I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[2257]
Open Access
Abstract: The use of silica as a lithium‐ion battery anode material requires a pretreatment step to induce electrochemical activity. The partially reversible electrochemical reduction reaction between silica and lithium has been postulated to produce silicon, which can subsequently reversibly react with lithium, providing stable capacities higher than graphite materials. Up to now, the electrochemical reduction pathway and the nature of the products were unknown, thereby hampering the design, optimization, and wider uptake of silica‐based anodes. Here, the electrochemical reduction pathway is uncovered and, for the first time, elemental silicon is identified as a reduction product. These insights, gleaned from analysis of the current response and capacity increase during reduction, conclusively demonstrated that silica must be reduced to introduce reversible capacity and the highest capacities of 600 mAh g−1 are achieved by using a constant load discharge at elevated temperature. Characterization via total scattering X‐ray pair distribution function analysis reveal the reduction products are amorphous in nature, highlighting the need for local structural methods to uncover vital information often inaccessible by traditional diffraction. These insights contribute toward understanding the electrochemical reduction of silica and can inform the development of pretreatment processes to enable their incorporation into next‐generation lithium‐ion batteries.
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Sep 2020
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[20038]
Open Access
Abstract: Recently, there has been growing interest in the amorphous states of metal–organic frameworks (MOFs). Particular focus has been given to melt-quenched MOF glasses. In this work, to improve our understanding of the factors influencing melting, the thermal response of four closely related zeolitic imidazolate frameworks (ZIFs) was studied. Electron withdrawing ligands were found to lower both the melting and glass transition temperatures, providing a promising strategy for improving the processability of MOFs in the liquid state. Crucially, dense frameworks appear to be essential for melting, with their presence also initiating the melting of open pore frameworks. This opens up the rich polymorphic landscape of ZIFs to the preparation of novel MOF liquids and glasses.
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May 2020
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I15-Extreme Conditions
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Diamond Proposal Number(s):
[19339]
Open Access
Abstract: A new diamond-anvil cell apparatus for in situ synchrotron X-ray diffraction measurements of liquids and glasses, at pressures from ambient to 5 GPa and temperatures from ambient to 1300 K, is reported. This portable setup enables in situ monitoring of the melting of complex compounds and the determination of the structure and properties of melts under moderately high pressure and high temperature conditions relevant to industrial processes and magmatic processes in the Earth's crust and shallow mantle. The device was constructed according to a modified Bassett-type hydrothermal diamond-anvil cell design with a large angular opening (θ = 95°). This paper reports the successful application of this device to record in situ synchrotron X-ray diffraction of liquid Ga and synthetic PbSiO3 glass to 1100 K and 3 GPa.
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Mar 2020
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I15-1-X-ray Pair Distribution Function (XPDF)
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Jingwei
Hou
,
María Laura
Ríos Gómez
,
Andraž
Krajnc
,
Aoife
Mccaul
,
Shichun
Li
,
Alice M.
Bumstead
,
Adam F.
Sapnik
,
Zeyu
Deng
,
Rijia
Lin
,
Philip A.
Chater
,
Dean S.
Keeble
,
David A.
Keen
,
Dominique
Appadoo
,
Bun
Chan
,
Vicki
Chen
,
Gregor
Mali
,
Thomas D.
Bennett
Diamond Proposal Number(s):
[20038]
Abstract: The synthesis of four novel crystalline zeolitic imidazolate framework (ZIF) structures using a mixed-ligand approach is reported. The inclusion of both imidazolate and halogenated benzimidazolate-derived linkers leads to glass-forming behavior by all four structures. Melting temperatures are observed to depend on both electronic and steric effects. Solid-state NMR and terahertz (THz)/Far-IR demonstrate the presence of a Zn-F bond for fluorinated ZIF glasses. In situ THz/Far-IR spectroscopic techniques reveal the dynamic structural properties of crystal, glass and liquid phases of the halogenated ZIFs, linking the melting behavior of ZIFs to the propensity of the ZnN4 tetrahedra to undergo thermally-induced deformation. The inclusion of halogenated ligands within MOF-glasses improves their gas uptake properties.
