their most recent trends and future prospects.

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“…One of the difficulties in understanding how powder composites of reactive fuel/oxidizer − systems behave is the lack of control of the mixing length. On the other hand, there is a considerable body of work on the formation of nanolaminate structures with alternating reactive layers typically created by sputter deposition.…”

Section: Introductionmentioning

confidence: 99%

“…Energetic particulate composites have been extensively investigated through macroscopic characterization approaches to characterize temperature, burn rates, and thermal decomposition properties − However, characterization at the microscopic scale has been less readily available. Given that the composition of these composites consists of nano or micro-sized reactants, observation at smaller length scales is needed to better understand the role of mass and heat transfer. ,− Previously, we employed a recently developed microscopic dynamic imaging system to probe the reaction zone of sputter-deposited Al/CuO nanolaminates with μs and μm temporal and spatial resolution respectively, which is more comparable to the reactant dimensions and reaction timescales .…”

Section: Introductionmentioning

confidence: 99%

Direct Imaging and Simulation of the Interface Reaction of Metal/Metal Oxide Nanoparticle Laminates

2022

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One of the difficulties in understanding how powder composites of reactive fuel/oxidizer systems behave is the lack of control of the mixing length. In this study, we have prepared Al/CuO particle laminates using a direct writing approach. With as little as 10 wt % polymers, we were able to obtain free-standing microscale particle-based laminates. Using these composites, we were able to image the cross section of the laminates to directly probe the interface reaction with highspeed microscopic imaging and pyrometry. We show quantitatively how the burn rate can be altered by changing the layer thicknesses of the printed laminates and under high-speed microscopy imaging asymmetry heat transfer resulting in fingering in the temperature profiles in the reaction front. Numerical simulations of the heat and mass transport processes are able to reproduce the finger-structured reaction fronts. We find that for Al/CuO particle-based laminates, the lateral O 2 diffusion rate from the CuO layer to the Al layer appears to be rate-limiting. The finger-like profiles appear due to the combined effects from the faster propagation of the interfacial reaction over the bulk, and the thermal diffusivity differences between the Al/CuO layers. Interestingly we see no evidence of layer intermixing even on postcombustion inspection. These results are to our knowledge the first imaging of interface reactions between particle composites and provide a valuable testbed for probing mechanisms and validating models.

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Rerouting Pathways of Solid-State Ammonia Borane Energy Release

Cited by 11 publications

References 66 publications

In-Situ Thermochemical Shock-Induced Stress at the Metal/Oxide Interface Enhances Reactivity of Aluminum Nanoparticles

In-Situ Thermochemical Shock-Induced Stress at the Metal/Oxide Interface Enhances Reactivity of Aluminum Nanoparticles

Recent Development in Nanoconfined Hydrides for Energy Storage

Direct Imaging and Simulation of the Interface Reaction of Metal/Metal Oxide Nanoparticle Laminates

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