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Kuang, Jason

Publications and source records attributed to Kuang, Jason.

Elucidating the Discharge Behavior of Aqueous Zinc Sulfur Batteries in the Presence of Molybdenum(IV) Chalcogenide Catalyst: The Criticality of Interfacial Electrochemistry

The aqueous zinc-sulfur battery holds promise for significant capacity and energy density with low cost and safe operation based on environmentally benign materials. However, it suffers from the sluggish kinetics of the conversion reaction. Here, we highlight the efficacy of molybdenum(IV) sulfide (MoS 2 ) to reduce the overpotential of S-ZnS conversion in aqueous electrolytes and study the discharge products formed at the solid-solid and solid-liquid interfaces using experimental and theoretical approaches. Specifically, the MoS 2 -catalyzed electrochemical conversion reaction is characterized via ex situ X-ray diffraction (XRD), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), Raman spectroscopy, synchrotron-based Mo K-edge X-ray absorption spectroscopy (XAS), and in situ synchrotron-based X-ray computed tomography (XCT). Additionally, operando synchrotron-based S K-edge XAS and X-ray fluorescence (XRF) maps are collected to determine the spatial evolution of sulfur-based species at the electrode-electrolyte interface. Further, coupling the operando S K-edge XAS data with the simulated spectra and fitting the data suggested a possible ZnS 2 intermediate phase.

25 ENERGY STORAGE↗

Unveiling Charge Transport and Degradation Mechanisms of Aqueous Zn|α-MoO 3 Batteries in Conventional Concentration and Water-in-Salt Electrolytes: A Multi-Modal In Situ and Operando Study

Herein charge storage and transport properties are elucidated and cell degradation mechanisms of rechargeable aqueous Zn|alpha-MoO 3 batteries in three electrolyte systems (3 m ZnSO 4 , 3 m ZnCl 2 , and 30 m ZnCl 2 [12.5 m] water-in-salt (WIS)) are distinguished by a combination of in situ X-ray diffraction (XRD), in situ X-ray absorption spectroscopy (XAS), operando optoelectrochemistry, and operando energy dispersive X-ray diffraction (EDXRD). In conventional concentration 3 m electrolytes, in situ XRD and XAS, as well as ex situ scanning transmission electron microscopy data collectively support Zn 2+ as the primary charge carrier. In addition, these systems are susceptible to cathode dissolution, Zn corrosion coupled with the hydrogen evolution reaction, and the resultant formation of basic zinc salt phases. The multi-modal in situ and operando experimental analyses validate facile H+ intercalation and extraction in concentrated 30 m ZnCl 2 WIS electrolyte. Via operando EDXRD, reaction front and charge transport limitation during discharge and charge in the viscous WIS electrolyte are spatially tracked. Here this work provides new insight into the stability and degradation mechanisms of aqueous zinc batteries during static storage and upon dynamic cycling, and highlights the utility of in situ and operando techniques in understanding the superior stability of WIS electrolytes.

25 ENERGY STORAGE↗

The Dopamine Assisted Synthesis of MoO3/Carbon Electrodes With Enhanced Capacitance in Aqueous Electrolyte

