Xu, Ting; Walter, Erich C.; Agrawal, Amit; Bohn, Christopher; Velmurugan, Jeyavel; Zhu, Wenqi; Lezec, Henri J.; Talin, A.A.
With vibrant colours and simple, roomerature processing methods, electrochromic polymers have attracted attention as active materials for flexible, low-power-consuming devices. However, slow switching speeds in devices realized to date, as well as the complexity of having to combine several distinct polymers to achieve a full-colour gamut, have limited electrochromic materials to niche applications. Here we achieve fast, high-contrast electrochromic switching by significantly enhancing the interaction of light-propagating as deep-subwavelength-confined surface plasmon polaritons through arrays of metallic nanoslits, with an electrochromic polymer-present as an ultra-thin coating on the slit sidewalls. The switchable configuration retains the short temporal charge-diffusion characteristics of thin electrochromic films, while maintaining the high optical contrast associated with thicker electrochromic coatings. We further demonstrate that by controlling the pitch of the nanoslit arrays, it is possible to achieve a full-colour response with high contrast and fast switching speeds, while relying on just one electrochromic polymer.
Gong, Chen; Ruzmetov, Dmitry; Pearse, Alexander; Ma, Dakang; Munday, Jeremy N.; Rubloff, Gary; Talin, A.A.; Leite, Marina S.
The further development of all-solid-state batteries is still limited by the understanding/engineering of the interfaces formed upon cycling. Here, we correlate the morphological, chemical, and electrical changes of the surface of thin-film devices with Al negative electrodes. The stable Al-Li-O alloy formed at the stress-free surface of the electrode causes rapid capacity fade, from 48.0 to 41.5 μAh/cm2 in two cycles. Surprisingly, the addition of a Cu capping layer is insufficient to prevent the device degradation. Nevertheless, Si electrodes present extremely stable cycling, maintaining >92% of its capacity after 100 cycles, with average Coulombic efficiency of 98%.
Metal-organic frameworks (MOFs) are crystalline nanoporous materials comprised of organic electron donors linked to metal ions by strong coordination bonds. Applications such as gas storage and separations are currently receiving considerable attention, but if the unique properties of MOFs could be extended to electronics, magnetics, and photonics, the impact on material science would greatly increase. Recently, we obtained "emergent properties," such as electronic conductivity and energy transfer, by infiltrating MOF pores with "guest" molecules that interact with the framework electronic structure. In this Perspective, we define a path to emergent properties based on the Guest@MOF concept, using zinc-carboxylate and copper-paddlewheel MOFs for illustration. Energy transfer and light harvesting are discussed for zinc carboxylate frameworks infiltrated with triplet-scavenging organometallic compounds and thiophene- and fullerene-infiltrated MOF-177. In addition, we discuss the mechanism of charge transport in TCNQ-infiltrated HKUST-1, the first MOF with electrical conductivity approaching conducting organic polymers. These examples show that guest molecules in MOF pores should be considered not merely as impurities or analytes to be sensed but also as an important aspect of rational design.
This report documents work that was performed under the Laboratory Directed Research and Development project, Science of Battery Degradation. The focus of this work was on the creation of new experimental and theoretical approaches to understand atomistic mechanisms of degradation in battery electrodes that result in loss of electrical energy storage capacity. Several unique approaches were developed during the course of the project, including the invention of a technique based on ultramicrotoming to cross-section commercial scale battery electrodes, the demonstration of scanning transmission x-ray microscopy (STXM) to probe lithium transport mechanisms within Li-ion battery electrodes, the creation of in-situ liquid cells to observe electrochemical reactions in real-time using both transmission electron microscopy (TEM) and STXM, the creation of an in-situ optical cell utilizing Raman spectroscopy and the application of the cell for analyzing redox flow batteries, the invention of an approach for performing ab initio simulation of electrochemical reactions under potential control and its application for the study of electrolyte degradation, and the development of an electrochemical entropy technique combined with x-ray based structural measurements for understanding origins of battery degradation. These approaches led to a number of scientific discoveries. Using STXM we learned that lithium iron phosphate battery cathodes display unexpected behavior during lithiation wherein lithium transport is controlled by nucleation of a lithiated phase, leading to high heterogeneity in lithium content at each particle and a surprising invariance of local current density with the overall electrode charging current. We discovered using in-situ transmission electron microscopy that there is a size limit to lithiation of silicon anode particles above which particle fracture controls electrode degradation. From electrochemical entropy measurements, we discovered that entropy changes little with degradation but the origin of degradation in cathodes is kinetic in nature, i.e. lower rate cycling recovers lost capacity. Finally, our modeling of electrode-electrolyte interfaces revealed that electrolyte degradation may occur by either a single or double electron transfer process depending on thickness of the solid-electrolyte-interphase layer, and this cross-over can be modeled and predicted.
