Exploring the influence of iron substitution in lithium rich layered oxides Li2Ru1-:XFexO3: Triggering the anionic redox reaction

Lithium rich layered materials are an interesting class of materials which exploit both anionic and cationic redox reactions to store energy upwards of 250 mA h g-1. This paper aims to understand the nature of the redox reactions taking place in these compounds. Li2RuO3 was used as the base compound, which is then compared with compounds generated by partially substituting Ru with Ti and Fe respectively. Electrochemical tests indicate that Fe substitution in the sample leads to an improvement in capacity, cycle life and reduction of potential decay. To elucidate the reason for this improvement in operando diffraction experiments were carried out, highlighting the formation of a secondary de-lithiated phase. The distortion of the pristine structure eventually induces frontier orbital reorganization leading to the oxygen redox reaction resulting in extra capacity. Local changes at Fe and Ru ions are recorded using in operando X-ray absorption spectroscopy (XAS). It was noted that while Ru undergoes a reversible redox reaction, Fe undergoes a significant irreversible change in its coordination environment during cycling. The changes in the coordination environment of oxygen and formation of O2n- type species were probed in situ using soft X-rays

Exploring the influence of iron substitution in lithium rich layered oxides Li2Ru1-xFexO3: triggering the anionic redox reaction

Lithium rich layered materials are an interesting class of materials which exploit both anionic and cationic redox reactions to store energy upwards of 250 mA h g−1. This paper aims to understand the nature of the redox reactions taking place in these compounds. Li2RuO3 was used as the base compound, which is then compared with compounds generated by partially substituting Ru with Ti and Fe respectively. Electrochemical tests indicate that Fe substitution in the sample leads to an improvement in capacity, cycle life and reduction of potential decay. To elucidate the reason for this improvement in operando diffraction experiments were carried out, highlighting the formation of a secondary de-lithiated phase. The distortion of the pristine structure eventually induces frontier orbital reorganization leading to the oxygen redox reaction resulting in extra capacity. Local changes at Fe and Ru ions are recorded using in operando X-ray absorption spectroscopy (XAS). It was noted that while Ru undergoes a reversible redox reaction, Fe undergoes a significant irreversible change in its coordination environment during cycling. The changes in the coordination environment of oxygen and formation of O2n− type species were probed in situ using soft X-rays

Chemical Evolution of CoCrMo Wear Particles: An in Situ Characterization Study

The unexpected high failure rates of CoCrMo hip implants are associated with the release of a large number of inflammatory wear particles. CoCrMo is nominally a stable material; however, previous chemical speciation studies on CoCrMo wear particles obtained from periprosthetic tissue revealed only trace amounts of Co remaining despite Co being the major component of the alloy. The unexpected high levels of Co dissolution in vivo raised significant clinical concerns particularly related to the Cr speciation in the dissolution process. At high electrochemical potentials, the alloy's Cr-rich passive film breaks down (transpassive polarization), facilitating alloy dissolution. The potential release of the carcinogenic Cr(VI) species in vivo has been a subject of debate. While the large-scale Co dissolution observed on in vivo produced particles could indicate a highly oxidizing in vivo environment, Cr(VI) species were not previously detected in periprosthetic tissue samples (except in the specific case of post-mortem tissue of diabetic patients). However, Cr(VI) is likely to be an unstable (transient) species in biological environments, and studies on periprosthetic tissue do not provide information about intermediate reaction products or the exposure history of the wear particles. Here, an in situ spectromicroscopy approach was developed, utilizing the high chemical resolution of synchrotron radiation, to study CoCrMo reactivity as a function of time and oxidizing conditions. The results reveal limited Co dissolution from CoCrMo particles, which increases dramatically at a critical electrochemical potential. Furthermore, in situ XAS detected only Cr(III) dissolution, even at potentials where Cr(VI) is known to be produced, suggesting that Cr(VI) species are extremely transient in simulated biological environments where the oxidation zone is small

Understanding the reactivity of CoCrMo-implant wear particles

CoCrMo-based metal-on-metal hip implants experienced unexpectedly high failure rates despite the high wear and corrosion resistance of the bulk material. Although they exhibit a lower volumetric wear compared to other implant materials, CoCrMo-based implants produced a significantly larger 'number' of smaller wear particles. CoCrMo is nominally an extremely stable material with high Cr content providing passivity. However, despite the Co:Cr ratio in the original alloy being 2:1; chemical analyses of wear particles from periprosthetic tissue have found the particles to be composed predominately of Cr species, with only trace amounts of Co remaining. Here a correlative spectroscopy and microscopy approach has shown that these particles dissolve via a non-stoichiometric, and geometrically inhomogeneous, mechanism similar to de-alloying. This mechanism is previously unreported for this material and was not apparent in any of the regulatory required tests, suggesting that such tests are insufficiently discriminating

