One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. However, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. Here, we show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O2 batteries. The heme’s oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. This study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage.
The rechargeable nonaqueous lithium-air (Li-O(2)) battery is receiving a great deal of interest because, theoretically, its specific energy far exceeds the best that can be achieved with lithium-ion cells. Operation of the rechargeable Li-O(2) battery depends critically on repeated and highly reversible formation/decomposition of lithium peroxide (Li(2)O(2)) at the cathode upon cycling. Here, we show that this process is possible with the use of a dimethyl sulfoxide electrolyte and a porous gold electrode (95% capacity retention from cycles 1 to 100), whereas previously only partial Li(2)O(2) formation/decomposition and limited cycling could occur. Furthermore, we present data indicating that the kinetics of Li(2)O(2) oxidation on charge is approximately 10 times faster than on carbon electrodes.
Silicon-Few Layer Graphene (Si-FLG) composite electrodes are investigated using a scalable electrode manufacturing method. A comprehensive study on the electrochemical performance and the impedance response is measured using electrochemical impedance spectroscopy. The study demonstrates that the incorporation of few-layer graphene (FLG) results in significant improvement in terms of cyclability, electrode resistance and diffusion properties. Additionally, the diffusion impedance responses that occur during the phase changes in silicon is elucidated through Staircase Potentio Electrochemical Impedance Spectroscopy (SPEIS): a more comprehensive and straightforward approach than previous state-of-charge based diffusion studies.
Short-term transients, including those related to wind and solar sources, present challenges to the electrical grid. Stationary energy storage systems that can operate for many cycles, at high power, with high round-trip energy efficiency, and at low cost are required. Existing energy storage technologies cannot satisfy these requirements. Here we show that crystalline nanoparticles of copper hexacyanoferrate, which has an ultra-low strain open framework structure, can be operated as a battery electrode in inexpensive aqueous electrolytes. After 40,000 deep discharge cycles at a 17 C rate, 83% of the original capacity of copper hexacyanoferrate is retained. Even at a very high cycling rate of 83 C, two thirds of its maximum discharge capacity is observed. At modest current densities, round-trip energy efficiencies of 99% can be achieved. The low-cost, scalable, room-temperature co-precipitation synthesis and excellent electrode performance of copper hexacyanoferrate make it attractive for large-scale energy storage systems.
Optimal decision-making requires balancing fast but error-prone and more accurate but slower decisions through adjustments of decision thresholds. Here, we demonstrate two distinct correlates of such speed-accuracy adjustments by recording subthalamic nucleus (STN) activity and electroencephalography in eleven Parkinson’s disease patients during a perceptual decision-making task; STN low-frequency oscillatory (LFO) activity (2-8 Hz), coupled to activity at prefrontal electrode Fz, and STN beta activity (13-30 Hz) coupled to electrodes C3/C4 close to motor cortex. These two correlates not only differed in their cortical topography and spectral characteristics, but also in the relative timing of recruitment and in their precise relationship with decision thresholds. Increases of STN LFO power preceding the response predicted increased thresholds only after accuracy instructions, while cue-induced reductions of STN beta power decreased thresholds irrespective of instructions. These findings indicate that distinct neural mechanisms determine whether a decision will be made in haste or with caution.
The spin-polarized organic light-emitting diode (spin-OLED) has been a long-sought device within the field of organic spintronics. We designed, fabricated, and studied a spin-OLED with ferromagnetic electrodes that acts as a bipolar organic spin valve (OSV), based on a deuterated derivative of poly(phenylene-vinylene) with small hyperfine interaction. In the double-injection limit, the device shows ~1% spin valve magneto-electroluminescence (MEL) response, which follows the ferromagnetic electrode coercive fields and originates from the bipolar spin-polarized space charge-limited current. In stark contrast to the response properties of homopolar OSV devices, the MEL response in the double-injection device is practically independent of bias voltage, and its temperature dependence follows that of the ferromagnetic electrode magnetization. Our findings provide a pathway for organic displays controlled by external magnetic fields.
