Jagjit Nanda

Single-exciton optical gain in semiconductor nanocrystals

Nanocrystal quantum dots have favourable light-emitting properties. They show photoluminescence with high quantum yields, and their emission colours depend on the nanocrystal size—owing to the quantum-confinement effect—and are therefore tunable. However, nanocrystals are difficult to use in optical amplification and lasing. Because of an almost exact balance between absorption and stimulated emission in nanoparticles excited with single electron–hole pairs (excitons), optical gain can only occur in nanocrystals that contain at least two excitons. A complication associated with this multiexcitonic nature of light amplification is fast optical-gain decay induced by non-radiative Auger recombination, a process in which one exciton recombines by transferring its energy to another. Here we demonstrate a practical approach for obtaining optical gain in the single-exciton regime that eliminates the problem of Auger decay. Specifically, we develop core/shell hetero-nanocrystals engineered in such a way as to spatially separate electrons and holes between the core and the shell (type-II heterostructures). The resulting imbalance between negative and positive charges produces a strong local electric field, which induces a giant (∼100 meV or greater) transient Stark shift of the absorption spectrum with respect to the luminescence line of singly excited nanocrystals. This effect breaks the exact balance between absorption and stimulated emission, and allows us to demonstrate optical amplification due to single excitons.

Atomically localized plasmon enhancement in monolayer graphene

Plasmons in graphene can be tuned by using electrostatic gating or chemical doping, and the ability to confine plasmons in very small regions could have applications in optoelectronics, plasmonics and transformation optics. However, little is known about how atomic-scale defects influence the plasmonic properties of graphene. Moreover, the smallest localized plasmon resonance observed in any material to date has been limited to around 10 nm. Here, we show that surface plasmon resonances in graphene can be enhanced locally at the atomic scale. Using electron energy-loss spectrum imaging in an aberration-corrected scanning transmission electron microscope, we find that a single point defect can act as an atomic antenna in the petahertz (10(15) Hz) frequency range, leading to surface plasmon resonances at the subnanometre scale.

Influence of Lithium Salts on the Discharge Chemistry of Li-Air Cells.

In this work, we show that the use of a high boiling point ether solvent (tetraglyme) promotes the formation of Li2O2 in a lithium-air cell. However, another major constituent in the discharge product of a Li-air cell contains halides from the lithium salts and C-O from the tetraglyme used as the solvent. This information is critical to the development of Li-air electrolytes, which are stable and promote the formation of the desired Li2O2 products.

Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling

Understanding the evolution of chemical composition and morphology of battery materials during electrochemical cycling is fundamental to extending battery cycle life and ensuring safety. This is particularly true for the much debated high energy density (high voltage) lithium–manganese rich cathode material of composition Li1 + xM1 – xO2 (M = Mn, Co, Ni). In this study we combine full-field transmission X-ray microscopy (TXM) with X-ray absorption near edge structure (XANES) to spatially resolve changes in chemical phase, oxidation state, and morphology within a high voltage cathode having nominal composition Li1.2Mn0.525Ni0.175Co0.1O2. Nanoscale microscopy with chemical/elemental sensitivity provides direct quantitative visualization of the cathode, and insights into failure. Single-pixel (∼30 nm) TXM XANES revealed changes in Mn chemistry with cycling, possibly to a spinel conformation and likely including some Mn(II), starting at the particle surface and proceeding inward. Morphological analysis of the particles revealed, with high resolution and statistical sampling, that the majority of particles adopted nonspherical shapes after 200 cycles. Multiple-energy tomography showed a more homogeneous association of transition metals in the pristine particle, which segregate significantly with cycling. Depletion of transition metals at the cathode surface occurs after just one cycle, likely driven by electrochemical reactions at the surface.

Absorption cross sections and Auger recombination lifetimes in inverted core-shell nanocrystals: Implications for lasing performance

We study inverted core-shell nanocrystals (NCs), in which a core of a wide-gap semiconductor (ZnSe) is overcoated with a shell of a narrower gap material (CdSe). Depending on the core radius and the shell thickness, these NCs can exhibit either type-I or type-II behavior. We show that these heterostructures can be used to significantly increase the absorption cross sections and simultaneously decrease the efficiency of Auger recombination compared to monocomponent CdSe NCs emitting at the same wavelength. These properties enhance the lasing performance of inverted core-shell structures and allow, in particular, efficient amplified spontaneous emission in the range of blue colors.

Artificial solid electrolyte interphase to address the electrochemical degradation of silicon electrodes.

