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7. Optimization of the Mechanical Properties and the Cytocompatibility for the PMMA Nanocomposites Reinforced with the Hydroxyapatite Nanofibers and the Magnesium Phosphate Nanosheets

Author

Shirdar, Mostafa Rezazadeh, primary, Taheri, Mohammad Mahdi, additional, Qi, Mei-Li, additional, Gohari, Soheil, additional, Farajpour, Nasim, additional, Narayanan, Surya, additional, Foroozan, Tara, additional, Sharifi-Asl, Soroosh, additional, Shahbazian-Yassar, Reza, additional, and Shokuhfar, Tolou, additional

Published
2021
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10. Highly‐Cyclable Room‐Temperature Phosphorene Polymer Electrolyte Composites for Li Metal Batteries

Author

Rojaee, Ramin, primary, Cavallo, Salvatore, additional, Mogurampelly, Santosh, additional, Wheatle, Bill K., additional, Yurkiv, Vitaliy, additional, Deivanayagam, Ramasubramonian, additional, Foroozan, Tara, additional, Rasul, Md Golam, additional, Sharifi‐Asl, Soroosh, additional, Phakatkar, Abhijit H., additional, Cheng, Meng, additional, Son, Seoung‐Bum, additional, Pan, Yayue, additional, Mashayek, Farzad, additional, Ganesan, Venkat, additional, and Shahbazian‐Yassar, Reza, additional

Published
2020
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21. Anti‐Oxygen Leaking LiCoO 2

Author

Sharifi‐Asl, Soroosh, primary, Soto, Fernando A., additional, Foroozan, Tara, additional, Asadi, Mohammad, additional, Yuan, Yifei, additional, Deivanayagam, Ramasubramonian, additional, Rojaee, Ramin, additional, Song, Boao, additional, Bi, Xuanxuan, additional, Amine, Khalil, additional, Lu, Jun, additional, Salehi‐khojin, Amin, additional, Balbuena, Perla B., additional, and Shahbazian‐Yassar, Reza, additional

Published
2019
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29. Facet-Dependent Thermal Instability in LiCoO2

Author

Sharifi-Asl, Soroosh, primary, Soto, Fernando A., additional, Nie, Anmin, additional, Yuan, Yifei, additional, Asayesh-Ardakani, Hasti, additional, Foroozan, Tara, additional, Yurkiv, Vitaliy, additional, Song, Boao, additional, Mashayek, Farzad, additional, Klie, Robert F., additional, Amine, Khalil, additional, Lu, Jun, additional, Balbuena, Perla B., additional, and Shahbazian-Yassar, Reza, additional

Published
2017
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30. Revealing Sintering Kinetics of MoS2-Supported Metal Nanocatalysts in Atmospheric Gas Environments via OperandoTransmission Electron Microscopy

Author

Song, Boao, Yang, Timothy T., Yuan, Yifei, Sharifi-Asl, Soroosh, Cheng, Meng, Saidi, Wissam A., Liu, Yuzi, and Shahbazian-Yassar, Reza

Abstract

The decoration of two-dimensional (2D) substrates with nanoparticles (NPs) serve as heterostructures for various catalysis applications. Deep understanding of catalyst degradation mechanisms during service conditions is crucial to improve the catalyst durability. Herein, we studied the sintering behavior of Pt and bimetallic Au-core Pt-shell (Au@Pt core–shell) NPs on MoS2supports at high temperatures under vacuum, nitrogen (N2), hydrogen (H2), and air environments by in situgas-cell transmission electron microscopy (TEM). The key observations are summarized as effect of environment:while particle migration and coalescence (PMC) was the main mechanism that led to Pt and Au@Pt NPs degradation under vacuum, N2, and H2environments, the degradation of MoS2substrate was prominent under exposure to air at high temperatures. Pt NPs were less stable in H2environment when compared with the Pt NPs under vacuum or N2, due to Pt–H interactions that weakened the adhesion of Pt on MoS2. Effect of NP composition:under H2, the stability of Au@Pt NPs was higher in comparison to Pt NPs. This is because H2promotes the alloying of Pt–Au, thus reducing the number of Pt at the surface (reducing H2interactions) and increasing Pt atoms in contact with MoS2. Effect of NP size:The alloying effect promoted by H2was more pronounced in small size Au@Pt NPs resulting in their higher sintering resistance in comparison to large size Au@Pt NPs and similar size Pt NPs. The present work provides key insights into the parameters affecting the catalyst degradation mechanisms on 2D supports.