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Jan 2020
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[17685]
Abstract: The structural dynamics of a quasi-one-dimensional (1D) mixed-metal cyanide,
C
u
1
/
3
A
g
1
/
3
A
u
1
/
3
CN
, with intriguing thermal properties is explored. All the current known related compounds with straight-chain structures, such as group 11 cyanides CuCN, AgCN, AuCN, and bimetallic cyanides
M
x
M
′
1
−
x
CN
(
M
,
M
′
=
Cu
, Ag, Au), exhibit 1D negative thermal expansion (NTE) along the chains and positive thermal expansion (PTE) perpendicular to them.
C
u
1
/
3
A
g
1
/
3
A
u
1
/
3
CN
exhibits similar PTE perpendicular to the chains, however PTE, rather than NTE, is also observed along the chains. In order to understand the origin of this unexpected behavior, inelastic neutron scattering measurements were carried out, underpinned by lattice-dynamical density-functional-theory (DFT) calculations. Synchrotron-based pair-distribution-function analysis and
13
C
solid-state nuclear-magnetic-resonance measurements were also performed to build an input structural model for the lattice dynamical study. The results indicate that transverse motions of the metal ions are responsible for the PTE perpendicular to the chains, as is the case for the related group 11 cyanides. However, NTE along the chain due to the tension effect of these transverse motions is not observed. As there are different metal-to-cyanide bond lengths in
C
u
1
/
3
A
g
1
/
3
A
u
1
/
3
CN
, the metals in neighboring chains cannot all be truly coplanar in a straight-chain model. For this system, DFT-based phonon calculations predict small PTE along the chain due to low-energy chain-slipping modes induced by a bond-rotation effect on the weak metallophilic bonds. However the observed PTE is greater than that predicted with the straight-chain model. Small bends in the chain provide an alternative explanation for thermal behavior. These would mitigate the tension effect induced by the transverse motions of the metals and, as temperature increases and the chains move further apart, a straightening could occur resulting in the observed PTE. This hypothesis is further supported by unusual evolution in the phonon spectra, which suggest small changes in local symmetry with temperature.
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Nov 2019
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I15-1-X-ray Pair Distribution Function (XPDF)
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Lei
Tan
,
Alston J.
Misquitta
,
Andrei
Sapelkin
,
Le
Fang
,
Rory M.
Wilson
,
Dean S.
Keeble
,
Baowei
Zhang
,
Tingting
Zhu
,
Frank S.
Riehle
,
Shuo
Han
,
Kui
Yu
,
Martin T.
Dove
Diamond Proposal Number(s):
[22866, 23168]
Abstract: Four types of magic-size CdS clusters and three different CdS quantum dots have been studied using the technique of X-ray total scattering and pair distribution function analysis. We found that the CdS quantum dots could be modelled as a mixed phase of atomic structures based on the two bulk crystalline phases, which is interpreted as representing the effects of random stacking of layers. However, the results for the magic-size clusters are significantly different. On one hand, the short-range features in the pair distribution function reflect the bulk, indicating that these structures are based on the same tetrahedral coordination found in the bulk phases (and therefore excluding new types of structures such as cage-like arrangements of atoms). But on the other hand, the longer-range atomic structure clearly does not reflect the layer structures found in the bulk and the quantum dots. We compare the effect of two ligands, phenylacetic acid and oleic acid, showing that in one case the ligand has little effect on the atomic structure of the magic-size nanocluster, and in another it has a significant effect.
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Oct 2019
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[21486]
Abstract: Protic Ionic Liquids (PIL) prepared from super-strong base 1,7-diazabicyclo[5.4.0]undec-7-ene (DBU) and super-strong acids, trifluoromethane sulfonic acid (TfOH) and (trifluoromethanesulfonyl)-(nonafluorobutylsulfonyl)imide, (IM14H), have been prepared ([DBUH][TfO] and [DBUH][IM14], respectively; the latter for the first time) and their chemical physical properties and structural features been explored using a synergy of experimental and computational tools. The short range order in neat DBU, as well as the long range structural correlations induced by charge correlation and hydrogen bonding interactions in the ionic liquids, have been explored at ambient conditions, where these compounds are proposed for a variety of applications. Similarly to other [DBUH]-based PILs, the probed ones behave as good ionic liquids. Molecular Dynamics-rationalised X-ray diffraction patterns show the major role played by hydrogen bonding in affecting morphology in these systems. Additionally we find further evidence of the existence of fluorous domains in [DBUH][IM14], thus potentially extending the range of applications for these PILs.