Electrochemical degradation on silicon (Si) anodes prevents them from being successfully used in lithium (Li)-ion battery full cells. Unlike the case of graphite anodes, the natural solid electrolyte interphase (SEI) films generated from carbonate electrolytes do not self-passivate on Si, causing continuous electrolyte decomposition and loss of Li ions. In this work, we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphorus oxynitride (Lipon), which conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, a significant effect is observed in suppressing electrolyte decomposition, while Lipon of thinner than 40 nm has a limited effect. Ionic and electronic conductivity measurements reveal that the artificial SEI is effective when it is a pure ionic conductor, but electrolyte decomposition is only partially suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40-50 nm. This work provides guidance for designing artificial SEI films for high-capacity Li-ion battery electrodes using solid electrolyte materials.

Conductive surface modification of LiFePO4 with nitrogen-doped carbon layers for lithium-ion batteries

The surface of rod-like LiFePO4 modified with a conductive nitrogen-doped carbon layer has been prepared using hydrothermal processing followed by post-annealing in the presence of an ionic liquid. The conductive surface modified rod-like LiFePO4 exhibits good capacity retention and high rate capability as the nitrogen-doped carbon layer improves conductivity and prevents aggregation of the rods during cycling.

Facet-Dependent Disorder in Pristine High-Voltage Lithium–Manganese-Rich Cathode Material

Defects and surface reconstructions are thought to be crucial for the long-term stability of high-voltage lithium-manganese-rich cathodes. Unfortunately, many of these defects arise only after electrochemical cycling which occurs under harsh conditions, making it difficult to fully comprehend the role they play in degrading material performance. Recently, it has been observed that defects are present even in the pristine material. This study, therefore, focuses on examining the nature of the disorder observed in pristine Li1.2Ni0.175Mn0.525Co0.1O2 (LNMCO) particles. Using atomic-resolution Z-contrast imaging and electron energy loss spectroscopy measurements, we show that there is indeed a significant amount of antisite defects present in this material, with transition metals substituting on Li metal sites. Furthermore, we find a strong segregation tendency of these types of defects toward open facets (surfaces perpendicular to the layered arrangement of atoms) rather than closed facets (surfaces parallel to the layered arrangement of atoms). First-principles calculations identify antisite defect pairs of Ni swapping with Li ions as the predominant defect in the material. Furthermore, energetically favorable swapping of Ni on the Mn sites was observed to lead to Mn depletion at open facets. Relatively, low Ni migration barriers also support the notion that Ni is the predominant cause of disorder. These insights suggest that certain facets of the LNMCO particles may be more useful for inhibiting surface reconstruction and improving the stability of these materials through careful consideration of the exposed surface.

Advanced Lithium Battery Cathodes Using Dispersed Carbon Fibers as the Current Collector

To fabricate LiFePO4 battery cathodes, highly conductive carbon fibers of 10-20 m in diameter have been used to replace a conventional aluminum (Al) foil current collector. This disperses the current collector throughout the cathode sheet and increases the contact area with the LiFePO4 (LFP) particles. In addition, the usual organic binder plus carbon-black can be replaced by a high temperature binder of <5 weight % carbonized petroleum pitch (P-pitch). Together these replacements increase the specific energy density and energy per unit area of the electrode. Details of the coating procedure, characterization and approach for maximizing the energy density are discussed. In a side-by-side comparison with conventional cathodes sheets of LFP on Al foil, the carbon fiber composite cathodes have a longer cycle life, higher thermal stability, and high capacity utilization with little sacrifice of the rate performance.

Controlled formation of mixed nanoscale domains of high capacity Fe2O3-FeF3 conversion compounds by direct fluorination.

We report a direct fluorination method under fluorine gas atmosphere using a fluidized bed reactor for converting nanophase iron oxide (n-Fe2O3) to an electrochemically stable and higher energy density iron oxyfluoride/fluoride phase. Interestingly, no noticeable bulk iron oxyfluoride phase (FeOF) phase was observed even at fluorination temperature close to 300 °C. Instead, at fluorination temperatures below 250 °C, scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) and X-ray photoelectron spectroscopy (XPS) analysis showed surface fluorination with nominal composition, Fe2O3-xF2x (x < 1). At fluorination temperatures of 275 °C, STEM-EELS results showed porous interconnected nanodomains of FeF3 and Fe2O3 coexisting within the same particle, and overall the particles become less dense after fluorination. We performed potentiometric intermittent titration and electrochemical impedance spectroscopy studies to understand the lithium diffusion (or apparent diffusion) in both the oxyfluoride and mixed phase FeF3 + Fe2O3 composition, and correlate the results to their electrochemical performance. Further, we analyze from a thermodynamical perspective, the observed formation of the majority fluoride phase (77% FeF3) and the absence of the expected oxyfluoride phase based on the relative formation energies of oxide, fluoride, and oxyfluorides.