Insights into the Cathode-Electrolyte Interphases of High-Energy-Density Cathodes in Lithium-Ion Batteries.

We present a comprehensive study of cycled high-Ni (LiNi1-xMxO2, M = metals), Li-rich (Li1+xMnyM1-x-yO2), and high-voltage spinel (LiMn1.5Ni0.5O4) electrodes with time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy in conjunction with electrochemical techniques to better understand their evolving cathode-electrolyte interphase structure during cycling. TOF-SIMS provides fragment-specific information regarding the surface film content for each of the electrodes. High-Ni cathodes show thick surface films initially containing Li2CO3, later developing oxidized organic carbonates throughout cycling. Li-rich electrode surface films develop strong characteristics during their first activation cycles, where released O2 oxidizes organic carbonates to form polymeric carbons and decomposes LiPF6. High-voltage spinel electrodes operate outside the standard electrolyte stability window, generating reactive oxidized electrolyte species that further decompose LiPF6. The distribution and concentration of these different chemical fragments measured by TOF-SIMS are finally summarized by color-coded high-resolution images of cycled high-Ni, Li-rich, and high-voltage spinel electrodes.

Oxygen reduction reaction induced pH-responsive chemo-mechanical hydrogel actuators.

We describe and characterize elementary designs for electrochemical micro- and macro-scale chemomechanical hydrogel actuators. The actuation of a pH-sensitive cross-linked polyacrylic acid (PAA) hydrogel is driven in the model devices through the oxygen reduction reaction (ORR) occurring at the electrodes of an embedded Au mesh micro-electrochemical array. Proton consumption by the ORR at the cathode of the embedded electrochemical cell leads to the formation of a localized pH gradient that in turn drives the strain response in the composite actuators. The dynamics result from the ionization of the carboxylic acid moieties of the PAA network in the high pH region, yielding an osmotic pressure that drives a volumetric expansion due to water imbibition. This system actuates both stably and reversibly; when the electrochemically-induced ORR is halted, the localized pH gradient dissipates due to diffusive mixing, which in turn relaxes the induced strains. Two approaches to the fabrication of hydrogel actuators were examined in this work. The first method adopted a design based on small flagella (∼0.2 mm × 1.5 mm × 60 µm, width × length × height) in which the actuating PAA structures are molded atop a set of fixed electrodes mounted on a supporting substrate. These hydrogel actuators show fast, large-amplitude, and largely reversible responses in the ORR mediated chemomechanical dynamics. We also investigated larger hydrogel actuators (∼4.5 mm × 11 mm × 1 mm, width × length × height), based on an autonomous design that embeds an open mesh stretchable micro-electrode array within the hydrogel. The significant and design-dependent impacts of mass transfer on the chemomechanical dynamics are evidenced in each case, a feature examined to elucidate more efficient mesoscopic design rules for actuators of this form.

A comparison of atomistic and continuum approaches to the study of bonding dynamics in electrocatalysis: microcantilever stress and in situ EXAFS observations of platinum bond expansion due to oxygen adsorption during the oxygen reduction reaction.

Microcantilever stress measurements are examined to contrast and compare their attributes with those from in situ X-ray absorption spectroscopy to elucidate bonding dynamics during the oxygen reduction reaction (ORR) on a Pt catalyst. The present work explores multiple atomistic catalyst properties that notably include features of the Pt-Pt bonding and changes in bond strains that occur upon exposure to O2 in the electrochemical environment. The alteration of the Pt electronic and physical structures due to O2 exposure occurs over a wide potential range (1.2 to 0.4 V vs normal hydrogen electrode), a range spanning potentials where Pt catalyzes the ORR to those where Pt-oxide forms and all ORR activity ceases. We show that Pt-Pt surface bond strains due to oxygen interactions with Pt-Pt bonds are discernible at macroscopic scales in cantilever-based bending measurements of Pt thin films under O2 and Ar. Complementary extended X-ray absorption fine structure (EXAFS) measurements of nanoscale Pt clusters supported on carbon provide an estimate of the magnitude and direction of the in-operando bond strains. The data show that under O2 the M-M bonds elongate as compared to an N2 atmosphere across a broad range of potentials and ORR rates, an interfacial bond expansion that falls within a range of 0.23 (±0.15)% to 0.40 (±0.20)%. The EXAFS-measured Pt-Pt bond strains correspond to a stress thickness and magnitude that is well matched to the predictions of a mechanics mode applied to experimentally determined data obtained via the cantilever bending method. The data provide new quantitative understandings of bonding dynamics that will need to be considered in theoretical treatments of ORR catalysis and substantiate the subpicometer resolution of electrochemically mediated bond strains detected on the macroscale.

New Horizons for Conventional Lithium Ion Battery Technology.

Secondary lithium ion battery technology has made deliberate, incremental improvements over the past four decades, providing sufficient energy densities to sustain a significant mobile electronic device industry. Because current battery systems provide ∼100-150 km of driving distance per charge, ∼5-fold improvements are required to fully compete with internal combustion engines that provide >500 km range per tank. Despite expected improvements, the authors believe that lithium ion batteries are unlikely to replace combustion engines in fully electric vehicles. However, high fidelity and safe Li ion batteries can be used in full EVs plus range extenders (e.g., metal air batteries, generators with ICE or gas turbines). This perspective article describes advanced materials and directions that can take this technology further in terms of energy density, and aims at delineating realistic horizons for the next generations of Li ion batteries. This article concentrates on Li intercalation and Li alloying electrodes, relevant to the term Li ion batteries.

In situ electrochemical X-ray absorption spectroscopy of oxygen reduction electrocatalysis with high oxygen flux.

An in situ electrochemical X-ray absorption spectroscopy (XAS) cell has been fabricated that enables high oxygen flux to the working electrode by utilizing a thin poly(dimethylsiloxane) (PDMS) window. This cell design enables in situ XAS investigations of the oxygen reduction reaction (ORR) at high operating current densities greater than 1 mA in an oxygen-purged environment. When the cell was used to study the ORR for a Pt on carbon electrocatalyst, the data revealed a progressive evolution of the electronic structure of the metal clusters that is both potential-dependent and strongly current-dependent. The trends establish a direct correlation to d-state occupancies that directly tracks the character of the Pt-O bonding present.

Optimization of a permeation-based microfluidic direct formic acid fuel cell (DFAFC).

A design for a passive, air-breathing microfluidic fuel cell utilizing formic acid (FA) as a fuel is described and its performance characterized. The fuel cell integrates high surface area platinum (cathode) and palladium-platinum (anode) alloy electrodes within a PDMS microfluidic network that keeps them fully immersed in a liquid electrolyte. The polymer network that comprises the device also serves as a self-supporting membrane through which FA and oxygen are supplied to the alloy anode and cathode, respectively, by passive permeation from external sources. The cell is based on a planar form-factor and in its operation exploits FA concentration gradients that form across the PDMS membrane. These latter gradients allow the device to operate stably, producing a nearly constant limiting power density of ~0.2 mW/cm², without driven laminar flow of fluids or the incorporation of an in-channel separator between the anodic and the cathodic compartments. The power output of this elementary device in air is subject to electrolyte mass transport impacts, which can be reduced for a given design rule by decreasing the internal ohmic resistance of the cell. The results suggest that operational stability can be improved by decreasing the kinetic losses imposed on the cathode side of the cell due to FA crossover and modalities for doing so, such as by increasing the efficiency of fuel capture at the anode.