Published
2020
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31. Revealing Grain-Boundary-Induced Degradation Mechanisms in Li-Rich Cathode Materials

Author

Sharifi-Asl, Soroosh, Yurkiv, Vitaliy, Gutierrez, Arturo, Cheng, Meng, Balasubramanian, Mahalingam, Mashayek, Farzad, Croy, Jason, and Shahbazian-Yassar, Reza

Abstract

Despite their high energy densities, Li- and Mn-rich, layered–layered, xLi2MnO3·(1 – x)LiTMO2(TM = Ni, Mn, Co) (LMR-NMC) cathodes require further development in order to overcome issues related to bulk and surface instabilities such as Mn dissolution, impedance rise, and voltage fade. One promising strategy to modify LMR-NMC properties has been the incorporation of spinel-type, local domains to create “layered–layered–spinel” cathodes. However, precise control of local structure and composition, as well as subsequent characterization of such materials, is challenging and elucidating structure–property relationships is not trivial. Therefore, detailed studies of atomic structures within these materials are still critical to their development. Herein, aberration corrected-scanning transmission electron microscopy (AC-STEM) is utilized to study atomic structures, prior to and subsequent to electrochemical cycling, of LMR-NMC materials having integrated spinel-type components. The results demonstrate that strained grain boundaries with various atomic configurations, including spinel-type structures, can exist. These high energy boundaries appear to induce cracking and promote dissolution of Mn by increasing the contact surface area to electrolyte as well as migration of Ni during cycling, thereby accelerating performance degradation. These results present insights into the important role that local structures can play in the macroscopic degradation of the cathode structures and reiterate the complexity of how synthesis and composition affect structure–electrochemical property relationships of advanced cathode designs.

Published
2020
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34. The influence of large cations on the electrochemical properties of tunnel-structured metal oxides

Author

Yuan, Yifei, primary, Zhan, Chun, additional, He, Kun, additional, Chen, Hungru, additional, Yao, Wentao, additional, Sharifi-Asl, Soroosh, additional, Song, Boao, additional, Yang, Zhenzhen, additional, Nie, Anmin, additional, Luo, Xiangyi, additional, Wang, Hao, additional, Wood, Stephen M., additional, Amine, Khalil, additional, Islam, M. Saiful, additional, Lu, Jun, additional, and Shahbazian-Yassar, Reza, additional

Published
2016
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37. Ultrafast and Highly Reversible Sodium Storage in Zinc‐Antimony Intermetallic Nanomaterials

Author

Nie, Anmin, primary, Gan, Li‐yong, additional, Cheng, Yingchun, additional, Tao, Xinyong, additional, Yuan, Yifei, additional, Sharifi‐Asl, Soroosh, additional, He, Kun, additional, Asayesh‐Ardakani, Hasti, additional, Vasiraju, Venkata, additional, Lu, Jun, additional, Mashayek, Farzad, additional, Klie, Robert, additional, Vaddiraju, Sreeram, additional, Schwingenschlögl, Udo, additional, and Shahbazian‐Yassar, Reza, additional

Published
2015
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38. Facet-Dependent Thermal Instability in LiCoO2.

Author

Sharifi-Asl, Soroosh, Soto, Fernando A., Nie, Anmin, Yifei Yuan, Asayesh-Ardakani, Hasti, Foroozan, Tara, Yurkiv, Vitaliy, Boao Song, Mashayek, Farzad, Klie, Robert F., Amine, Khalil, Jun Lu, Balbuena, Perla B., and Shahbazian-Yassar, Reza

Subjects
*LITHIUM-ion batteries, *THERMAL instability, *LITHIUM cobalt oxide, *OXYGEN, *CATHODES, *SCANNING transmission electron microscopy
Abstract

