Beyond Constant Current: Origin of Pulse-Induced Activation in Phase-Transforming Battery Electrodes.

Mechanistic understanding of phase transformation dynamics during battery charging and discharging is crucial toward rationally improving intercalation electrodes. Most studies focus on constant-current conditions. However, in real battery operation, such as in electric vehicles during discharge, the current is rarely constant. In this work we study current pulsing in LiXFePO4 (LFP), a model and technologically important phase-transforming electrode. A current-pulse activation effect has been observed in LFP, which decreases the overpotential by up to ∼70% after a short, high-rate pulse. This effect persists for hours or even days. Using scanning transmission X-ray microscopy and operando X-ray diffraction, we link this long-lived activation effect to a pulse-induced electrode homogenization on both the intra- and interparticle length scales, i.e., within and between particles. Many-particle phase-field simulations explain how such pulse-induced homogeneity contributes to the decreased electrode overpotential. Specifically, we correlate the extent and duration of this activation to lithium surface diffusivity and the magnitude of the current pulse. This work directly links the transient electrode-level electrochemistry to the underlying phase transformation and explains the critical effect of current pulses on phase separation, with significant implication on both battery round-trip efficiency and cycle life. More broadly, the mechanisms revealed here likely extend to other phase-separating electrodes, such as graphite.

Highly Efficient Uniaxial In-Plane Stretching of a 2D Material via Ion Insertion.

On-chip dynamic strain engineering requires efficient micro-actuators that can generate large in-plane strains. Inorganic electrochemical actuators are unique in that they are driven by low voltages (≈1 V) and produce considerable strains (≈1%). However, actuation speed and efficiency are limited by mass transport of ions. Minimizing the number of ions required to actuate is thus key to enabling useful "straintronic" devices. Here, it is shown that the electrochemical intercalation of exceptionally few lithium ions into WTe2 causes large anisotropic in-plane strain: 5% in one in-plane direction and 0.1% in the other. This efficient stretching of the 2D WTe2 layers contrasts to intercalation-induced strains in related materials which are predominantly in the out-of-plane direction. The unusual actuation of Lix WTe2 is linked to the formation of a newly discovered crystallographic phase, referred to as Td', with an exotic atomic arrangement. On-chip low-voltage (<0.2 V) control is demonstrated over the transition to the novel phase and its composition. Within the Td'-Li0.5- δ WTe2 phase, a uniaxial in-plane strain of 1.4% is achieved with a change of δ of only 0.075. This makes the in-plane chemical expansion coefficient of Td'-Li0.5-δ WTe2 far greater than of any other single-phase material, enabling fast and efficient planar electrochemical actuation.

Fictitious phase separation in Li layered oxides driven by electro-autocatalysis.

Layered oxides widely used as lithium-ion battery electrodes are designed to be cycled under conditions that avoid phase transitions. Although the desired single-phase composition ranges are well established near equilibrium, operando diffraction studies on many-particle porous electrodes have suggested phase separation during delithiation. Notably, the separation is not always observed, and never during lithiation. These anomalies have been attributed to irreversible processes during the first delithiation or reversible concentration-dependent diffusion. However, these explanations are not consistent with all experimental observations such as rate and path dependencies and particle-by-particle lithium concentration changes. Here, we show that the apparent phase separation is a dynamical artefact occurring in a many-particle system driven by autocatalytic electrochemical reactions, that is, an interfacial exchange current that increases with the extent of delithiation. We experimentally validate this population-dynamics model using the single-phase material Lix(Ni1/3Mn1/3Co1/3)O2 (0.5 < x < 1) and demonstrate generality with other transition-metal compositions. Operando diffraction and nanoscale oxidation-state mapping unambiguously prove that this fictitious phase separation is a repeatable non-equilibrium effect. We quantitatively confirm the theory with multiple-datastream-driven model extraction. More generally, our study experimentally demonstrates the control of ensemble stability by electro-autocatalysis, highlighting the importance of population dynamics in battery electrodes (even non-phase-separating ones).