Leite, Marina S.; Ruzmetov, Dmitry; Li, Zhipeng; Bendersky, Leonid A.; Bartelt, Norman C.; Kolmakov, Andrei; Talin, A.A.
The atomistic mechanism for lithiation/delithiation in all-solid-state batteries is still an open question, and the 'holy grail' to engineer devices with extended lifetime. Here, by combining real-time scanning electron microscopy in ultra-high vacuum with electrochemical cycling, we quantify the dynamic degradation of Al anodes in Li-ion all-solid-state batteries, a promising alternative for ultra lightweight devices. We find that AlLi alloy mounds are formed on the top surface of the Al anode and that degradation of battery capacity occurs because of Li trapped in them. Our approach establishes a new platform for probing the real-time degradation of electrodes, and can be expanded to other complex systems, allowing for high throughput characterization of batteries with nanoscale resolution.
Leite, Marina S.; Abashin, Maxim; Lezec, Henri J.; Gianfrancesco, Anthony; Talin, A.A.; Zhitenev, Nikolai B.
The local collection characteristics of grain interiors and grain boundaries in thin-film CdTe polycrystalline solar cells are investigated using scanning photocurrent microscopy. The carriers are locally generated by light injected through a small aperture (50-300 nm) of a near-field scanning optical microscope in an illumination mode. Possible influence of rough surface topography on light coupling is examined and eliminated by sculpting smooth wedges on the granular CdTe surface. By varying the wavelength of light, nanoscale spatial variations in external quantum efficiency are mapped. We find that the grain boundaries (GBs) are better current collectors than the grain interiors (GIs). The increased collection efficiency is caused by two distinct eff ects associated with the material composition of GBs. First, GBs are charged, and the corresponding built-in field facilitates the separation and the extraction of the photogenerated carriers. Second, the GB regions generate more photocurrent at long wavelength corresponding to the band edge, which can be caused by a smaller local band gap. Resolving carrier collection with nanoscale resolution in solar cell materials is crucial for optimizing the polycrystalline device performance through appropriate thermal processing and passivation of defects and surfaces. (Figure Presented).
Oleshko, Vladimir P.; Lam, Thomas; Ruzmetov, Dmitry; Haney, Paul; Lezec, Henri J.; Davydov, Albert V.; Krylyuk, Sergiy; Cumings, John; Talin, A.A.
