Honors & Awards


  • NSF Graduate Research Fellowship, National Science Foundation (May 2017)
  • Ford Foundation Fellowship, National Academy of Sciences, Ford Foundation (May 2017)
  • EDGE Fellowship, Stanford University (May 2017)

Education & Certifications


  • B.S., Pennsylvania State University, Materials Science and Engineering (2016)
  • A.S., Cochise College, Engineering (2013)

Patents


  • Rafael A. Vilá. "United States Patent 62/398,751 Vertical 2D Structures for Advanced Electronic and Optoelectronic Systems", Pennsylvania State University, Oct 14, 2015

2021-22 Courses


All Publications


  • Bright and stable light-emitting diodes made with perovskite nanocrystals stabilized in metal-organic frameworks NATURE PHOTONICS Tsai, H., Shrestha, S., Vila, R. A., Huang, W., Liu, C., Hou, C., Huang, H., Wen, X., Li, M., Wiederrecht, G., Cui, Y., Cotlet, M., Zhang, X., Ma, X., Nie, W. 2021
  • Cryogenic Electron Microscopy for Energy Materials. Accounts of chemical research Zhang, Z., Cui, Y., Vila, R., Li, Y., Zhang, W., Zhou, W., Chiu, W., Cui, Y. 2021

    Abstract

    ConspectusThe development of clean energy generation, transmission, and distribution technology, for example, high energy density batteries and high efficiency solar cells, is critical to the progress toward a sustainable future. Such advancement in both scientific understanding and technological innovations entail an atomic- and molecular-resolution understanding of the key materials and fundamental processes governing the operation and failure of the systems. These dynamic processes span multiple length and time scales bridging materials and interfaces involved across the entire device architecture. However, these key components are often highly sensitive to air, moisture, and electron-beam radiation and therefore remain resistant to conventional nanoscale interrogation by electron-optical methods, such as high-resolution (scanning) transmission electron microscopy and spectroscopy.Fortunately, the rapid progress in cryogenic electron microscopy (cryo-EM) for physical sciences starts to offer researchers new tools and methods to probe these otherwise inaccessible length scales of components and phenomena in energy science. Specifically, weakly bonded and reactive materials, interfaces and phases that typically degrade under high energy electron-beam irradiation and environmental exposure can potentially be protected and stabilized by cryogenic methods, bringing up thrilling opportunities to address many crucial yet unanswered questions in energy science, which can eventually lead to new scientific discoveries and technological breakthroughs.Thus, in this Account, we aim to highlight the significance of cryo-EM to energy related research and the impactful results that can be potentially spawned from there. Due to the limited space, we will mainly review representative examples of cryo-EM methodology for lithium (Li)-based batteries, hybrid perovskite solar cells, and metal-organic-frameworks, which have shown great promise in revealing atomic resolution of both structural and chemical information on the sensitive yet critical components in these systems. We will first emphasize the application of cryo-EM to resolve the nanostructure and chemistry of solid-electrolyte interphases, cathode-electrolyte interphase, and electrode materials in batteries to reflect how cryo-EM could inspire rational materials design and guide battery research toward practical applications. We then discuss how cryo-EM helped to reveal guest intercalation chemistry in weakly bonded metal-organic-frameworks to develop a complete picture of host-guest interaction. Next, we summarize efforts in hybrid perovskite materials for solar cells where cryo-EM preserved the volatile organic molecules and protected perovskites from any air or moisture contamination. Finally, we conclude with perspectives and brief discussion on future directions for cryo-EM in energy and materials science.

    View details for DOI 10.1021/acs.accounts.1c00183

    View details for PubMedID 34278783

  • Potentiometric Measurement to Probe Solvation Energy and Its Correlation to Lithium Battery Cyclability. Journal of the American Chemical Society Kim, S. C., Kong, X., Vila, R. A., Huang, W., Chen, Y., Boyle, D. T., Yu, Z., Wang, H., Bao, Z., Qin, J., Cui, Y. 2021

    Abstract

    The electrolyte plays a critical role in lithium-ion batteries, as it impacts almost every facet of a battery's performance. However, our understanding of the electrolyte, especially solvation of Li+, lags behind its significance. In this work, we introduce a potentiometric technique to probe the relative solvation energy of Li+ in battery electrolytes. By measuring open circuit potential in a cell with symmetric electrodes and asymmetric electrolytes, we quantitatively characterize the effects of concentration, anions, and solvents on solvation energy across varied electrolytes. Using the technique, we establish a correlation between cell potential (Ecell) and cyclability of high-performance electrolytes for lithium metal anodes, where we find that solvents with more negative cell potentials and positive solvation energies-those weakly binding to Li+-lead to improved cycling stability. Cryogenic electron microscopy reveals that weaker solvation leads to an anion-derived solid-electrolyte interphase that stabilizes cycling. Using the potentiometric measurement for characterizing electrolytes, we establish a correlation that can guide the engineering of effective electrolytes for the lithium metal anode.