Metal-oxygen decoordination stabilizes anion redox in Li-rich oxides.

Reversible high-voltage redox chemistry is an essential component of many electrochemical technologies, from (electro)catalysts to lithium-ion batteries. Oxygen-anion redox has garnered intense interest for such applications, particularly lithium-ion batteries, as it offers substantial redox capacity at more than 4 V versus Li/Li+ in a variety of oxide materials. However, oxidation of oxygen is almost universally correlated with irreversible local structural transformations, voltage hysteresis and voltage fade, which currently preclude its widespread use. By comprehensively studying the Li2-xIr1-ySnyO3 model system, which exhibits tunable oxidation state and structural evolution with y upon cycling, we reveal that this structure-redox coupling arises from the local stabilization of short approximately 1.8 Å metal-oxygen π bonds and approximately 1.4 Å O-O dimers during oxygen redox, which occurs in Li2-xIr1-ySnyO3 through ligand-to-metal charge transfer. Crucially, formation of these oxidized oxygen species necessitates the decoordination of oxygen to a single covalent bonding partner through formation of vacancies at neighbouring cation sites, driving cation disorder. These insights establish a point-defect explanation for why anion redox often occurs alongside local structural disordering and voltage hysteresis during cycling. Our findings offer an explanation for the unique electrochemical properties of lithium-rich layered oxides, with implications generally for the design of materials employing oxygen redox chemistry.

Fluid-enhanced surface diffusion controls intraparticle phase transformations.

Phase transformations driven by compositional change require mass flux across a phase boundary. In some anisotropic solids, however, the phase boundary moves along a non-conductive crystallographic direction. One such material is LiXFePO4, an electrode for lithium-ion batteries. With poor bulk ionic transport along the direction of phase separation, it is unclear how lithium migrates during phase transformations. Here, we show that lithium migrates along the solid/liquid interface without leaving the particle, whereby charge carriers do not cross the double layer. X-ray diffraction and microscopy experiments as well as ab initio molecular dynamics simulations show that organic solvent and water molecules promote this surface ion diffusion, effectively rendering LiXFePO4 a three-dimensional lithium-ion conductor. Phase-field simulations capture the effects of surface diffusion on phase transformation. Lowering surface diffusivity is crucial towards supressing phase separation. This work establishes fluid-enhanced surface diffusion as a key dial for tuning phase transformation in anisotropic solids.

Electrochemical trapping of metastable Mn3+ ions for activation of MnO2 oxygen evolution catalysts.

Electrodeposited manganese oxide films are promising catalysts for promoting the oxygen evolution reaction (OER), especially in acidic solutions. The activity of these catalysts is known to be enhanced by the introduction of Mn3+ We present in situ electrochemical and X-ray absorption spectroscopic studies, which reveal that Mn3+ may be introduced into MnO2 by an electrochemically induced comproportionation reaction with Mn2+ and that Mn3+ persists in OER active films. Extended X-ray absorption fine structure (EXAFS) spectra of the Mn3+-activated films indicate a decrease in the Mn-O coordination number, and Raman microspectroscopy reveals the presence of distorted Mn-O environments. Computational studies show that Mn3+ is kinetically trapped in tetrahedral sites and in a fully oxidized structure, consistent with the reduction of coordination number observed in EXAFS. Although in a reduced state, computation shows that Mn3+ states are stabilized relative to those of oxygen and that the highest occupied molecular orbital (HOMO) is thus dominated by oxygen states. Furthermore, the Mn3+(Td) induces local strain on the oxide sublattice as observed in Raman spectra and results in a reduced gap between the HOMO and the lowest unoccupied molecular orbital (LUMO). The confluence of a reduced HOMO-LUMO gap and oxygen-based HOMO results in the facilitation of OER on the application of anodic potentials to the δ-MnO2 polymorph incorporating Mn3+ ions.

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides.

