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Transition metal dissolution and degradation in nmc811-graphite electrochemical cells
Nickel-rich lithium nickel-manganese-cobalt oxide cathodes, in particular Li(Ni0.8Mn0.1Co0.1)O2 (NMC811), are currently being commercialized as next generation cathode materials, due to their increased capacities compared to current materials. Unfortunately, the higher nickel content has been shown to accelerate cell degradation and a better understanding is needed to maximize cell lifetimes. NMC811/graphite cells were tested under stressed conditions (elevated temperature and cell voltages) to accelerate degradation focusing on transition metal (TM) dissolution from the cathode. Increasing the cell temperature, upper cut-off voltage (UCV) and number of cycles all accelerated capacity fade and diffraction studies showed that under stressed conditions, additional degradation mechanisms beyond lithium loss to the SEI are present. Significant TM dissolution and subsequent deposition on the graphite anode is seen, particularly at stressed conditions. The concentration of TMs in the electrolyte remained invariant with cycling conditions, presumably reflecting the limited solubility of these ions and emphasizing the role that TM deposition on the anode plays in continuing to drive dissolution. Significant deposits of metals from the cell casings and current collectors were also detected at all cycling conditions, indicating that corrosion and metal leaching can be as important as TM dissolution from the active material in some cell formats.We thank Ms. Jennifer Allen, Prof. Mary Ryan and Dr Daniel
Abraham for helpful discussions. We thank Stephen Young and Nigel
Howard for assistance with the ICP-OES measurements. This work is
supported by the Faraday Institution under grant no. FIRG00
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Phase Behavior during Electrochemical Cycling of Ni-Rich Cathode Materials for Li-Ion Batteries
Although layered lithium nickel-rich oxides have become the state-of-the-art cathode materials for lithium-ion batteries in EV applications, they can suffer from rapid performance failure – particularly when operated under conditions of stress (temperature, high voltage), the underlying mechanisms of which are not fully understood. In this essay, we aim to connect the electrochemical performance with changes in structure during cycling. First, we compare the structural properties of LiNiO2, to the substituted Ni-rich compounds NMCs (LiNixMnyCo1-x-yO2) and NCAs (LiNixCoyAl1-x-yO2). Particular emphasis is placed on decoupling intrinsic behaviour and extrinsic “two-phases” reactions observed during initial cycles, as well as after extensive cycling for NMC and NCA cathodes. We highlight the need to revisit the various high-voltage structural change processes that occur in LiNiO2 with modern characterization tools to aid the understanding of the accelerated degradation for Ni- rich cathodes at high voltages
STAT3 controls COL1A2 enhancer activation cooperatively with JunB, regulates type I collagen synthesis post-transcriptionally and is essential for lung myofibroblast differentiation
Fibroblast differentiation is key cellular process that underlies the process of fibrosis, a deadly complication of fibrotic diseases like Scleroderma (SSc). This transition coincides with the overproduction of Collagen type I (COL1) and other extracellular matrix proteins. High level expression of the collagen type 1α2 subunit (COL1A2), requires the engagement of a far upstream enhancer, whose activation is strongly dependent on the AP1 factor JunB. We now report that STAT3 also binds the COL1A2 enhancer and is essential for RNA polymerase recruitment, without affecting JunB binding. STAT3 is required for the increased COL1A2 expression observed in myofibroblasts.We also report that TGFβ partially activates STAT3 and show that inhibiting STAT3 potently blocks TGFβ signalling, matrix remodelling and TGFβ-induced myofibroblast differentiation. Activation of STAT3 with IL6 trans-signalling alone however only increased COL1A2 protein expression, leaving
COL1A2 mRNA levels unchanged. Our results suggest that activated STAT3 is not the limiting factor
for collagen enhancer activation in human lung fibroblasts. Yet, a certain threshold level of STAT3
38 activity is essential to support activation of the COL1A2 enhancer and TGFβ signalling in fibroblasts.
We propose that STAT3 operates at the post-transcriptional as well as the transcriptional level
Mechanics and dynamics of X-chromosome pairing at X inactivation
At the onset of X-chromosome inactivation, the vital process whereby female mammalian cells equalize X products with
respect to males, the X chromosomes are colocalized along their Xic (X-inactivation center) regions. The mechanism
inducing recognition and pairing of the X’s remains, though, elusive. Starting from recent discoveries on the molecular
factors and on the DNA sequences (the so-called "pairing sites") involved, we dissect the mechanical basis of Xic
colocalization by using a statistical physics model. We show that soluble DNA-specific binding molecules, such as those
experimentally identified, can be indeed sufficient to induce the spontaneous colocalization of the homologous
chromosomes but only when their concentration, or chemical affinity, rises above a threshold value as a consequence of a
thermodynamic phase transition. We derive the likelihood of pairing and its probability distribution. Chromosome dynamics
has two stages: an initial independent Brownian diffusion followed, after a characteristic time scale, by recognition and
pairing. Finally, we investigate the effects of DNA deletion/insertions in the region of pairing sites and compare model
predictions to available experimental data
Instantons and Killing spinors
We investigate instantons on manifolds with Killing spinors and their cones.