    View details for DOI 10.1021/jacs.1c03868

    View details for PubMedID 34184873

  • Microclusters of Kinked Silicon Nanowires Synthesized by a Recyclable Iodide Process for High-Performance Lithium-Ion Battery Anodes ADVANCED ENERGY MATERIALS Jeong, Y., Huang, W., Vila, R. A., Huang, W., Wang, J., Kim, S., Kim, Y., Zhao, J., Cui, Y. 2020
  • Nickel Impurities in the Solid-Electrolyte Interphase of Lithium-Metal Anodes Revealed by Cryogenic Electron Microscopy CELL REPORTS PHYSICAL SCIENCE Vila, R. A., Huang, W., Cui, Y. 2020; 1 (9)
  • Incorporating the nanoscale encapsulation concept from liquid electrolytes into solid-state lithium-sulfur batteries. Nano letters Gao, X., Zheng, X., Wang, J., Zhang, Z., Xiao, X., Wan, J., Ye, Y., Chou, L., Lee, H. K., Wang, J., Vila, R. A., Yang, Y., Zhang, P., Wang, L., Cui, Y. 2020

    Abstract

    Lithium-sulfur (Li-S) batteries are attractive due to their high specific energy and low-cost prospect. Most studies in the past decade are based on these batteries with liquid electrolytes, where many exciting material/structural designs are realized at the nanoscale to address problems of Li-S chemistry. Recently, there is a new promising direction to develop Li-S batteries with solid polymer electrolytes, although it is unclear whether the concepts from liquid electrolytes are applicable in the solid state to improve battery performance. Here we demonstrate that the nanoscale encapsulation concept based on Li2S-TiS2 core-shell particles, originally developed in liquid electrolytes, is very effective in solid polymer electrolytes. Using in situ optical cell measurement and sulfur K-edge X-ray absorption near edge spectroscopy, we find that polysulfides form and are well trapped inside individual particles by the nanoscale TiS2 encapsulation. This TiS2 encapsulation layer also functions to catalyze the oxidation reaction of Li2S to sulfur, even in solid-state electrolytes, proved by both experiments and density functional theory calculations. A high cell-level specific energy of 427 W∙h∙kg-1 at 60 °C (including the mass of the anode, cathode, and solid-state electrolyte, but excluding the current collector and packaging) is achieved by integrating TiS2 encapsulated Li2S cathode with ultrathin polyethylene oxide-based solid polymer electrolyte (10~20 m) and lithium metal anode. The solid-state cells show excellent stability over 150 charge/discharge cycles at 0.8 C at 80 °C. This study points to the fruitful direction of borrowing concepts from liquid electrolytes into solid-state Li-S batteries.

    View details for DOI 10.1021/acs.nanolett.0c02033

    View details for PubMedID 32515973

  • Tortuosity Effects in Lithium-Metal Host Anodes JOULE Chen, H., Pei, A., Wan, J., Lin, D., Vila, R., Wang, H., Mackanic, D., Steinruck, H., Huang, W., Li, Y., Yang, A., Xie, J., Wu, Y., Wang, H., Cui, Y. 2020; 4 (4): 938–52
  • Electrochemical generation of liquid and solid sulfur on two-dimensional layered materials with distinct areal capacities. Nature nanotechnology Yang, A. n., Zhou, G. n., Kong, X. n., Vilá, R. A., Pei, A. n., Wu, Y. n., Yu, X. n., Zheng, X. n., Wu, C. L., Liu, B. n., Chen, H. n., Xu, Y. n., Chen, D. n., Li, Y. n., Fakra, S. n., Hwang, H. Y., Qin, J. n., Chu, S. n., Cui, Y. n. 2020

    Abstract

    It has recently been shown that sulfur, a solid material in its elementary form S8, can stay in a supercooled state as liquid sulfur in an electrochemical cell. We establish that this newly discovered state could have implications for lithium-sulfur batteries. Here, through in situ studies of electrochemical sulfur generation, we show that liquid (supercooled) and solid elementary sulfur possess very different areal capacities over the same charging period. To control the physical state of sulfur, we studied its growth on two-dimensional layered materials. We found that on the basal plane, only liquid sulfur accumulates; by contrast, at the edge sites, liquid sulfur accumulates if the thickness of the two-dimensional material is small, whereas solid sulfur nucleates if the thickness is large (tens of nanometres). Correlating the sulfur states with their respective areal capacities, as well as controlling the growth of sulfur on two-dimensional materials, could provide insights for the design of future lithium-sulfur batteries.