Lithium-rich layered transition metal oxide positive electrodes offer access to anion redox at high potentials, thereby promising high energy densities for lithium-ion batteries. However, anion redox is also associated with several unfavorable electrochemical properties, such as open-circuit voltage hysteresis. Here we reveal that in Li1.17-x Ni0.21Co0.08Mn0.54O2, these properties arise from a strong coupling between anion redox and cation migration. We combine various X-ray spectroscopic, microscopic, and structural probes to show that partially reversible transition metal migration decreases the potential of the bulk oxygen redox couple by > 1 V, leading to a reordering in the anionic and cationic redox potentials during cycling. First principles calculations show that this is due to the drastic change in the local oxygen coordination environments associated with the transition metal migration. We propose that this mechanism is involved in stabilizing the oxygen redox couple, which we observe spectroscopically to persist for 500 charge/discharge cycles.

Facile synthesis of intense green light emitting LiGdF4:Yb,Er-based upconversion bipyramidal nanocrystals and their polymer composites.

A pathway for achieving intense green light emitting LiGdF4:Yb,Er upconversion nanophosphors (UCNPs) via Y(3+) doping is demonstrated. It was revealed that Y(3+) doping initiated the formation of a tetragonal phase and affected the particle size. Single tetragonal-phase LiGd0.4Y0.4F4:Yb(18%),Er(2%) (LGY0.4F:Yb,Er) UCNPs exhibited strong upconversion (UC) green luminescence and tetragonal bipyramidal morphologies. They showed 1325 and 325-fold higher photoluminescence intensity than the 0 and 80 mol% Y(3+)-doped LiGdF4:Yb,Er UCNPs, respectively. Additionally the particle size (edge length) of LiGdF4:Yb,Er-based upconversion tetragonal bipyramids (UCTBs) was controlled from 60.5 nm to an ultrasmall size of 9.3 nm with varying Y(3+) doping concentration. In an LGY0.4F:Yb,Er UCTB, uniform distribution of all constituent elements was directly confirmed by using high-angle annular dark-field scanning transmission electron microscopy and energy-filtered transmission electron microscopy (EFTEM) image analyses. In particular, existence of activator Er(3+) ions with extremely small quantity was clearly seen over a particle on the EFTEM image. Moreover, the LGY0.4F:Yb,Er UCTBs were successfully incorporated into the polydimethylsiloxane (PDMS) polymer and the highly transparent UCTB-PDMS composites showed bright green light under the excitation of 980 nm infrared light.

Prompt and synergistic antibacterial activity of silver nanoparticle-decorated silica hybrid particles on air filtration.

There is a significant need for materials that promptly exhibit antimicrobial activity upon contact. The large-scale fabrication of monodisperse silver nanoparticle (AgNP)-decorated silica (AgNP@SiO2) hybrid particles, and their prompt and synergistic antibacterial activity against both the Gram-negative bacteria Escherichia coli and the Gram-positive bacteria Staphylococcus epidermidis on air filtration units are presented. Monodisperse aminopropyl-functionalized silica colloids (406 nm) were used as a support material and were hybridized with AgNPs using a seeding, sorting-out, and growing strategy with Ag seeds (1-2 nm) into ∼30 nm AgNPs, successfully yielding 51 g of AgNP@SiO2 hybrid particles. Medium filter samples (glass fiber material, 4 × 4 cm2) were coated with AgNP@SiO2 particles and tested for antibacterial efficacy. SEM characterization of the bacterial morphology suggested prompt and synergistic antibacterial activity against both classes of bacteria. Moreover, antibacterial efficacies >99.99% for both bacteria were obtained using a filter sample with a coating areal density of 1 × 108 particles per cm2. Solutions of AgNP@SiO2 at 1.3% were stable even after 8 months. The hybrid particle AgNP@SiO2 and the air filter system coated with the particles are expected to be useful for future green environment applications.

Highly bright multicolor tunable ultrasmall ß-Na(Y,Gd)F4:Ce,Tb,Eu/ß-NaYF4 core/shell nanocrystals.