The ultimate goal of Li ion battery design should consist of fully accessible metallic current collectors, possibly of nanoscale dimensions, intimately in contact with high capacity stable electrode materials. Here we engineer three-dimensional porous nickel based current collector coated conformally with layers of silicon, which typically suffers from poor cycle life, to form high-capacity electrodes. These binder/conductive additive free silicon electrodes show excellent electrode adhesion resulting in superior cyclic stability and rate capability. The nickel current collector design also allows for an increase in silicon loading per unit area leading to high areal discharge capacities of up to 0.8 mAh/cm(2) without significant loss in rate capability. An excellent electrode utilization (∼85%) and improved cyclic stability for the metal/silicon system is attributed to reduced internal stresses/fracture upon electrode expansion during cycling and shorter ionic/electronic diffusion pathways that help in improving the rate capability of thicker silicon layers.
Lithium metal is a promising anode candidate for the next-generation rechargeable battery due to its highest specific capacity (3860 mA h g(-1)) and lowest potential, but low Coulombic efficiency and formation of lithium dendrites hinder its practical application. Here, we report a self-formed flexible hybrid solid-electrolyte interphase layer through co-deposition of organosulfides/organopolysulfides and inorganic lithium salts using sulfur-containing polymers as an additive in the electrolyte. The organosulfides/organopolysulfides serve as “plasticizer” in the solid-electrolyte interphase layer to improve its mechanical flexibility and toughness. The as-formed robust solid-electrolyte interphase layers enable dendrite-free lithium deposition and significantly improve Coulombic efficiency (99% over 400 cycles at a current density of 2 mA cm(-2)). A lithium-sulfur battery based on this strategy exhibits long cycling life (1000 cycles) and good capacity retention. This study reveals an avenue to effectively fabricate stable solid-electrolyte interphase layer for solving the issues associated with lithium metal anodes.The practical application of lithium metal anodes suffers from the poor Coulombic efficiency and growth of lithium dendrites. Here, the authors report an approach to enable the self-formation of stable and flexible solid-electrolyte interphase layers which serve to address both issues.
Previous electromyographic (EMG) studies of gluteus medius (GMed) have not accurately quantified the function of the three proposed structurally and functionally unique segments (anterior, middle and posterior). Therefore this study used anatomically verified locations for intramuscular electrode recordings in three segments of GMed to determine whether the segments are functionally independent. Bipolar fine wire electrodes were inserted into each segment of GMed in 15 healthy individuals. Participants completed a series of four walking trials, followed by maximum voluntary isometric contractions (MVICs) in five different positions. Temporal and amplitude variables for each segment were compared across the gait cycle using ANOVA. The relative contributions of each segment to the MVIC trials were compared with non-parametric tests. All segments showed a biphasic response during the stance phase of gait. There were no differences in amplitude variables (% MVIC) between segments, but the anterior segment had a later peak during both the first and second bursts.For the MVIC trials, there were significant differences in amplitude between segments in four of the five test positions. These data indicate that GMed is composed of three functionally independent segments. This study contributes to the theoretical understanding of the role of GMed.
In the present study, the influence of Ti-containing inclusions on the development of acicular ferrite microstructure and mechanical properties in the multipass weld metals has been studied. Shielded metal arc weld deposits were prepared by varying titanium content in the range of 0.003-0.021%. The variation in the titanium content was obtained by the addition of different amounts of titanium oxide nanoparticles to the electrode coating. The dispersion of titanium oxide nanoparticles, composition of inclusions, microstructural analysis, tensile properties and Charpy impact toughness were evaluated. As the amount of Ti-containing inclusions in the weld metal was increased, the microstructure of the weld metal was changed from the grain boundary allotriomorphic ferrite structure to acicular ferrite with the intragranular nucleation of ferrite on the Ti-containing inclusions, and the mechanical properties were improved. This improvement is attributable to the increased percentage of acicular ferrite due to the uniform dispersion of Ti-containing inclusions and the pinning force of oxide nanoparticles against the growth of allotriomorphic ferrite and Widmanstätten ferrite from the austenite grain boundaries.