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Instruments / Technical Area	Publication Details	Published
I19-Small Molecule Single Crystal Diffraction	Synthesis, structure and electrochemical properties of a new cation ordered layered Li-Ni-Mg-Mo oxide Bo Dong , Javier Castells-Gil , Pengcheng Zhu , Laura L. Driscoll , Emma Kendrick , Phoebe K. Allan , Peter R. Slater Materials Advances DOI: 10.1039/D2MA00981A Open Access Show Abstract ▼ Abstract: Lithium-rich oxides are attracting intense interest as the next generation cathode materials for lithium-ion batteries due to their high theoretical capacity. Nevertheless, these materials suffer from a number of shortcomings, such as oxygen loss at high voltage, large hysteresis and poor rate capability. In this work, we show that through a dual cation doping strategy replacing Ti with Mo and Mg, the disordered rocksalt (DRS) Li1.2Ni0.4Ti0.4O2 is transformed into a new cation ordered layered phase Li1.2Ni0.4Mo0.2Mg0.2O2, with the high valence dopant Mo6+ on the (0,0,0) site. Li1.2Ni0.4Mo0.2Mg0.2O2 showed improved performance compared to that of the similarly prepared DRS Li1.2Ni0.4Ti0.4O2 material (~190 mAhg-1 vs ~105 mAhg-1 after 10 cycles, respectively). The characteristics of the electrochemical process were studied using ex situ XRD and XAS, which indicated the involvement of both Ni and Mo redox during the cycling as well as the electrochemical instability of the layered phase which changes to a disordered rocksalt phase on cycling.	Jan 2023
I15-1-X-ray Pair Distribution Function (XPDF)	X-ray pair distribution function analysis and electrical and electrochemical properties of cerium doped Li5La3Nb2O12 garnet solid-state electrolyte Bo Dong , Mark P. Stockham , Philip A. Chater , Peter R. Slater Dalton Transactions 414 DOI: 10.1039/D0DT02112A Diamond Proposal Number(s): [20877] Open Access Show Abstract ▼ Abstract: Garnet solid state electrolytes have been considered as potential candidates to enable next generation all solid state batteries (ASSBs). To facilitate the practical application of ASSBs, a high room temperature ionic conductivity and a low interfacial resistance between solid state electrolyte and electrodes are essential. In this work, we report a study of cerium doped Li5La3Nb2O12 through X-ray pair distribution function analysis, impedance spectroscopy and electrochemical testing. The successful cerium incorporation was confirmed by both X-ray diffraction refinement and X-ray pair distribution function analysis, showing the formation of an extensive solid solution. The local bond distances for Ce and Nb on the octahedral site were determined using X-ray pair distribution function analysis, illustrating the longer bond distances around Ce. This Ce doping strategy was shown to give a significant enhancement in conductivity (1.4 × 10−4 S cm−1 for Li5.75La3Nb1.25Ce0.75O12, which represents one of the highest conductivities for a garnet with less than 6 Li) as well as a dramatically decreased interfacial resistance (488 Ω cm2 for Li5.75La3Nb1.25Ce0.75O12). In order to demonstrate the potential of this doped system for use in ASSBs, the long term cycling of a Li//garnet//Li symmetric cell over 380 h has been demonstrated.	Aug 2020
B18-Core EXAFS	Evaluation of the effect of site substitution of Pr doping in the Lithium garnet system Li5La3Nb2O12 Mark P. Stockham , Bo Dong , Yongliang Li , Yulong Ding , Peter Slater Dalton Transactions DOI: 10.1039/D0DT01497D Diamond Proposal Number(s): [14239] Open Access Show Abstract ▼ Abstract: Li ion conducting garnets have been attracting considerable interest for use as the electrolyte in all solid-state batteries, due to their high ionic conductivity and wide electrochemical stability window. Consequently, there have been a number of doping studies aimed at optimising the conductivity, focusing on both doping in Li7La3Zr2O12 and Li5La3(Nb/Ta)2O12 systems. In this paper, we report a detailed study of Pr doping in Li5La3Nb2O12, and show that this is a rare example of an ambi-site dopant, being able to be doped onto either the La or Nb site. Interestingly the resultant Pr oxidation state is determined by the site substitution, with oxidation states of 3+ for the La site, and 4+ for the Nb site. While the conductivity is essentially unchanged for the La site substitution, Pr4+ substitution on the Nb site leads to a large increase in the conductivity associated with the increase in Li content (Li5+xLa3Nb2-xPrxO12) up to 0.56 mScm-1 (at 50˚C) for x=0.8. Overall, this work highlights the flexibility of these garnet materials to doping, and suggests that further consideration of site substitution be considered for other dopants.	May 2020
B18-Core EXAFS	Synthesis and characterisation of Sr4Fe3-xCrxO10-δ: Stabilisation of n=3 Ruddlesden-Popper phases through Cr doping A. Jarvis , F. J. Berry , J. F. Marco , M. Sanchez-Arenillas , G. Cibin , O. Clemens , P. R. Slater Journal Of Solid State Chemistry DOI: 10.1016/j.jssc.2020.121372 Show Abstract ▼ Abstract: Ruddlesden-Popper type compounds have the general formula, An+1MnO3n+1±x (typically A is a rare earth, alkaline earth, M is a transition metal), and are constructed of perovskite-type layers separated by rock salt type blocks. While n = 1, 2 phases are typically straightforward to prepare, the synthesis of higher order (n > 2) systems is difficult. In this paper we show that chromate (CrO42−) doping can be exploited to stabilise new n = 3 Ruddlesden-Popper systems, Sr4Fe3-xCrxO10-δ: without chromate doping, a mixture of the n = 2 phase Sr3Fe2O7-x and perovskite-type SrFeO3-x is obtained. This can be explained by the stabilisation of the central perovskite building block by chromate incorporation, similar to prior work on sulfate and carbonate doping in this system. The structure, and Fe/Cr oxidation states were evaluated by X-ray diffraction, 57Fe Mössbauer spectroscopy and X-ray absorption spectroscopy supporting the incorporation of Cr as CrO42−. In order to examine the potential of these new systems for use as a SOFC cathode material, conductivity studies were carried out, which showed semiconducting behaviour with slightly higher conductivities than the sulfate doped counterparts.	Apr 2020

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