Herein, we report highly bright multicolor-emitting ß-Na(Y,Gd)F4:Ce,Tb,Eu/ß-NaYF4 nanoparticles (NPs) with precise color tunability. First, highly bright sub-20 nm ß-Na(Y,Gd)F4:Ce,Tb,Eu NPs were synthesized via a heating-up method. By controlling the ratio of Eu(3+) to Tb(3+), we generated green, yellow-green, greenish yellow, yellow, orange, reddish orange, and red emissions from the NP solutions via energy transfer of Ce(3+)→ Gd(3+)→ Tb(3+) (green) and Ce(3+)→ Gd(3+)→ Tb(3+)→ Eu(3+) (red) ions under ultraviolet light illumination (254 nm). Because of Ce(3+) and Gd(3+) sensitization, Tb(3+) ions exhibited strong green emission. The decay time of Tb(3+) emission decreased from 4.0 to 1.4 ms as the Eu(3+) concentration was increased, suggesting that energy was transferred from Tb(3+) to Eu(3+). As a result, Eu(3+) emission peaks were generated and the emission color was transformed from green to red. Monodisperse sub-6 nm ß-Na(Y,Gd)F4:Ce,Tb,Eu NPs were synthesized through a simple reduction of the reaction temperature. Although fine color tunability was retained, their brightness was considerably decreased owing to an increase in the surface-to-volume ratio. The formation of a ß-NaYF4 shell on top of the sub-6 nm NP core to produce ß-Na(Y,Gd)F4:Ce,Tb,Eu/ß-NaYF4 significantly increased the emission intensity, while maintaining the sub-10 nm sizes (8.7-9.5 nm). Quantum yields of the ultrasmall NPs increased from 1.1-6.9% for the core NPs to 6.7-44.4% for the core/shell NPs. Moreover, highly transparent core/shell NP-polydimethylsiloxane (PDMS) composites featuring a variety of colors, excellent color tunability, and high brightness were also prepared.

Rational morphology control of ß-NaYF4:Yb,Er/Tm upconversion nanophosphors using a ligand, an additive, and lanthanide doping.

We report the systematic control of the morphology of ß-NaYF4:Yb,Er/Tm upconversion nanophosphors (UCNPs) from large spheres (37.9 nm) to rods (length = 60.1 nm, width = 21.5 nm) and from rods to hexagonal prisms (length = 48.8 nm, width = 44.0 nm) or small spheres (14.0 nm) by the use of a surfactant, an additive, and lanthanide doping. Increasing the ratio of oleic acid (OA) to 1-octadecene (ODE) caused a decrease in the size of the UCNPs, and increasing the OA/ODE ratio above a critical value caused the particle shape to change from a sphere to a rod. The length-to-width aspect ratio (AR) of upconversion nanorods (UCNRs) was finely manipulated from 1.28 to 2.80. The rounded tips of the UCNRs were flattened by adding Cl(-) ions, and the UCNRs changed to hexagonal prisms with a controllable AR depending on the quantity of Cl(-) ions. Additionally, the morphology of the ß-NaYF4-based UCNPs was controlled by lanthanide doping. The size and AR of the UCNRs decreased with Gd(3+) doping, and the UCNRs ultimately transformed into small spheres (14.0 nm) with high monodispersity. Doping with Ce(3+) ions also decreased the AR of the UCNRs from 2.80 to 1.27. In addition, highly transparent polymer composites for 3D volumetric displays were fabricated by blending high-AR ß-NaYF4:Yb,Er/Tm UCNRs with polydimethylsiloxane. These composites exhibited bright green and blue upconversion light during excitation with 980 nm light.

Synthesis of blue emitting InP/ZnS quantum dots through control of competition between etching and growth.

