Browsing by Author "Cowie, BCC"
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- ItemAverage and local ordering of Yb2(Ti2-xYbx)O7-x/2 ‘stuffed’ pyrochlores: the development of a robust structural model(Elsevier, 2021-10-01) Mullens, BG; Zhang, Z; Avdeev, M; Brand, HEA; Cowie, BCC; D'Angelo, AM; Múzquiz, MS; Kennedy, BJThe long-range (average) and short-range (local) structures in the Yb2(Ti2-xYbx)O7-x/2 (x = 0.00–0.67) series were studied using a combination of diffraction and spectroscopic techniques. The average structure, established from synchrotron X-ray and neutron powder diffraction data, shows the development of multiphase regions from x = 0.134 and the formation of anti-site disorder from x = 0.335. The local structure, established from X-ray absorption near-edge structure (XANES), shows a gradual evolution of short-range disorder. The crystal field splitting energy of the Ti4+ ions decreases from 2.15 to 1.91 eV with increasing Yb3+ content, reflecting the increase in coordination number from 6 to predominantly 7. Electrochemical impedance spectroscopic studies show an increase in oxygen ionic conductivity by almost a factor of 3 upon doping with small amounts of Yb3+ (x = 0.067). These results imply that the disordering across the anion and cation sublattices are different and inducing small amounts of disorder into the pyrochlore structure may lead to applications in solid-oxide fuel cells. © 2021 Elsevier Inc.
- ItemEffect of long- and short-range disorder on the oxygen ionic conductivity of Tm2(Ti2–xTmx)O7–x/2 “stuffed” pyrochlores(American Chemical Society, 2021-03-10) Mullens, BG; Zhang, Z; Avdeev, M; Brand, HEA; Cowie, BCC; Múzquiz, MS; Kennedy, BJThe long-range average and short-range local structures in the Tm2(Ti2–xTmx)O7–x/2 (x = 0.00–0.67) series were studied using a combination of diffraction and spectroscopic techniques. The long-range average structure, established from synchrotron X-ray and neutron powder diffraction data, shows the development of multiphase regions from x = 0.134 and the formation of antisite cation disorder from x = 0.402. The crystal field splitting of the Ti4+ ions, as derived from the Ti L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, decreases gradually from 2.17 to 1.92 eV with increasing Tm3+ content (x), reflecting the increase in coordination number from 6 to predominantly 7. This is consistent with a gradual evolution of the short-range local disorder from x = 0.00 to 0.67. These results suggest that local disorder develops gradually throughout the entire composition range, whereas changes in the long-range disorder occur more suddenly. Electrochemical impedance spectroscopic results show an increase in oxygen ionic conductivity at 1000 °C, by a factor of 4 upon doping at x = 0.268. This suggests that inducing small amounts of disorder into the pyrochlore structure, by stuffing, may lead to applications of this material as a solid electrolyte in solid-oxide fuel cells. © 2021 American Chemical Society
- ItemIntroducing 4s–2p orbital hybridization to stabilize spinel oxide cathodes for lithium-ion batteries(Wiley-VCH GmbH, 2022-04-25) Liang, GM; Olsson, E; Zou, JS; Wu, ZB; Li, JX; Lu, CZ; D'Angelo, AM; Johannessen, B; Thomsen, L; Cowie, BCC; Peterson, VK; Cai, Q; Pang, WK; Guo, ZPOxides composed of an oxygen framework and interstitial cations are promising cathode materials for lithium-ion batteries. However, the instability of the oxygen framework under harsh operating conditions results in fast battery capacity decay, due to the weak orbital interactions between cations and oxygen (mainly 3d–2p interaction). Here, a robust and endurable oxygen framework is created by introducing strong 4s–2p orbital hybridization into the structure using LiNi0.5Mn1.5O4 oxide as an example. The modified oxide delivers extraordinarily stable battery performance, achieving 71.4 % capacity retention after 2000 cycles at 1 C. This work shows that an orbital-level understanding can be leveraged to engineer high structural stability of the anion oxygen framework of oxides. Moreover, the similarity of the oxygen lattice between oxide electrodes makes this approach extendable to other electrodes, with orbital-focused engineering a new avenue for the fundamental modification of battery materials. © 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH - Open access.