Thermal runaways triggered by the oxygen release from oxide cathode materials pose a major safety concern for widespread application of lithium ion batteries. Utilizing in situ aberration-corrected scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) at high temperatures, we show that oxygen release from LixCoO2 cathode crystals is occurring at the surface of particles. We correlated this local oxygen evolution from the LixCoO2 structure with local phase transitions spanning from layered to spinel and then to rock salt structure upon exposure to elevated temperatures. Ab initio molecular dynamics simulations (AIMD) results show that oxygen release is highly dependent on LixCoO2 facet orientation. While the [001] facets are stable at 300 °C, oxygen release is observed from the [012] and [104] facets, where under-coordinated oxygen atoms from the delithiated structures can combine and eventually evolve as O2. The novel understanding that emerges from the present study provides in-depth insights into the thermal runaway mechanism of Li-ion batteries and can assist the design and fabrication of cathode crystals with the most thermally stable facets. [ABSTRACT FROM AUTHOR]

Published
2017
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39. Facet-Dependent Thermal Instability in LiCoO2.

Author

Sharifi-Asl, Soroosh, Soto, Fernando A., Nie, Anmin, Yifei Yuan, Asayesh-Ardakani, Hasti, Foroozan, Tara, Yurkiv, Vitaliy, Boao Song, Mashayek, Farzad, Klie, Robert F., Amine, Khalil, Jun Lu, Balbuena, Perla B., and Shahbazian-Yassar, Reza

Published
2017
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40. Cations controlled growth of β-MnO2crystals with tunable facets for electrochemical energy storage

Author

Yao, Wentao, Odegard, Gregory M., Huang, Zhennan, Yuan, Yifei, Asayesh-Ardakani, Hasti, Sharifi-Asl, Soroosh, Cheng, Meng, Song, Boao, Deivanayagam, Ramasubramonian, Long, Fei, Friedrich, Craig R., Amine, Khalil, Lu, Jun, and Shahbazian-Yassar, Reza

Abstract

Engineering crystal facets to enhance their functionalities often require complex processing routes to suppress the growth of surfaces with the lowest thermodynamic energies. Herein, we report a unique method to control the morphologies of β-MnO2crystals with different occupancy of {100}/{111} facets through the effect of K+cations. Combining aberration-corrected scanning transmission electron microscopy (STEM), ultramicrotomy, and dynamic functional theory (DFT) simulation, we clarified that the β-MnO2crystals were formed through a direct solid-state phase transition process. Increasing the concentration of K+cations in the precursor gradually changed the morphology of β-MnO2from bipyramid prism ({100}+{111} facets) to an octahedron structure ({111} facets). The K+cations controlled the morphology of β-MnO2by affecting the formation of α-K0.5Mn4O8intermediate phase and the subsequent phase transition. Utilizing the β-MnO2crystals as the cathode for Li-ion batteries showed that highly exposed {111} facets offered β-MnO2crystal better rate performance, with ~70% capacity retention when the charge-discharge rate increased from 20 mA/g to 200 mA/g. Our work revealed a new mechanism to tune the morphology of this earth-abundant metal oxide crystal, which could be used to adjust its electrochemical performance for different applications, such as supercapacitors and catalysts for metal-air batteries and fuel cells.

Published
2018
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41. Ultrafast and Highly Reversible Sodium Storage in Zinc-Antimony Intermetallic Nanomaterials.

Author

Nie, Anmin, Gan, Li‐yong, Cheng, Yingchun, Tao, Xinyong, Yuan, Yifei, Sharifi‐Asl, Soroosh, He, Kun, Asayesh‐Ardakani, Hasti, Vasiraju, Venkata, Lu, Jun, Mashayek, Farzad, Klie, Robert, Vaddiraju, Sreeram, Schwingenschlögl, Udo, and Shahbazian‐Yassar, Reza

Subjects
NANOSTRUCTURED materials, SODIUM ions, STORAGE batteries, ZINC compounds, ANTIMONY compounds, INTERMETALLIC compounds, OXIDATION-reduction reaction
Abstract

