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

Electronic bulk and domain wall properties in B-site doped hexagonal ErMnO3_3

Acceptor and donor doping is a standard for tailoring semiconductors. More recently, doping was adapted to optimize the behavior at ferroelectric domain walls. In contrast to more than a century of research on semiconductors, the impact of chemical substitutions on the local electronic response at domain walls is largely unexplored. Here, the hexagonal manganite ErMnO$_3$ is donor doped with Ti$^{4+}$. Density functional theory calculations show that Ti$^{4+}$ goes to the B-site, replacing Mn$^{3+}$. Scanning probe microscopy measurements confirm the robustness of the ferroelectric domain template. The electronic transport at both macro- and nanoscopic length scales is characterized. The measurements demonstrate the intrinsic nature of emergent domain wall currents and point towards Poole-Frenkel conductance as the dominant transport mechanism. Aside from the new insight into the electronic properties of hexagonal manganites, B-site doping adds an additional degree of freedom for tuning the domain wall functionality

Turbulent primary breakup of round and plane liquid jets in still air

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/76929/1/AIAA-2002-1115-390.pd

Magnetoelastics of a spin liquid: X-ray diffraction studies of Tb2Ti2O7 in pulsed magnetic fields

We report high resolution single crystal x-ray diffraction measurements of the frustrated pyrochlore magnet Tb2Ti2O7, collected using a novel low temperature pulsed magnet system. This instrument allows characterization of structural degrees of freedom to temperatures as low as 4.4 K, and in applied magnetic fields as large as 30 Tesla. We show that Tb2Ti2O7 manifests intriguing structural effects under the application of magnetic fields, including strongly anisotropic giant magnetostriction, a restoration of perfect pyrochlore symmetry in low magnetic fields, and ultimately a structural phase transition in high magnetic fields. It is suggested that the magnetoelastic coupling thus revealed plays a significant role in the spin liquid physics of Tb2Ti2O7 at low temperatures.Comment: 4 pages, 4 figures, submitted for publicatio

Multimaterial Piezoelectric Fibres

Fibre materials span a broad range of applications ranging from simple textile yarns to complex modern fibre-optic communication systems. Throughout their history, a key premise has remained essentially unchanged: fibres are static devices, incapable of controllably changing their properties over a wide range of frequencies. A number of approaches to realizing time-dependent variations in fibres have emerged, including refractive index modulation1, 2, 3, 4, nonlinear optical mechanisms in silica glass fibres5, 6, 7, 8 and electroactively modulated polymer fibres9. These approaches have been limited primarily because of the inert nature of traditional glassy fibre materials. Here we report the composition of a phase internal to a composite fibre structure that is simultaneously crystalline and non-centrosymmetric. A ferroelectric polymer layer of 30 μm thickness is spatially confined and electrically contacted by internal viscous electrodes and encapsulated in an insulating polymer cladding hundreds of micrometres in diameter. The structure is thermally drawn in its entirety from a macroscopic preform, yielding tens of metres of piezoelectric fibre. The fibres show a piezoelectric response and acoustic transduction from kilohertz to megahertz frequencies. A single-fibre electrically driven device containing a high-quality-factor Fabry–Perot optical resonator and a piezoelectric transducer is fabricated and measured.National Science Foundation (U.S.) (Materials Research Science and Engineering Centers Program, award number DMR-0819762)United States. Defense Advanced Research Projects Agency (Griggs)United States. Army Research Office (Institute for Soldier Nanotechnologies, contract no. W911NF-07-D-0004

Susceptibility anisotropy in an iron arsenide superconductor revealed by x-ray diffraction in pulsed magnetic fields

In addition to unconventional high-Tc superconductivity, the iron arsenides exhibit strong magnetoelastic coupling and a notable electronic anisotropy within the a-b plane. We relate these properties by studying underdoped Ba(Fe{1-x}Co{x})2As2 by x-ray diffraction in pulsed magnetic fields up to 27.5 Tesla. We exploit magnetic detwinning effects to demonstrate anisotropy in the in-plane susceptibility, which develops at the structural phase transition despite the absence of magnetic order. The degree of detwinning increases smoothly with decreasing temperature, and a single- domain condition is realized over a range of field and temperature. At low temperatures we observe an activated behavior, with a large hysteretic remnant effect. Detwinning was not observed within the superconducting phase for accessible magnetic fields.Comment: 5 pages, 3 figure

Optically transparent dense colloidal gels.

