All‐Manganese‐Based Binder‐Free Stretchable Lithium‐Ion Batteries

Advanced electrode materials with bendability and stretchability are critical for the rapid development of fully flexible/stretchable lithium‐ion batteries. However, the sufficiently stretchable lithium‐ion battery is still underdeveloped that is one of the biggest challenges preventing from realizing fully deformable power sources. Here, a low‐temperature hydrothermal synthesis of a cathode material for stretchable lithium‐ion battery is reported by the in situ growth of LiMn₂O₄ (LMO) nanocrystals inside 3D carbon nanotube (CNT) film networks. The LMO/CNT film composite has demonstrated the chemical bonding between the LMO active materials and CNT scaffolds, which is the most important characteristic of the stretchable electrodes. When coupled with a wrinkled MnO_x /CNT film anode, a binder‐free, all‐manganese‐based stretchable full battery cell is assembled which delivers a high average specific capacity of ≈97 mA h g^?1 and stabilizes after over 300 cycles with an enormous strain of 100%. Furthermore, combining with other merits such as low cost, natural abundance, and environmentally friendly, the all‐manganese design is expected to accelerate the practical applications of stretchable lithium‐ion batteries for fully flexible and biomedical electronics.     

Direct electrochemistry of hemoglobin in dimethyldioctadecyl ammonium bromide film and its electrocatalysis to nitric oxide

Hemoglobin (Hb) was successfully immobilized in dimethyldioctadecyl ammonium bromide (DOAB) film at pyrolytic graphite (PG) electrode. Electrochemical experiments revealed that Hb in DOAB film exhibited a pair of well-defined, quasi-reversible cyclic voltammetric peaks at about -0.160 V versus saturated calomel electrode (SCE) in pH 5.0 buffer, characteristic of the heme Fe(III)/Fe(II) redox couple of Hb. The electron transfer (eT) rate between Hb and the PG electrode was 0.10 s(-1). Positions of the Soret absorbance band indicated that the Hb retained its secondary structure and was similar to its native state. Furthermore, the Hb in DOAB film acted as a biological catalyst towards the reduction of nitric oxide (NO). The voltammetric response of NO at the Hb-DOAB modified electrode could be used to determine the concentration of NO in solution.     

Ion fluxes in giant excised cardiac membrane patches detected and quantified with ion-selective microelectrodes

We have used ion-selective electrodes (ISEs) to quantify ion fluxes across giant membrane patches by measuring and simulating ion gradients on both membrane sides. Experimental conditions are selected with low concentrations of the ions detected on the membrane side being monitored. For detection from the cytoplasmic (bath) side, the patch pipette is oscillated laterally in front of an ISE. For detection on the extracellular (pipette) side, ISEs are fabricated from flexible quartz capillary tubing (tip diameters, 2-3 microns), and an ISE is positioned carefully within the patch pipette with the tip at a controlled distance from the mouth of the patch pipette. Transport activity is then manipulated by solution changes on the cytoplasmic side. Ion fluxes can be quantified by simulating the ion gradients with appropriate diffusion models. For extracellular (intrapatch pipette) recordings, ion diffusion coefficients can be determined from the time courses of concentration changes. The sensitivity and utility of the methods are demonstrated with cardiac membrane patches by measuring (a) potassium fluxes via ion channels, valinomycin, and Na/K pumps; (b) calcium fluxes mediated by Na/Ca exchangers; (c) sodium fluxes mediated by gramicidin and Na/K pumps; and (d) proton fluxes mediated by an unknown electrogenic mechanism. The potassium flux-to-current ratio for the Na/K pump is approximately twice that determined for potassium channels and valinomycin, as expected for a 3Na/2K pump stoichiometery (i.e., 2K/charge moved). For valinomycin-mediated potassium currents and gramicidin-mediated sodium currents, the ion fluxes calculated from diffusion models are typically 10-15% smaller than expected from the membrane currents. As presently implemented, the ISE methods allow reliable detection of calcium and proton fluxes equivalent to monovalent cation currents <1 pA in magnitude, and they allow detection of sodium and potassium fluxes equivalent to <5 pA currents. The capability to monitor ion fluxes, independent of membrane currents, should facilitate studies of both electrogenic and electroneutral ion-coupled transporters in giant patches.     