A capacitance increase phenomenon is observed for MoO 3 electrodes synthesized via a sol-gel process in the presence of dopamine hydrochloride (Dopa HCl) as compared to α-MoO 3 electrodes in 5M ZnCl 2 aqueous electrolyte. The synthesis approach is based on a hydrogen peroxide-initiated sol-gel reaction to which the Dopa HCl is added. The powder precursor (Dopa) x MoO y , is isolated from the metastable gel using freeze-drying. Hydrothermal treatment (HT) of the precursor results in the formation of MoO 3 accompanied by carbonization of the organic molecules; designated as HT-MoO 3 /C. HT of the precipitate formed in the absence of dopamine in the reaction produced α-MoO 3 , which was used as a reference material in this study (α-MoO 3 -ref). Scanning electron microscopy (SEM) images show a nanobelt morphology for both HT-MoO 3 /C and α-MoO 3 -ref powders, but with distinct differences in the shape of the nanobelts. The presence of carbonaceous content in the structure of HT-MoO 3 /C is confirmed by FTIR and Raman spectroscopy measurements. X-ray diffraction (XRD) and Rietveld refinement analysis demonstrate the presence of α-MoO 3 and h-MoO 3 phases in the structure of HT-MoO 3 /C. The increased specific capacitance delivered by the HT-MoO 3 /C electrode as compared to the α-MoO 3 -ref electrode in 5M ZnCl 2 electrolyte in a −0.25–0.70 V vs. Ag/AgCl potential window triggered a more detailed study in an expanded potential window. In the 5M ZnCl 2 electrolyte at a scan rate of 2 mV s −1 , the HT-MoO 3 /C electrode shows a second cycle capacitance of 347.6 F g −1 . The higher electrochemical performance of the HT-MoO 3 /C electrode can be attributed to the presence of carbon in its structure, which can facilitate electron transport. Our study provides a new route for further development of metal oxides for energy storage applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bifunctional MnO x electrocatalysts for zinc–air batteries in alkaline electrolytes

The growing need for rechargeable zinc–air batteries has led researchers to look for low-cost and robust catalytic candidates. Furthermore, manganese oxides are promising for their low toxicity, natural abundance and low cost. In this review, we summarize the versatility of manganese oxides which is achievable by adjusting synthetic parameters. In addition, we highlight how manganese oxides impact zinc–air electrochemistry.

25 ENERGY STORAGE↗

Zinc–air batteries in neutral/near-neutral electrolytes

The need to fully utilize intermittent renewable energy and have energy security, large-scale batteries are necessary. The aqueous zinc–air battery (ZAB) is a promising potential candidate for its safety, low-cost, and theoretical capacity. This research on ZAB mainly focused on alkaline electrolytes. These are favored for their conductivity, but greatly reduce the stability of the battery by zinc corrosion from the hydrogen evolution reaction (HER), dendrite formation, and carbonate formation. To address these issues, recently neutral and near-neutral electrolytes have been applied to aqueous ZAB to suppress HER, dendrite formation, and minimize carbonate formation. These include the use of chloride-based, potassium nitrate, aqueous organic, solid-state electrolytes supplemented with additives to improve the performance and stability. This field is still young with significant opportunities available for research.

25 ENERGY STORAGE↗

Lithium vanadium oxide (Li 1.1 V 3 O 8 ) thick porous electrodes with high rate capacity: utilization and evolution upon extended cycling elucidated via operando energy dispersive X-ray diffraction and continuum simulation

The phase distribution of lithiated LVO in thick (~500 μm) porous electrodes (TPEs) designed to facilitate both ion and electron transport was determined using synchrotron-based operando energy dispersive X-ray diffraction (EDXRD). Probing 3 positions in the TPE while cycling at a 1C rate revealed a homogeneous phase transition across the thickness of the electrode at the 1st and 95th cycles. Additionally, continuum modelling indicated uniform lithiation across the TPE in agreement with the EDXRD results and ascribed decreasing accessible active material to be the cause of loss in delivered capacity between the 1st and 95th cycles. The model was supported by the observation of significant particle fracture by SEM consistent with loss of electrical contact. Overall, the combination of operando EDXRD, continuum modeling, and ex situ measurements enabled a deeper understanding of lithium vanadium oxide transport properties under high rate extended cycling within a thick highly porous electrode architecture.