Taming Charge Transport in Semiconducting Polymers with Branched Alkyl Side Chains

National Research Fund of Luxembourg. Grant Number: 6932623; Croucher Foundation; Kodak Graduate Fellowship; Office of Naval Research. Grant Number: N00014-17-1-2214; U.S. Department of Energy. Grant Number: DE-AC02-76SF0051

Direct in situ observation of ZnO nucleation and growth via transmission X-ray microscopy

The nucleation and growth of a nanostructure controls its size and morphology, and ultimately its functional properties. Hence it is crucial to investigate growth mechanisms under relevant growth conditions at the nanometer length scale. Here we image the nucleation and growth of electrodeposited ZnO nanostructures in situ, using a transmission X-ray microscope and specially designed electrochemical cell. We show that this imaging technique leads to new insights into the nucleation and growth mechanisms in electrodeposited ZnO including direct, in situ observations of instantaneous versus delayed nucleation

Non-Conjugated Flexible Linkers in Semiconducting Polymers: A Pathway to Improved Processability without Compromising Device Performance

Semiconducting polymers, in contrast to inorganic silicon, are solution processable and can potentially be printed cost efficiently on flexible large‐area substrates. However to do so it is of paramount importance to formulate the polymeric semiconductors into inks with specific viscosities. Herein, the synthesis of a new highly soluble isoindigo monomer and its incorporation into low bandgap semiconducting polymers is presented. Non‐conjugated flexible linkers are introduced into the conjugated backbone in order to modulate the materials processability. The viscoelastic properties of the new polymers are studied in detail by means of rheometry and dynamical mechanical analysis. The solution viscosity is directly proportional to the content of non‐conjugated linkers in the polymer backbone. In organic field‐effect transistors maximum hole mobilities of 1.7 cm2 V−1 s−1 are achieved with the new polymers. Due to the enhanced solubility all‐polymer solar cells are fabricated by solution shearing, reaching power conversion efficiency values of 3.7%

Acoustic phonon lifetimes limit thermal transport in methylammonium lead iodide

Hybrid organic–inorganic perovskites (HOIPs) have become an important class of semiconductors for solar cells and other optoelectronic applications. Electron–phonon coupling plays a critical role in all optoelectronic devices, and although the lattice dynamics and phonon frequencies of HOIPs have been well studied, little attention has been given to phonon lifetimes. We report high-precision momentum-resolved measurements of acoustic phonon lifetimes in the hybrid perovskite methylammonium lead iodide (MAPI), using inelastic neutron spectroscopy to provide high-energy resolution and fully deuterated single crystals to reduce incoherent scattering from hydrogen. Our measurements reveal extremely short lifetimes on the order of picoseconds, corresponding to nanometer mean free paths and demonstrating that acoustic phonons are unable to dissipate heat efficiently. Lattice-dynamics calculations using ab initio third-order perturbation theory indicate that the short lifetimes stem from strong three-phonon interactions and a high density of low-energy optical phonon modes related to the degrees of freedom of the organic cation. Such short lifetimes have significant implications for electron–phonon coupling in MAPI and other HOIPs, with direct impacts on optoelectronic devices both in the cooling of hot carriers and in the transport and recombination of band edge carriers. These findings illustrate a fundamental difference between HOIPs and conventional photovoltaic semiconductors and demonstrate the importance of understanding lattice dynamics in the effort to develop metal halide perovskite optoelectronic devices

Taming Charge Transport in Semiconducting Polymers with Branched Alkyl Side Chains

The solid-state packing and polymer orientation relative to the substrate are key properties to control in order to achieve high charge carrier mobilities in organic field effect transistors (OFET). Intuitively, shorter side chains are expected to yield higher charge carrier mobilities because of a denser solid state packing motif and a higher ratio of charge transport moieties. However our findings suggest that the polymer chain orientation plays a crucial role in high-performing diketopyrrolopyrrole-based polymers. By synthesizing a series of DPP-based polymers with different branched alkyl side chain lengths, it is shown that the polymer orientation depends on the branched alkyl chain lengths and that the highest carrier mobilities are obtained only if the polymer adopts a mixed face-on/edge-on orientation, which allows the formation of 3D carrier channels in an otherwise edge-on-oriented polymer chain network. Time-of-flight measurements performed on the various polymer films support this hypothesis by showing higher out-of-plane carrier mobilities for the partially face-on-oriented polymers. Additionally, a favorable morphology is mimicked by blending a face-on polymer into an exclusively edge-on oriented polymer, resulting in higher charge carrier mobilities and opening up a new avenue for the fabrication of high performing OFET devices