The progress on sodium-ion battery technology faces many grand challenges, one of which is the considerably lower rate of sodium insertion/deinsertion in electrode materials due to the larger size of sodium (Na) ions and complicated redox reactions compared to the lithium-ion systems. Here, it is demonstrated that sodium ions can be reversibly stored in Zn-Sb intermetallic nanowires at speeds that can exceed 295 nm s−1. Remarkably, these values are one to three orders of magnitude higher than the sodiation rate of other nanowires electrochemically tested with in situ transmission electron micro­scopy. It is found that the nanowires display about 161% volume expansion after the first sodiation and then cycle with an 83% reversible volume expansion. Despite their massive expansion, the nanowires can be cycled without any cracking or facture during the ultrafast sodiation/desodiation process. In addition, most of the phases involved in the sodiation/desodiation process possess high electrical conductivity. More specifically, the NaZnSb exhibits a layered structure, which provides channels for fast Na+ diffusion. This observation indicates that Zn-Sb intermetallic nanomaterials offer great promise as high rate and good cycling stability anodic materials for the next generation of sodium-ion batteries. [ABSTRACT FROM AUTHOR]

Published
2016
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42. Tailoring the Edge Structure of Molybdenum Disulfide toward Electrocatalytic Reduction of Carbon Dioxide

Author

Abbasi, Pedram, Asadi, Mohammad, Liu, Cong, Sharifi-Asl, Soroosh, Sayahpour, Baharak, Behranginia, Amirhossein, Zapol, Peter, Shahbazian-Yassar, Reza, Curtiss, Larry A., and Salehi-Khojin, Amin

Abstract

Electrocatalytic conversion of carbon dioxide (CO2) into energy-rich fuels is considered to be the most efficient approach to achieve a carbon neutral cycle. Transition-metal dichalcogenides (TMDCs) have recently shown a very promising catalytic performance for CO2reduction reaction in an ionic liquid electrolyte. Here, we report that the catalytic performance of molybdenum disulfide (MoS2), a member of TMDCs, can be significantly improved by using an appropriate dopant. Our electrochemical results indicate that 5% niobium (Nb)-doped vertically aligned MoS2in ionic liquid exhibits 1 order of magnitude higher CO formation turnover frequency (TOF) than pristine MoS2at an overpotential range of 50–150 mV. The TOF of this catalyst is also 2 orders of magnitude higher than that of Ag nanoparticles over the entire range of studied overpotentials (100–650 mV). Moreover, the in situdifferential electrochemical mass spectrometry experiment shows the onset overpotential of 31 mV for this catalyst, which is the lowest onset potential for CO2reduction reaction reported so far. Our density functional theory calculations reveal that low concentrations of Nb near the Mo edge atoms can enhance the TOF of CO formation by modifying the binding energies of intermediates to MoS2edge atoms.

Published
2017
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48. Anti‐Oxygen Leaking LiCoO2.

Author

Sharifi‐Asl, Soroosh, Soto, Fernando A., Foroozan, Tara, Asadi, Mohammad, Yuan, Yifei, Deivanayagam, Ramasubramonian, Rojaee, Ramin, Song, Boao, Bi, Xuanxuan, Amine, Khalil, Lu, Jun, Salehi‐khojin, Amin, Balbuena, Perla B., and Shahbazian‐Yassar, Reza

Subjects
*ELECTRON energy loss spectroscopy, *MASS spectrometry, *HEAT transfer, *THERMAL instability, *DIFFERENTIAL scanning calorimetry, *TRANSMISSION electron microscopy
Abstract

LiCoO2 is a prime example of widely used cathodes that suffer from the structural/thermal instability issues that lead to the release of their lattice oxygen under nonequilibrium conditions and safety concerns in Li‐ion batteries. Here, it is shown that an atomically thin layer of reduced graphene oxide can suppress oxygen release from LixCoO2 particles and improve their structural stability. Electrochemical cycling, differential electrochemical mass spectroscopy, differential scanning calorimetry, and in situ heating transmission electron microscopy are performed to characterize the effectiveness of the graphene‐coating on the abusive tolerance of LixCoO2. Electrochemical cycling mass spectroscopy results suggest that oxygen release is hindered at high cutoff voltage cycling when the cathode is coated with reduced graphene oxide. Thermal analysis, in situ heating transmission electron microscopy, and electron energy loss spectroscopy results show that the reduction of Co species from the graphene‐coated samples is delayed when compared with bare cathodes. Finally, density functional theory and ab initio molecular dynamics calculations show that the rGO layers could suppress O2 formation more effectively due to the strong COcathode bond formation at the interface of rGO/LCO where low coordination oxygens exist. This investigation uncovers a reliable approach for hindering the oxygen release reaction and improving the thermal stability of battery cathodes. [ABSTRACT FROM AUTHOR]

Published
2019
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49. Anti‐Oxygen Leaking LiCoO2.