25 ENERGY STORAGE↗

Quantifying Uncertainty in Tortuosity Estimates for Porous Electrodes

Measuring tortuosity in porous electrodes is important for understanding rate capability and optimizing design. Here, we describe an approach to determine electrode tortuosities and quantify the associated uncertainties by fitting a P2D model to discharge profiles from a standard rate capability test. A dimensionless current is identified as a design-of-experiment parameter that can be used to identify experiments that return confident estimates of tortuosity, even when other model parameters are not known with certainty. This approach is applied to analysis of L i x V 3 O 8 (LVO) electrodes and L i x N i 0.33 M n 0.33 C o 0.33 O 2 (NMC) electrodes. The details of the assumptions made in these measurements and their impact on the reported uncertainties are discussed. We also perform an uncertainty analysis on the standard method for quantifying tortuosity in the literature: electrochemical impedance spectroscopy collected under blocking electrolyte conditions. We find that confident estimates can be obtained using this approach even when uncertainties in equivalent circuit model parameters are considered.

25 ENERGY STORAGE↗

Achieving Stable Molybdenum Oxide Cathodes for Aqueous Zinc-Ion Batteries in Water-in-Salt Electrolyte

A layered MoO 3 material with large interlayer spacing represents a promising cathode for aqueous rechargeable Zn-ion batteries (ARZIBs), but the implementation of this material is limited due to the intrinsically low conductivity and poor structural stability. A 30 m ZnCl 2 water-in-salt electrolyte (WISE) was introduced to a MoO 3 nanobelt cathode for the first time, significantly increasing the stability of MoO 3 cathodes compared to those in 3 M ZnSO 4 and 3 M ZnCl2 electrolyte. The Zn/MoO 3 cell in WISE unambiguously demonstrated significantly improved rate performance delivering 349, 253, and 222 mAh/g at 100, 500, and 1000 mA/g, denoting a 2×, and 12× capacity increase of those achieved in 3 M electrolytes at 500 and 1000 mA/g, respectively. A capacity retention rate of 73% was achieved after (dis)charging at 100 mA/g for 100 cycles, and no obvious capacity fading was observed at higher current densities of 500 mA/g and 2A/g. A compilation of structural and morphological characterization was systematically performed to provide insight into the mechanisms of the improved performance in ZnCl 2 WISE for the MoO3 cathode materials. Specifically, our data collectively suggested that the drastic fading in 3M electrolytes can be attributed to the parasitic surface deposits on Zn originated from Mo dissolution and H 2 formation due to Zn corrosion and hydrogen evolution reaction (HER), which were significantly suppressed in the ZnCl 2 WISE. The direct visualization of these side reactions was achieved for the first time in the Zn-MoO 3 system, using an in situ optoelectrochemical measurement.

25 ENERGY STORAGE↗

Achieving Stable Molybdenum Oxide Cathodes for Aqueous Zinc‐Ion Batteries in Water‐in‐Salt Electrolyte

Abstract Layered MoO 3 represents a promising cathode for aqueous rechargeable Zn‐ion batteries, but the implementation of this material is limited due to the low conductivity and poor structural stability. A 30 m ZnCl 2 water‐in‐salt electrolyte (WISE) is introduced to a MoO 3 nanobelt cathode for the first time, significantly increasing the stability of MoO 3 cathodes compared to those in 3 m ZnSO 4 and 3 m ZnCl 2 . The Zn/MoO 3 cell in WISE unambiguously demonstrate significantly improved rate performance delivering 349, 253, and 222 mAh g −1 at 100, 500, and 1000 mA g −1 , denoting a 12× capacity increase of those achieved in 3 m electrolytes at 1000 mA g −1 . A capacity retention rate of 73% is achieved after (dis)charging at 100 mA g −1 for 100 cycles, and no obvious capacity fading is observed at higher current densities of 500 mA g −1 and 2 A g −1 . Specifically, the data suggest that the drastic fading in 3 m electrolytes can be attributed to the parasitic surface deposits on Zn originated from Mo dissolution and H 2 formation due to Zn corrosion and hydrogen evolution reaction, which are significantly suppressed in the WISE. The direct visualization of these side reactions is achieved for the first time in the Zn‐MoO 3 system, using an in situ optoelectrochemical measurement.

Wang, Lei↗