Examples of manifolds with Killing spinors include nearly Kaehler 6-manifolds,
nearly parallel G_2-manifolds in dimension 7, Sasaki-Einstein manifolds, and
3-Sasakian manifolds. We construct a connection on the tangent bundle over
these manifolds which solves the instanton equation, and also show that the
instanton equation implies the Yang-Mills equation, despite the presence of
torsion. We then construct instantons on the cones over these manifolds, and
lift them to solutions of heterotic supergravity. Amongst our solutions are new
instantons on even-dimensional Euclidean spaces, as well as the well-known
BPST, quaternionic and octonionic instantons.Comment: 40 pages, 2 figures v2: author email addresses and affiliations adde
Designing Optimal Perovskite Structure for High Ionic Conduction.
Solid-oxide fuel/electrolyzer cells are limited by a dearth of electrolyte materials with low ohmic loss and an incomplete understanding of the structure-property relationships that would enable the rational design of better materials. Here, using epitaxial thin-film growth, synchrotron radiation, impedance spectroscopy, and density-functional theory, the impact of structural parameters (i.e., unit-cell volume and octahedral rotations) on ionic conductivity is delineated in La0.9 Sr0.1 Ga0.95 Mg0.05 O3- δ . As compared to the zero-strain state, compressive strain reduces the unit-cell volume while maintaining large octahedral rotations, resulting in a strong reduction of ionic conductivity, while tensile strain increases the unit-cell volume while quenching octahedral rotations, resulting in a negligible effect on the ionic conductivity. Calculations reveal that larger unit-cell volumes and octahedral rotations decrease migration barriers and create low-energy migration pathways, respectively. The desired combination of large unit-cell volume and octahedral rotations is normally contraindicated, but through the creation of superlattice structures both expanded unit-cell volume and large octahedral rotations are experimentally realized, which result in an enhancement of the ionic conductivity. All told, the potential to tune ionic conductivity with structure alone by a factor of ≈2.5 at around 600 °C is observed, which sheds new light on the rational design of ion-conducting perovskite electrolytes
Real-time correlators in warped AdS/CFT correspondence
We study real-time correlators in the warped AdS/CFT correspondence. We apply
the prescription used in the usual AdS/CFT correspondence and obtain the
retarded Green's functions for the scalar and vector fields in the spacelike
warped and the null warped black hole backgrounds. We find that the retarded
Green's functions and the cross sections are well consistent with the
predictions from dual CFT. Our results not only support strongly the
conjectured warped AdS/CFT correspondence, but also show that the usual
relativistic AdS/CFT prescription of obtaining the real-time correlators remain
effective in more general backgrounds with anisotropic conformal infinity.Comment: 27 page
NKX2-5 regulates vessel remodelling in scleroderma-associated pulmonary arterial hypertension.
NKX2-5 is a member of the homeobox-containing transcription factors critical in regulating tissue differentiation in development. Here, we report a role for NKX2-5 in vascular smooth muscle cell phenotypic modulation in vitro and in vascular remodelling in vivo. NKX2-5 is up-regulated in scleroderma (SSc) patients with pulmonary arterial hypertension. Suppression of NKX2-5 expression in smooth muscle cells, halted vascular smooth muscle proliferation and migration, enhanced contractility and blocked the expression of the extracellular matrix genes. Conversely, overexpression of NKX2-5 suppressed the expression of contractile genes (ACTA2, TAGLN, CNN1) and enhanced the expression of matrix genes (COL1) in vascular smooth muscle cells. In vivo, conditional deletion of NKX2-5 attenuated blood vessel remodelling and halted the progression to hypertension in the mouse chronic hypoxia mouse model. This study revealed that signals related to injury such as serum and low confluence, which induce NKX2-5 expression in cultured cells, is potentiated by TGFβ and further enhanced by hypoxia. The effect of TGFβ was sensitive to ERK5 and PI3K inhibition. Our data suggest a pivotal role for NKX2-5 in the phenotypic modulation of smooth muscle cells during pathological vascular remodelling and provide proof of concept for therapeutic targeting of NKX2-5 in vasculopathies
SREBP1c-CRY1 signalling represses hepatic glucose production by promoting FOXO1 degradation during refeeding
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