Author

Sharifi‐Asl, Soroosh, Soto, Fernando A., Foroozan, Tara, Asadi, Mohammad, Yuan, Yifei, Deivanayagam, Ramasubramonian, Rojaee, Ramin, Song, Boao, Bi, Xuanxuan, Amine, Khalil, Lu, Jun, Salehi‐khojin, Amin, Balbuena, Perla B., and Shahbazian‐Yassar, Reza

Subjects
ELECTRON energy loss spectroscopy, MASS spectrometry, HEAT transfer, THERMAL instability, DIFFERENTIAL scanning calorimetry, TRANSMISSION electron microscopy
Abstract

LiCoO2 is a prime example of widely used cathodes that suffer from the structural/thermal instability issues that lead to the release of their lattice oxygen under nonequilibrium conditions and safety concerns in Li‐ion batteries. Here, it is shown that an atomically thin layer of reduced graphene oxide can suppress oxygen release from LixCoO2 particles and improve their structural stability. Electrochemical cycling, differential electrochemical mass spectroscopy, differential scanning calorimetry, and in situ heating transmission electron microscopy are performed to characterize the effectiveness of the graphene‐coating on the abusive tolerance of LixCoO2. Electrochemical cycling mass spectroscopy results suggest that oxygen release is hindered at high cutoff voltage cycling when the cathode is coated with reduced graphene oxide. Thermal analysis, in situ heating transmission electron microscopy, and electron energy loss spectroscopy results show that the reduction of Co species from the graphene‐coated samples is delayed when compared with bare cathodes. Finally, density functional theory and ab initio molecular dynamics calculations show that the rGO layers could suppress O2 formation more effectively due to the strong COcathode bond formation at the interface of rGO/LCO where low coordination oxygens exist. This investigation uncovers a reliable approach for hindering the oxygen release reaction and improving the thermal stability of battery cathodes. [ABSTRACT FROM AUTHOR]

Published
2019
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50. Revealing Sintering Kinetics of MoS 2 -Supported Metal Nanocatalysts in Atmospheric Gas Environments via Operando Transmission Electron Microscopy.

Author

Song B, Yang TT, Yuan Y, Sharifi-Asl S, Cheng M, Saidi WA, Liu Y, and Shahbazian-Yassar R

Abstract

The decoration of two-dimensional (2D) substrates with nanoparticles (NPs) serve as heterostructures for various catalysis applications. Deep understanding of catalyst degradation mechanisms during service conditions is crucial to improve the catalyst durability. Herein, we studied the sintering behavior of Pt and bimetallic Au-core Pt-shell (Au@Pt core-shell) NPs on MoS 2 supports at high temperatures under vacuum, nitrogen (N 2 ), hydrogen (H 2 ), and air environments by in situ gas-cell transmission electron microscopy (TEM). The key observations are summarized as effect of environment: while particle migration and coalescence (PMC) was the main mechanism that led to Pt and Au@Pt NPs degradation under vacuum, N 2 , and H 2 environments, the degradation of MoS 2 substrate was prominent under exposure to air at high temperatures. Pt NPs were less stable in H 2 environment when compared with the Pt NPs under vacuum or N 2 , due to Pt-H interactions that weakened the adhesion of Pt on MoS 2 . Effect of NP composition: under H 2 , the stability of Au@Pt NPs was higher in comparison to Pt NPs. This is because H 2 promotes the alloying of Pt-Au, thus reducing the number of Pt at the surface (reducing H 2 interactions) and increasing Pt atoms in contact with MoS 2 . Effect of NP size: The alloying effect promoted by H 2 was more pronounced in small size Au@Pt NPs resulting in their higher sintering resistance in comparison to large size Au@Pt NPs and similar size Pt NPs. The present work provides key insights into the parameters affecting the catalyst degradation mechanisms on 2D supports.

Published
2020
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