- ItemInvestigating the local structure of lanthanoid hafnates Ln2Hf2O7 via diffraction and spectroscopy(American Chemical Society, 2013-02-07) Blanchard, PER; Liu, S; Kennedy, BJ; Ling, CD; Avdeev, M; Aitken, JB; Cowie, BCC; Tadich, AThe lanthanoid hafnates Ln2Hf2O7 (Ln = La, Pr, Nd, Sm?Tm) were studied using a combination of synchrotron X-ray and neutron powder diffraction together with X-ray absorption and Raman spectroscopy. Spectroscopic methods revealed a gradual increase in disorder from the ideal pyrochlore structure to the defect fluorite structure as the size of the Ln cation increases. The line shape of the Hf L3-edge X-ray absorption near edge spectra which is sensitive to the local coordination environment changed with increasing disorder. The general line shape of the O K-edge XANES and Raman spectra also indicated an increase in disorder across the Ln2Hf2O7 series. Differences in the diffraction and spectroscopy analysis reflect the greater sensitivity of the spectroscopy techniques to local ordering. © 2013, American Chemical Society
- ItemInvestigating the order-disorder phase transition in Nd2-xYxZr2O7via diffraction and spectroscopy(Royal Society of Chemistry, 2013-01-01) Blanchard, PER; Liu, S; Kennedy, BJ; Ling, CD; Zhang, Z; Avdeev, M; Cowie, BCC; Thomsen, L; Jang, LYThe pyrochlore-defect fluorite phase transition in the mixed-metal zirconate Nd2-xYxZr2O7 (0 <= x <= 2) solid solution was investigated using synchrotron X-ray and neutron diffraction, as well as X-ray absorption spectroscopy. Diffraction analysis revealed a two-phase region between 1.0 <= x <= 1.2. In the pyrochlore phase, Zr L-3-edge XANES analysis demonstrated a gradual change in the local coordination environment of the B site with increasing Y content that was consistent with an increase in disorder. Although Y L-3-edge XANES analysis suggested that the Y cations remained in an ordered coordination environment in the pyrochlore phase, disorder did gradually increase once the fluorite phase formed. It was found that Y cations prefer an ordered coordination environment near the phase boundary whereas Zr cations prefer a disordered coordination environment. © 2013, Royal Society of Chemistry
- ItemInvestigation of K modified P2 Na 0.7 Mn 0.8 Mg 0.2 O 2 as a cathode material for sodium-ion batteries(Royal Society of Chemistry, 2018-11-19) Sehrawat, D; Cheong, S; Rawal, A; Glushenkov, AM; Brand, HEA; Cowie, BCC; Gonzalo, E; Rojo, T; Naeyaert, PJP; Ling, CD; Avdeev, M; Sharma, NSodium-ion batteries (NIBs) are emerging as a potentially cheaper alternative to lithium-ion batteries (LIBs) due to the larger abundance of sodium and in some cases the similar intercalation chemistry to LIBs. Here we report the solid state synthesized K-modified P2 Na0.7Mn0.8Mg0.2O2 which adopts hexagonal P63/mmc symmetry. The second charge/discharge capacity for the as-prepared material is 115/111 mA h g−1 between 1.5–4.2 V at a current density of 15 mA g−1, which reduces to 61/60 mA h g−1 after 100 cycles. Scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy (STEM-EDS) analysis shows a heterogeneous distribution of K and solid state 23Na NMR illustrates that the presence of K perturbs the local environment of Na within the P2 Na0.7Mn0.8Mg0.2O2 crystal structure. Larger scale X-ray absorption near-edge structure (XANES) data on the K L-edge also illustrate that K is present on the surface of electrodes in preference to the bulk. In situ synchrotron X-ray diffraction (XRD) data illustrates that the P2 structural motif is preserved, featuring a solid solution reaction for most of charge–discharge except at the charged and discharged states where multiple phases are present. The K-modified sample of P2 Na0.7Mn0.8Mg0.2O2 is compared with the K-free samples in terms of both structural evolution and electrochemical performance. © The Royal Society of Chemistry 2019
- ItemKey role of Bismuth in the magnetoelastic transitions of Ba3BiIr2O9 and Ba3BiRu2O9 as revealed by chemical doping(America Chemical Society, 2013-12-24) Blanchard, PER; Huang, ZX; Kennedy, BJ; Liu, S; Miiller, W; Reynolds, EM; Zhou, QD; Avdeev, M; Zhang, ZM; Aitken, JB; Cowie, BCC; Jang, LY; Tan, TT; Li, S; Ling, CDThe key role played by bismuth in an average intermediate oxidation state in the magnetoelastic spin-gap compounds Ba3BiRu2O9 and Ba3BiIr2O9 has been confirmed by systematically replacing bismuth with La3+ and Ce4+. Through a combination of powder diffraction (neutron and synchrotron), X-ray absorption spectroscopy, and magnetic properties measurements, we show that Ru/Ir cations in Ba3BiRu2O9 and Ba3BiIr2O9 have oxidation states between +4 and +4.5, suggesting that Bi cations exist in an unusual average oxidation state intermediate between the conventional +3 and +5 states (which is confirmed by the Bi L3-edge spectrum of Ba3BiRu2O9). Precise measurements of lattice parameters from synchrotron diffraction are consistent with the presence of intermediate oxidation state bismuth cations throughout the doping ranges. We find that relatively small amounts of doping (∼10 at%) on the bismuth site suppress and then completely eliminate the sharp structural and magnetic transitions observed in pure Ba3BiRu2O9 and Ba3BiIr2O9, strongly suggesting that the unstable electronic state of bismuth plays a critical role in the behavior of these materials. © 2013 American Chemical Society.