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Oct 2019
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I15-1-X-ray Pair Distribution Function (XPDF)
Optics
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Open Access
Abstract: The Diamond Light Source (DLS) beamline I15-1 measures atomic pair distribution functions (PDF) using scattering of 40-80 keV X-rays. A unique focusing element was needed to condense these X-rays from an initial large cross section (11.0 mm H × 4.2 mm V) into a required spot size of FWHM ≈680 μm (H) × 20 μm (V) at a variable position between the sample and the detector. The large numerical aperture is achieved by coating a silicon substrate over 1 m long with three multilayer stripes of Bragg angle 4.2 mrad. One stripe selects X-rays of each energy 40.0, 65.4, and 76.6 keV. Sixteen piezoelectric bimorph actuators attached to the sides of the mirror substrate adjusted the reflecting surface’s shape. Focal spots of vertical width < 15 µm were obtained at three positions over a 0.92 m range, with fast, easy switching from one focal position to another. Minimized root mean square slope errors were close to 0.5 µrad after subtraction of a uniform curvature. Reflectivity curves taken along each stripe showed consistent high peaks with generally small angular variation of peak positions. This is the first application of a 1 m long multilayer-coated bimorph mirror at a synchrotron beamline. Data collected with its help on a slice of a lithium ion battery’s cathode are presented.
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May 2019
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B18-Core EXAFS
I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[16168, 19240, 16460]
Abstract: K0.5Bi0.5TiO3 (KBT) – one of the few perovskite-like ferroelectric compounds with room-temperature tetragonal symmetry – differs from other members of this family (BaTiO3 and PbTiO3) by the presence of a disordered mixture of K and Bi on cuboctahedral sites. This disorder is expected to affect local atomic displacements and their response to an applied electric field. We have derived nanoscale atomistic models of KBT by refining atomic coordinates to simultaneously fit neutron/X-ray total-scattering and extended X-ray absorption fine-structure data. Both Bi and Ti ions were found to be offset relative to their respective oxygen cages in the high-temperature cubic phase; in contrast, the coordination environment of K remained relatively undistorted. In the cubic structure, Bi displacements prefer the <100> directions and the probability-density distribution of Bi features six well-separated sites; a similar preference exists for the much smaller Ti displacements although the split sites for Ti could not be resolved. The cation displacements are correlated, yielding polar nanoregions, while on average the structure appears as cubic. The cubic<->tetragonal phase transition involves both order-disorder and displacive mechanisms. A qualitative change in the form of the Bi probability-density distribution occurs in the tetragonal phase on cooling to room temperature because Bi displacements “branch off” to <111> directions. This change, which preserves the average symmetry, is accompanied by the development of nanoscale polar heterogeneities that exhibit significant deviations of their polarization vectors from the average polar axis.
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Mar 2019
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I15-1-X-ray Pair Distribution Function (XPDF)
Optics
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Open Access
Abstract: The X-ray pair distribution function beamline I15-1 at Diamond Light Source requires optical elements that focus a wiggler X-ray beam of high energy (40-80 keV) and large area (11.0 mm × 4.4 mm) into a small spot (FWHM ~ 700 μm (h) × 20 μm (v)) at a variable distance between sample and detector. X-ray lenses do not reach the necessary effective apertures because of absorption and the limits of fabrication technology. The aperture of conventional silicon X-ray mirrors, even with metal coatings, is likewise limited by the shallow critical angle for high-energy X-rays. As a solution, CINEL Strumenti Scientifici delivered the first multilayer-coated bimorph mirror for use at a synchrotron beamline. A silicon substrate was polished by Thales-SESO to have an elliptically curved surface. The mirror was then coated with three multilayer stripes (Ni/B4C, W/B4C, Pt/B4C) of unmatched 1 m length by Rigaku Innovative Technologies. Each stripe’s d-spacing was chosen so that the Bragg angle of its first-order reflection would occur at 4.2 mrad at the center of the mirror. Moreover, each stripe’s d-spacing was graded along the mirror’s length to ensure high reflectivity from the whole stripe. Piezoelectric actuators were then glued to the sides of the coated substrate by Thales-SESO to convert it to a bimorph deformable mirror. This enables the mirror to vary its focusing distance from 3.6 m to 4.8 m, and to compensate for residual long-wavelength slope errors. The mirror’s capability to provide vertical focusing exceeding specifications was demonstrated by ex-situ metrology and in-situ X-ray measurements. Representative results are presented.
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Jan 2019
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