    View details for DOI 10.1038/s41565-019-0624-6

    View details for PubMedID 31988508

  • Electrochemical generation of liquid and solid sulfur on two-dimensional layered materials with distinct areal capacities Nature Nanotechnology Yang, A., Zhou, G., et al 2020
  • Unravelling Degradation Mechanisms and Atomic Structure of Organic-Inorganic Halide Perovskites by Cryo-EM JOULE Li, Y., Zhou, W., Li, Y., Huang, W., Zhang, Z., Chen, G., Wang, H., Wu, G., Rolston, N., Vila, R., Chiu, W., Cui, Y. 2019; 3 (11): 2854–66
  • Unravelling Atomic Structure and Degradation Mechanisms of Organic-Inorganic Halide Perovskites by Cryo-EM. Joule Li, Y., Zhou, W., Li, Y., Huang, W., Zhang, Z., Chen, G., Wang, H., Wu, G. H., Rolston, N., Vila, R., Chiu, W., Cui, Y. 2019; 3 (11): 2854-2866

    Abstract

    Despite rapid progress of hybrid organic-inorganic halide perovskite solar cells, using transmission electron microscopy to study their atomic structures has not been possible because of their extreme sensitivity to electron beam irradiation and environmental exposure. Here, we develop cryogenic-electron microscopy (cryo-EM) protocols to preserve an extremely sensitive perovskite, methylammonium lead iodide (MAPbI3) under various operating conditions for atomic-resolution imaging. We discover the precipitation of lead iodide nanoparticles on MAPbI3 nanowire's surface after short UV illumination and surface roughening after only 10 s exposure to air, while these effects remain undetected in conventional x-ray diffraction. We establish a definition for critical electron dose, and find this value for MAPbI3 at cryogenic condition to be 12 e-/Å2 at 1.49 Å spatial resolution. Our results highlight the importance of cryo-EM since traditional techniques cannot capture important nanoscale changes in morphology and structure that have important implications for perovskite solar cell stability and performance.

    View details for DOI 10.1016/j.joule.2019.08.016

    View details for PubMedID 34109301

    View details for PubMedCentralID PMC8186345

  • Cryo-EM Structures of Atomic Surfaces and Host-Guest Chemistry in Metal-Organic Frameworks MATTER Li, Y., Wang, K., Zhou, W., Li, Y., Vila, R., Huang, W., Wang, H., Chen, G., Wu, G., Tsao, Y., Wang, H., Sinclair, R., Chiu, W., Cui, Y. 2019; 1 (2): 428–38
  • Cryo-EM structures of atomic surfaces and host-guest chemistry in metal-organic frameworks. Matter Li, Y., Wang, K., Zhou, W., Li, Y., Vila, R., Huang, W., Wang, H., Chen, G., Wu, G. H., Tsao, Y., Wang, H., Sinclair, R., Chiu, W., Cui, Y. 2019; 1 (2): 428-438

    Abstract

    Host-guest interactions govern the chemistry of a broad range of functional materials, but direct imaging using conventional transmission electron microscopy (TEM) has not been possible. This problem is exacerbated in metal-organic framework (MOF) materials, which are easily damaged by the electron beam. Here, we use cryogenic-electron microscopy (cryo-EM) to stabilize the host-guest structure and resolve the atomic surface of zeolitic imidazolate framework (ZIF-8) and its interaction with guest CO2 molecules. We image step-edge sites on the ZIF-8 surface that provides insight to its growth behavior. Furthermore, we observe two distinct binding sites for CO2 within the ZIF-8 pore, which are predicted by density functional theory (DFT) to be energetically favorable. This CO2 insertion induces an apparent ~3% lattice expansion along the <002> and <011> directions of the ZIF-8 unit cell. The ability to stabilize and preserve host-guest chemistry opens a rich materials space for scientific exploration and discovery using cryo-EM.

    View details for DOI 10.1016/j.matt.2019.06.001

    View details for PubMedID 34104881

    View details for PubMedCentralID PMC8184120

  • Wrinkled Graphene Cages as Hosts for High-Capacity Li Metal Anodes Shown by Cryogenic Electron Microscopy. Nano letters Wang, H., Li, Y., Li, Y., Liu, Y., Lin, D., Zhu, C., Chen, G., Yang, A., Yan, K., Chen, H., Zhu, Y., Li, J., Xie, J., Xu, J., Zhang, Z., Vila, R., Pei, A., Wang, K., Cui, Y. 2019