Discovery of Calcium‐Metal Alloy Anodes for Reversible Ca‐Ion Batteries

Ca‐ion batteries (CIBs) show promise to achieve the high energy density required by emerging applications like electric vehicles because of their potentially improved capacities and high operating voltages. The development of CIBs is hindered by the failure of traditional graphite and calcium metal anodes due to the intercalation difficulty and the lack of efficient electrolytes. Recently, a high voltage (4.45 V) CIB cell using Sn as the anode has been reported to achieve a remarkable cyclability (>300 cycles). The calciation of Sn is observed to end at Ca₇Sn₆, which is surprising, since higher Ca‐content compounds are known (e.g., Ca₂Sn). Here, the Sn electrochemical calciation reaction process is investigated computationally and the reaction driving force as a function of Ca content is explored using density functional theory (DFT) calculations. This exploration allows the identification of threshold voltages which govern the limits of the calciation process. This information is then used to design a four‐step screening strategy and high‐throughput DFT is utilized to search for anode materials with higher properties. Many metalloids (Si, Sb, Ge), (post‐)transition metals (Al, Pb, Cu, Cd, CdCu₂) are predicted to be promising inexpensive anode candidates and warrant further experimental investigations.     

Fabrication of Low‐Tortuosity Ultrahigh‐Area‐Capacity Battery Electrodes through Magnetic Alignment of Emulsion‐Based Slurries

High energy‐density, low‐cost batteries are critically important to a variety of applications ranging from portable electronics to electric vehicles (EVs) and grid‐scale storage. While tremendous research effort has been focused on new materials or chemistries with high energy‐density potential, design innovations such as low‐tortuosity thick electrodes are another promising path toward higher energy density and lower cost. Growing demand for fast‐charging batteries has also highlighted the need for negative electrodes that can accept high rate charging without metal deposition; low tortuosity can be a benefit in this regard. However, a general and scalable fabrication method for low‐tortuosity electrodes is currently lacking. Here an emulsion‐based, magnetic‐alignment approach to producing thick electrodes (>400 µm thickness) with ultrahigh areal capacity (up to ≈14 mAh cm^?2 vs 2–4 mAh cm^?2 for conventional lithium ion) is reported. The process is demonstrated for LiCoO₂ and meso‐carbon microbead graphite. The LiCoO₂ cathodes are confirmed to have low tortuosity via DC‐depolarization experiments and deliver high areal capacity (>10 mAh cm^?2) in galvanostatic discharge tests at practical C‐rates and model EV drive‐cycle tests. This simple fabrication method can potentially be applied to many other active materials to enable thick, low‐tortuosity electrodes.     

Paramelaconite‐Enriched Copper‐Based Material as an Efficient and Robust Catalyst for Electrochemical Carbon Dioxide Reduction

A copper‐oxide‐based catalyst enriched with paramelaconite (Cu₄O₃) is presented and investigated as an electrocatalyst for facilitating electroreduction of CO₂ to ethylene and other hydrocarbons. Cu₄O₃ is a member of the copper‐oxide family and possesses an intriguing mixed‐valance nature, incorporating an equal number of Cu⁺ and Cu²⁺ ions in its crystal structure. The material is synthesized using a solvothermal synthesis route and its structure is confirmed via powder X‐ray diffraction, transmission electron microscope based selected area electron diffraction, and X‐ray photoelectron spectroscopy. A flow reactor equipped with a gas diffusion electrode is utilized to test a copper‐based catalyst enriched with the Cu₄O₃ phase under CO₂ reduction conditions. The Cu₄O₃‐rich catalyst (PrC) shows a Faradaic efficiency for ethylene over 40% at 400 mA cm^?2. At ?0.64 versus reversible hydrogen electrode, the highest C₂₊/C₁ product ratio of 4.8 is achieved, with C₂₊ Faradaic efficiency over 61%. Additionally, the catalyst exhibits a stable performance for 24 h at a constant current density of 200 mA cm^?2.     