- ItemNEXAFS spectroscopy of CVD diamond films exposed to fusion, relevant hydrogen plasma(Elsevier, 2013-04-01) Guenette, MC; Deslandes, A; Samuell, CM; Tadich, A; Thomsen, L; Cowie, BCC; Corr, CS; Riley, DPA series of CVD diamond films have been exposed to hydrogen plasma in the linear magnetized plasma device, MAGPIE, with various applied sample stage biases between 0 V (no applied bias) to − 500 V. The plasma-induced damage to the surface structure of the diamond films has been investigated by Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy in both the Auger electron yield (AEY) and total fluorescence yield (TFY) modes. The key diamond NEXAFS spectral features (diamond core exciton and second absolute band gap) are found to be diminished following plasma exposure as measured in the surface sensitive, AEY spectra, whilst these features remain unchanged relative to an unexposed diamond reference film as measured using the bulk sensitive, TFY spectra. These results, in conjunction with SRIM simulations, show definitively that the damage to the surface of the diamond films is restricted to the scale of the penetration depth of the H ions and no damage is induced at greater depths. The power and sensitivity of NEXAFS spectroscopy in assessing damage to the surface of diamond from fusion-relevant plasma-surface interactions are demonstrated. © 2013, Elsevier B.V.
- ItemProbing long- and short-range disorder in Y2Ti2–xHfxO7 by diffraction and spectroscopy techniques(American Chemical Society, 2016-11-01) Zhang, ZM; Avdeev, M; de los Reyes, M; Lumpkin, GR; Kennedy, BJ; Blanchard, PER; Liu, S; Tadich, A; Cowie, BCCWe studied the long-range average and short-range local structures in Y2Ti2–xHfxO7 (x = 0–2.0) using diffraction and spectroscopy techniques, respectively. Both neutron and synchrotron X-ray powder diffraction data show a clear phase transition of the average structure from ordered pyrochlore to disordered defect-fluorite at x ≈ 1.6; the long-range anion disorder appears to develop gradually throughout the entire pyrochlore region in contrast to the rapid loss of cation ordering from x = 1.4 to 1.6. The commonly observed two-phase region around the pyrochlore/defect-fluorite phase boundary is absent in this system, demonstrating high sample quality. X-ray absorption near-edge structure (XANES) results at the Y L2-, Ti K- and L3,2-, Hf L3-, and O K-edges indicate a gradual local structural evolution across the whole compositional range; the Y coordination number (CN) decreases and the CN around Ti and Hf increases with increasing Hf content (x). The spectroscopic results suggest that the local disorder occurs long before the pyrochlore to defect-fluorite phase boundary as determined by diffraction, and this disorder evolves continuously from short- to medium- and eventually to long-range detectable by diffraction. This study highlights the complex disordering process in pyrochlore oxides and the importance of a multitechnique approach to tackle disorder over different length scales and in the anion and cation sublattices, respectively. The results are important in the context of potential applications of these oxides such as ionic conductors and radiation-resistant nuclear waste forms. © 2016 American Chemical Society
- ItemAn unconventional method for measuring the Tc L3-edge of technetium compounds(Journal of Synchrotron Radiation, 2014-01-01) Blanchard, PER; Reynolds, EM; Kennedy, BJ; Ling, CD; Zhang, Z; Thorogood, GJ; Cowie, BCC; Thomsen, LTc L3-edge XANES spectra have been collected on powder samples of SrTcO3 (octahedral Tc4+) and NH4TcO4 (tetrahedral Tc7+) immobilized in an epoxy resin. Features in the Tc L3-edge XANES spectra are compared with the pre-edge feature of the Tc K-edge as well as other 4d transition metal L3-edges. Evidence of crystal field splitting is obvious in the Tc L3-edge, which is sensitive to the coordination number and oxidation state of the Tc cation. The Tc L3 absorption edge energy difference between SrTcO3 (Tc4+) and NH4TcO4 (Tc7+) shows that the energy shift at the Tc L3-edge is an effective tool for studying changes in the oxidation states of technetium compounds. The Tc L3-edge spectra are compared with those obtained from Mo and Ru oxide standards with various oxidation states and coordination environments. Most importantly, fitting the Tc L3-edge to component peaks can provide direct evidence of crystal field splitting that cannot be obtained from the Tc K-edge. © International Union of Crystallography.
- ItemXPS and NEXAFS study of fluorine modified TiO2 nano-ovoids reveals dependence of Ti3+ surface population on the modifying agent(Royal Society of Chemistry, 2014-04-04) Ruzicka, JY; Bakar, FA; Thomsen, L; Cowie, BCC; McNicoll, C; Kemmitt, T; Brand, HEA; Ingham, B; Andersson, GG; Golovko, VBCrystalline titanium dioxide was synthesised under mild conditions by the thermal degradation of peroxotitanic acid in the presence of a number of fluoride-containing surface modifying agents (NH4F, NH4BF4, NH4PF6, NBu4F, NBu4BF4, NBu4PF6). The resulting materials were characterised by PXRD, SEM, HRTEM, XPS and NEXAFS. Particle phase, size, and surface area were noticeably affected by the choice of surface modifying agent. Both the cation and anion comprising the modifying agent affect the surface Ti3+ population of the materials, with two apparent trends observed: F− > BF4− > PF6− and NBu4+ > NH4+. All materials displayed evidence of fluorine doping on their surfaces, although no evidence of bulk doping was observed. © 2014 The Royal Society of Chemistry (Open Access)