Complex interfacial phenomena and phase transformations that govern the operation of Li-ion batteries require detailed nanoscale 3D structural and compositional characterization that can be directly related to their capacity and electrical transport properties. For this purpose, we have designed model miniature all solid-state radial heterostructure Li-ion batteries composed of LiCoO2 cathode, LiPON electrolyte and amorphous Si anode shells, which were deposited around metallized high-aspect-ratio Si nanowires as a scaffolding core. Such diagnostic batteries, the smallest, complete secondary Li-ion batteries realized to date, were specifically designed for in situ electrical testing in a field-emission scanning electron microscope and/or transmission electron microscope. The results of electrochemical testing were described in detail in a previous publication (Nano Lett., 2012, 12, 505-511). The model Li-ion batteries allow analysis of the correlations between electrochemical properties and their structural evolution during cycling in various imaging, diffraction and spectroscopic modes down to the atomic level. Employing multimode analytical scanning/transmission electron microscopy imaging coupled with correlative multivariate statistical analysis and tomography, we have analyzed and quantified the 3D morphological and structural arrangement of the batteries, including textured platelet-like LiCoO2 nanocrystallites, buried electrode-electrolyte interfaces and hidden internal defects to clarify effects of scaling on a battery's electrochemical performance. Characterization of the nanoscale interfacial processes using model heterostructure nanowire-based Li-ion batteries provides useful guidelines for engineering of prospective nano-sized building blocks in future electrochemical energy storage systems.
Electro-optical organic materials hold great promise for the development of high-efficiency devices based on exciton formation and dissociation, such as organic photovoltaics (OPV) and organic light-emitting devices (OLEDs). However, the external quantum efficiency (EQE) of both OPV and OLEDs must be improved to make these technologies economical. Efficiency rolloff in OLEDs and inability to control morphology at key OPV interfaces both reduce EQE. Only by creating materials that allow manipulation and control of the intimate assembly and communication between various nanoscale excitonic components can we hope to first understand and then engineer the system to allow these materials to reach their potential. The aims of this proposal are to: 1) develop a paradigm-changing platform for probing excitonic processes composed of Crystalline Nanoporous Frameworks (CNFs) infiltrated with secondary materials (such as a complimentary semiconductor); 2) use them to probe fundamental aspects of excitonic processes; and 3) create prototype OPVs and OLEDs using infiltrated CNF as active device components. These functional platforms will allow detailed control of key interactions at the nanoscale, overcoming the disorder and limited synthetic control inherent in conventional organic materials. CNFs are revolutionary inorganic-organic hybrid materials boasting unmatched synthetic flexibility that allow tuning of chemical, geometric, electrical, and light absorption/generation properties. For example, bandgap engineering is feasible and polyaromatic linkers provide tunable photon antennae; rigid 1-5 nm pores provide an oriented, intimate host for triplet emitters (to improve light emission in OLEDs) or secondary semiconducting polymers (creating a charge-separation interface in OPV). These atomically engineered, ordered structures will enable critical fundamental questions to be answered concerning charge transport, nanoscale interfaces, and exciton behavior that are inaccessible in disordered systems. Implementing this concept also creates entirely new dimensions for device fabrication that could both improve performance, increase durability, and reduce costs with unprecedented control of over properties. This report summarizes the key results of this project and is divided into sections based on publications that resulted from the work. We begin in Section 2 with an investigation of light harvesting and energy transfer in a MOF infiltrated with donor and acceptor molecules of the type typically used in OPV devices (thiophenes and fullerenes, respectively). The results show that MOFs can provide multiple functions: as a light harvester, as a stabilizer and organizer or the infiltrated molecules, and as a facilitator of energy transfer. Section 3 describes computational design of MOF linker groups to accomplish light harvesting in the visible and facilitate charge separation and transport. The predictions were validated by UV-visible absorption spectroscopy, demonstrating that rational design of MOFs for light-harvesting purposes is feasible. Section 4 extends the infiltration concept discussed in Section to, which we now designate as "Molecule@MOF" to create an electrically conducting framework. The tailorability and high conductivity of this material are unprecedented, meriting publication in the journal Science and spawning several Technical Advances. Section 5 discusses processes we developed for depositing MOFs as thin films on substrates, a critical enabling technology for fabricating MOF-based electronic devices. Finally, in Section 6 we summarize results showing that a MOF thin film can be used as a sensitizer in a DSSC, demonstrating that MOFs can serve as active layers in excitonic devices. Overall, this project provides several crucial proofs-of- concept that the potential of MOFs for use in optoelectronic devices that we predicted several years ago [ 3 ] can be realized in practice.