Blue (<480 nm) emitting Cd-free quantum dots (QDs) are in great demand for various applications. However, their synthesis has been challenging. Here we present blue emitting InP/ZnS core/shell QDs with a band edge emission of 475 nm and a full width at half maximum of 39 nm (215 meV) from their quantum confined states. The drastic temperature drop immediately after mixing of the precursors and holding them at a temperature below 150 °C was the critical factor for the synthesis of blue emitting QDs, because the blue QDs are formed by the etching of ultra-small InP cores by residual acetic acid below 150 °C. Etching was dominant at temperatures below 150 °C, whereas growth was dominant at temperatures above 150 °C. ZnS shells were formed successfully at 150 °C, yielding blue emitting InP/ZnS QDs. The colour of the InP/ZnS QDs depicted on the CIE 1931 chromaticity diagram is located close to the edge, indicating a pure blue colour compared to other InP-based QDs.

Effect of surface tension and coefficient of thermal expansion in 30 nm scale nanoimprinting with two flexible polymer molds.

We report on nanoimprinting of polymer thin films at 30 nm scale resolution using two types of ultraviolet (UV)-curable, flexible polymer molds: perfluoropolyether (PFPE) and polyurethane acrylate (PUA). It was found that the quality of nanopatterning at the 30 nm scale is largely determined by the combined effects of surface tension and the coefficient of thermal expansion of the polymer mold. In particular, the polar component of surface tension may play a critical role in clean release of the mold, as evidenced by much reduced delamination or broken structures for the less polarized PFPE mold when patterning a relatively hydrophilic PMMA film. In contrast, such problems were not notably observed with a relatively hydrophobic PS film for both polymer molds. In addition, the demolding characteristic was also influenced by the coefficient of thermal expansion so that no delamination or uniformity problems were observed when patterning a UV-curable polymer film at room temperature. These results suggest that a proper polymeric mold material needs to be chosen for patterning polymer films under different surface properties and processing conditions, providing insights into how a clean demolding characteristic can be obtained at 30 nm scale nanopatterning.

Facile synthesis and optical properties of colloidal silica microspheres encapsulating a quantum dot layer.

We present colloidal silica microspheres encapsulating a homogeneous quantum dot layer at radial equidistance from the centre by utilizing electrostatic interaction between surface-engineered silica microspheres and QDs. The microspheres show dramatically enhanced optical absorption and emission with an appropriate silica shell thickness.

Enhanced biomolecular detection based on localized surface plasmon resonance (LSPR) using enzyme-precipitation reaction.

An enzyme-catalyzed precipitation reaction was employed as a means to increase the change in the LSPR signal after intermolecular bindings between antigens and antibodies occurred on gold nanodot surfaces. The gold nanodot array with an diameter of 175 nm and a thickness of 20 nm was fabricated on a glass wafer using thermal nanoimprint lithography. The human interleukin (hIL) 5 antibody was immobilized on the gold nanodot, followed by binding of hIL 5 to the anti-hIL 5. Subsequently, a biotinylated anti-hIL 5 and a alkaline phosphatase conjugated with streptavidin were simultaneously introduced. A mixture of 5-bromo-4-chloro-3-indolyl phosphate p-toluidine (BCIP) and nitro blue tetrazolium (NBT) was then used for precipitation, which resulted from the biocatalytic reaction of the alkaline phosphatase on gold nanodot. The LSPR spectra were obtained after each binding process. Using this analysis, the enzyme-catalyzed precipitation reaction on gold nanodots was found to be effective in amplifying the change in the peak wavelength of LSPR after molecular bindings.

The fabrication scheme of a high resolution and high aspect ratio UV-nanoimprint mold.

We propose a new scheme of fabricating molds for UV-nanoimprint lithography (UV-NIL) that is both high resolution and has a high aspect ratio. The scheme involves the utilization of a hydrogen silsesquioxane (HSQ) electron beam resist for high resolution patterning and the sputter-deposited alpha-Si layer that defines the high-aspect-ratio mold pattern obtained from the high etch selectivity between the HSQ and the alpha-Si. We obtained high resolution line patterns and dot patterns with feature sizes of 40 nm and 25 nm, respectively. The aspect ratio of the patterns was about 3.5 for line patterns and about 5 for dot patterns. These molds also demonstrate successful UV-nanoimprint patterning.