Two‐Step Activated Carbon Cloth with Oxygen‐Rich Functional Groups as a High‐Performance Additive‐Free Air Electrode for Flexible Zinc–Air Batteries

A flexible air electrode (FAE) with both high oxygen electrocatalytic activity and excellent flexibility is the key to the performance of various flexible devices, such as Zn–air batteries. A facile two‐step method, mild acid oxidation followed by air calcination that directly activates commercial carbon cloth (CC) to generate uniform nanoporous and super hydrophilic surface structures with optimized oxygen‐rich functional groups and an enhanced surface area, is presented here. Impressively, this two‐step activated CC (CC‐AC) exhibits superior oxygen electrocatalytic activity and durability, outperforming the oxygen‐doped carbon materials reported to date. Especially, CC‐AC delivers an oxygen evolution reaction (OER) overpotential of 360 mV at 10 mA cm^?2 in 1 m KOH, which is among the best performances of metal‐free OER electrocatalysts. The practical application of CC‐AC is presented via its use as an FAE in a flexible rechargeable Zn–air battery. The bendable battery achieves a high open circuit voltage of 1.37 V, a remarkable peak power density of 52.3 mW cm^?3 at 77.5 mA cm^?3, good cycling performance with a small charge–discharge voltage gap of 0.98 V and high flexibility. This study provides a new approach to the design and construction of high‐performance self‐supported metal‐free electrodes.     

Multidimensional Ordered Bifunctional Air Electrode Enables Flash Reactants Shuttling for High‐Energy Flexible Zn‐Air Batteries

Direct growth of electrocatalysts on conductive substrates is an emerging strategy to prepare air electrodes for flexible Zn‐air batteries (FZABs). However, electrocatalysts grown on conductive substrates usually suffer from disorder and are densely packed with “prohibited zones”, in which internal blockages shut off the active sites from catalyzing the oxygen reaction. Herein, to minimize the “prohibited zones”, an ordered multidimensional array assembled by 1D carbon nanotubes and 2D carbon nanoridges decorated with 0D cobalt nanoparticles (referred as MPZ‐CC@CNT) is constructed on nickel foam. When the MPZ‐CC@CNT is directly applied as a self‐supported electrode for FZAB, it delivers a marginal voltage fading rate of 0.006 mV cycle^?1 over 1800 cycles (600 h) at a current density of 50 mA cm^?2 and an impressive energy density of 946 Wh kg^?1. Electrochemical impedance spectroscopy reveals that minimal internal resistance and electrochemical polarization, which is beneficial for the flash reactant shuttling among the triphase (i.e., oxygen, electrolyte, and catalyst) are offered by the open and ordered architecture. This advanced electrode design provides great potential to boost the electrochemical performance of other rechargeable battery systems.     

A Riemannian manifold analysis of endothelial cell monolayer impedance parameter precision

Endothelial cell adhesion and barrier function play a critical role in many biological and pathophysiological processes. The decomposition of endothelial cell adhesion and barrier function into cell–cell and cell–matrix components using frequency dependent cellular micro-impedance measurements has, therefore, received widespread application. Few if any studies, however, have examined the precision of these model parameters. This study presents a parameter sensitivity analysis of a representative cellular barrier function model using a concise geometric formulation that includes instrumental data acquisition settings. Both model state dependence and instrumental noise distributions are accounted for within the framework of Riemannian manifold theory. Experimentally acquired microimpedance measurements of attached endothelial cells define the model state domain, while experimentally measured noise statistics define the data space Riemannian metric based on the Fisher information matrix. The results of this analysis show that the sensitivity of cell–cell and cell–matrix impedance components are highly model state dependent and several well defined regions of low precision exist. The results of this study further indicate that membrane resistive components can significantly reduce the precision of the remaining parameters in these models. This work was supported by a National Science Foundation CAREER Award (AE), BES-0238905, and in part by the American Heart Association under Grant 0265029B (AE).