Traditionally it has been difficult to study the porous structure of dense colloidal gels and (macro) molecular transport through them simply because of the difference in refractive index between the colloid material and the continuous fluid phase surrounding it, rendering the samples opaque even at low colloidal volume fractions. Here, we demonstrate a novel colloidal gel that can be refractive index-matched in aqueous solutions owing to the low refractive index of fluorinated latex (FL)-particles (n = 1.37). Synthesizing them from heptafluorobutyl methacrylate using emulsion polymerization, we demonstrate that they can be functionalized with short DNA sequences via a dense brush-layer of polystyrene-b-poly(ethylene oxide) block-copolymers (PS-PEO). The block-copolymer, holding an azide group at the free PEO end, was grafted to the latex particle utilizing a swelling-deswelling method. Subsequently, DNA was covalently attached to the azide-end of the block copolymer via a strain-promoted alkyne-azide click reaction. For comparison, we present a structural study of single gels made of FL-particles only and composite gels made of a percolating FL-colloid gel coated with polystyrene (PS) colloids. Further we demonstrate that the diffusivity of tracer colloids dispersed deep inside a refractive index matched FL-colloidal gel can be measured as function of the local confinement using Dynamic Differential Microscopy (DDM).EE thanks the Winton Program for Sustainable Physics and the ETN-COLLDENSE (H2020-MCSA-ITN-2014, grant no. 642774), Clare P. Grey for collaborations and continued discussions as well as W. Frith. MZ is funded by a joint EPSRC and Unilever CASE award RG748000. DJ thanks the Udayan Care - Vcare grant, the Nehru Trust for Cambridge University, Schlumberger Foundation's FFTF program and Hughes Hall - Santander Bursary. ZR received funding from the Winton Program for the Physics of Sustainability and the EU ERC FP7 programme via an advanced fellowship for Clare P. Grey

Thermally reversible nanoparticle gels with tuneable porosity showing structural colour.

We present colloidal gels formed from dispersions of PEG- and PEG+DNA-coated silica nanoparticles showing structural colour. The PEG- and PEG+DNA-coated silica colloids are functionalized using exclusively covalent bonds in aqueous conditions. Both sets of colloids self-assemble into thermally-reversible colloidal gels with porosity that can be tuned by changing the colloid volume fraction, although the interaction potentials of the colloids in the two systems are different. Confocal microscopy and image analysis tools are used to characteraize the gels' microstructures. Optical reflection spectroscopy is employed to study the underlying gel nanostructure and to characterize the optical response of the gels. X-ray nanotomography is used to visualize the nanoscale phase separation between the colloid-rich gel branches and the colloid-free gel pores. These nanoparticle gels open new routes for creating structural colour where the gel structure is decoupled from the form factor of the individual colloids. This approach can be extended to create unexplored three dimensional macroscale materials with length scales spanning hundreds of nanometers, which has been difficult to achieve using other methods

A robust but disordered collapsed-volume phase in a cerium alloy under the application of pulsed magnetic fields

We report synchrotron x-ray powder diffraction measurements of Ce0.8La0.1Th0.1 subject to pulsed magnetic fields as high as 28 Tesla. This alloy is known to exhibit a continuous volume collapse on cooling at ambient pressure, which is a modification of the gamma -> alpha transition in elemental cerium. Recently, it has been suggested on the basis of field-cooled resistivity and pulsed field magnetization measurements that the volume collapse in this alloy can be suppressed by the application of magnetic fields. Conversely, our direct diffraction measurements show a robust collapsed phase, which persists in magnetic fields as high as 28 Tesla. We also observe nanoscale disorder in the collapsed phase, which increasingly contaminates the high temperature phase on thermal cycling.Comment: 6 pages, 6 figures, submitted to PR