    Abstract

    Lithium (Li) metal has long been considered the "holy grail" of battery anode chemistry but is plagued by low efficiency and poor safety due to its high chemical reactivity and large volume fluctuation, respectively. Here we introduce a new host of wrinkled graphene cage (WGC) for Li metal. Different from recently reported amorphous carbon spheres, WGC show highly improved mechanical stability, better Li ion conductivity, and excellent solid electrolyte interphase (SEI) for continuous robust Li metal protection. At low areal capacities, Li metal is preferentially deposited inside the graphene cage. Cryogenic electron microscopy characterization shows that a uniform and stable SEI forms on the WGC surface that can shield the Li metal from direct exposure to electrolyte. With increased areal capacities, Li metal is plated densely and homogeneously into the outer pore spaces between graphene cages with no dendrite growth or volume change. As a result, a high Coulombic efficiency (CE) of 98.0% was achieved under 0.5 mA/cm2 and 1-10 mAh/cm2 in commercial carbonate electrolytes, and a CE of 99.1% was realized with high-concentration electrolytes under 0.5 mA/cm2 and 3 mAh/cm2. Full cells using WGC electrodes with prestored Li paired with Li iron phosphate showed greatly improved cycle lifetime. With 10 mAh/cm2 Li metal deposition, the WGC/Li compositeanodewas able to provide a high specific capacity of 2785 mAh/g. With its roll-to-roll compatible fabrication procedure, WGC serves as a highly promising material for the practical realization of Li metal anodes in next-generation high energy density secondary batteries.

    View details for PubMedID 30676759

  • In situ crystallization kinetics of two-dimensional MoS2 2D Materials Vilá, R. A., Rao, R., Muratore, C., Bianco, E., Robinson, J. A., Maruyama, B., Glavin, N. R. 2017; 5 (1)

    View details for DOI 10.1088/2053-1583/aa9674

  • Bottom-up synthesis of vertically oriented two-dimensional materials 2D MATERIALS Vila, R. A., Momeni, K., Wang, Q., Bersch, B. M., Lu, N., Kim, M. J., Chen, L. Q., Robinson, J. A. 2016; 3 (4)
  • Two-dimensional gallium nitride realized via graphene encapsulation NATURE MATERIALS Al Balushi, Z. Y., Wang, K., Ghosh, R. K., Vila, R. A., Eichfeld, S. M., Caldwell, J. D., Qin, X., Lin, Y., DeSario, P. A., Stone, G., Subramanian, S., Paul, D. F., Wallace, R. M., Datta, S., Redwing, J. M., Robinson, J. A. 2016; 15 (11): 1166-?

    Abstract

    The spectrum of two-dimensional (2D) and layered materials 'beyond graphene' offers a remarkable platform to study new phenomena in condensed matter physics. Among these materials, layered hexagonal boron nitride (hBN), with its wide bandgap energy (∼5.0-6.0 eV), has clearly established that 2D nitrides are key to advancing 2D devices. A gap, however, remains between the theoretical prediction of 2D nitrides 'beyond hBN' and experimental realization of such structures. Here we demonstrate the synthesis of 2D gallium nitride (GaN) via a migration-enhanced encapsulated growth (MEEG) technique utilizing epitaxial graphene. We theoretically predict and experimentally validate that the atomic structure of 2D GaN grown via MEEG is notably different from reported theory. Moreover, we establish that graphene plays a critical role in stabilizing the direct-bandgap (nearly 5.0 eV), 2D buckled structure. Our results provide a foundation for discovery and stabilization of 2D nitrides that are difficult to prepare via traditional synthesis.

    View details for DOI 10.1038/NMAT4742

    View details for Web of Science ID 000386377000011

    View details for PubMedID 27571451

  • Growth and Tunable Surface Wettability of Vertical MoS2 Layers for Improved Hydrogen Evolution Reactions ACS APPLIED MATERIALS & INTERFACES Bhimanapati, G. R., Hankins, T., Lei, Y., Vila, R. A., Fuller, I., Terrones, M., Robinson, J. A. 2016; 8 (34): 22190-22195

    Abstract

    Layered materials, especially the transition metal dichalcogenides (TMDs), are of interest for a broad range of applications. Among the class of TMDs, molybdenum disulfide (MoS2) is perhaps the most studied because of its natural abundance and use in optoelectronics, energy storage and energy conversion applications. Understanding the fundamental structure-property relations is key for tailoring the enhancement in the above-mentioned applications. Here, we report a controlled powder vaporization synthesis of MoS2 flower-like structures consisting of vertically grown layers of MoS2 exhibiting exposed edges. This growth is readily achievable on multiple substrates, such as graphite, silicon, and silicon dioxide. The resulting MoS2 flowers are highly crystalline and stoichiometric. Further observations using contact angle indicate that MoS2 flowers exhibit the highest reported contact angle of ∼160 ± 10°, making the material super hydrophobic. This surface wettability was further tuned by changing the edge chemistry of the MoS2 flowers using an ozone etching treatment. Hydrogen evolution reaction (HER) measurements indicate that the surface treated with UV-ozone showed a reduction in the Tafel slope from 185 to 54 mV/dec, suggesting an increase in the amount of reactive surface to generate hydrogen.

    View details for DOI 10.1021/acsami.6b05848

    View details for Web of Science ID 000382514100041

    View details for PubMedID 27500662