Tables for
Volume H
Powder diffraction
Edited by C. J. Gilmore, J. A. Kaduk and H. Schenk

International Tables for Crystallography (2018). Vol. H, ch. 2.9, p. 194

Section Large-volume cells for energy-dispersive diffraction

W. van Beeka* and P. Pattisona,b

aSwiss–Norwegian Beamlines at ESRF, CS 40220, 38043 Grenoble CEDEX 9, France, and bLaboratory for Quantum Magnetism, Institute of Physics, Ecole Polytechnique Federale de Lausanne, CH-1015 Lausanne, Switzerland
Correspondence e-mail: Large-volume cells for energy-dispersive diffraction

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Large-volume cells have been used to date with great success almost exclusively with energy-dispersive diffraction (EDXRD). Early work on this was carried out by Munn et al. (1992[link]) and He et al. (1992[link]) using the synchrotron source at Daresbury Laboratory. Walton & O'Hare (2000[link]), who continued the pioneering work, provide a good historical overview of the kinds of studies that can be performed. Norby (2006[link]) also provides excellent references to and explanations of work in this field. In brief, the main advantages of EDXRD are that the X-ray high energies (i.e. 50–120 keV) present in the beam can penetrate and probe into large vessels. Furthermore, only minor modifications to create small entrance and exit windows on commercial autoclaves, which are standard equipment in many laboratories, are necessary in order to turn them into extreme-condition in situ reaction vessels. An additional advantage arises from the fact that there is no bias due to volume differences between the laboratory experiments and in situ reactions studied at the synchrotron (see Fig. 2.9.8[link]).

[Figure 2.9.8]

Figure 2.9.8 | top | pdf |

A schematic of the Oxford/Daresbury hydrothermal autoclave used for energy-dispersive X-ray diffraction studies. Adapted from Walton & O'Hare (2000[link]) with permission of The Royal Society of Chemistry.

The variety of scientific applications is huge: pressure-induced phase transitions of inorganic solids, hydrothermal synthesis of microporous solids, intercalation, growth of layered perovskites and breathing in metal-organic frameworks, to name a few examples (see Walton & O'Hare, 2000[link]). Extreme conditions can be reached in terms of temperature (∼1273 K) in an autoclave with subsecond XRD time resolution. EDXRD in combi­nation with large-volume autoclaves has provided otherwise-inaccessible information on many processes: intermediates in crystallization routes, activation energies for reactions, and kinetic parameters crucial for their understanding and optimization. The major disadvantage of EDXRD is that the resolution in the diffraction pattern is limited, since it is defined by the energy resolution of the solid-state detector. This effectively excludes all access to precise structural information. However, recent efforts have allowed quantitative phase analysis (Rowles, 2011[link]; Rowles et al., 2012[link]). With the advent of third-generation synchrotrons, which provide orders of magnitude more flux at high energies, and the availability of high-energy flat-panel detectors, angular-dispersive diffraction data can successfully be collected from samples in large-volume cells. Their use expands the available information dramatically. To date, however, there are very few high-energy angular-dispersive beamlines, and the use of the large-volume cells in combination with EDXRD remains an active field and has recently been developed further by, for example, Moorhouse et al. (2012[link]) at the Diamond Light Source. The cell there can be equipped with various reaction vessels made of alumina, steel, PTFE-lined steel or glassy carbon tubes depending on the chemical reaction to be studied. It can achieve temperatures as high as 1473 K with infrared lamps and has a magnetic stirrer to avoid sedimentation of the reaction products. In addition, Styles et al. (2012[link]) have developed a large furnace and in situ cell for salt electrolysis.

Rijssenbeek et al. (2011[link]) have studied a full-size battery cell with EDXRD (see Fig. 2.9.9[link]). Diffraction data were collected during charge/discharge at high temperature of the sodium metal halide (Na/MCl2, M = Ni and/or Fe) cells. They were able to assess the charge-state variations as a function of space and time in the cell during many charge/discharge cycles, and identify local crystal structures and phase distributions. The data confirm the propagation of a known well-defined chemical reaction front beginning at the ceramic separator and proceeding inward.

[Figure 2.9.9]

Figure 2.9.9 | top | pdf |

(a) Schematic of a sodium-halide cell in an in situ synchrotron EDXRD experimental setup. (b) Cross-sectional computed tomography image of a cell. The arrow along the cell diagonal denotes the path of the X-ray line scans used in this work. This corresponds to an X-ray penetration depth of up to 50 mm. Adapted from Rijssenbeek et al. (2011[link]) with permission from Elsevier.


He, H., Barnes, P., Munn, J., Turrillas, X. & Klinowski, J. (1992). Autoclave synthesis and thermal transformations of the alumino­phosphate molecular sieve VPI-5: an in situ X-ray diffraction study. Chem. Phys. Lett. 196, 267–273.Google Scholar
Moorhouse, S. J., Vranješ, N., Jupe, A., Drakopoulos, M. & O'Hare, D. (2012). The Oxford–Diamond in situ cell for studying chemical reactions using time-resolved X-ray diffraction. Rev. Sci. Instrum. 83, 084101.Google Scholar
Munn, J., Barnes, P., Haüsermann, D., Axon, S. A. & Klinowski, J. (1992). In-situ studies of the hydrothermal synthesis of zeolites using synchrotron energy-dispersive X-ray diffraction. J. Phase Transit. 39, 129–134.Google Scholar
Norby, P. (2006). In-situ XRD as a tool to understanding zeolite crystallization. Curr. Opin. Colloid Interf. Sci. 11, 118–125.Google Scholar
Rijssenbeek, J., Gao, Y., Zhong, Z., Croft, M., Jisrawi, N., Ignatov, A. & Tsakalakos, T. (2011). In situ X-ray diffraction of prototype sodium metal halide cells: time and space electrochemical profiling. J. Power Sources, 196, 2332–2339.Google Scholar
Rowles, M. R. (2011). On the calculation of the gauge volume size for energy-dispersive X-ray diffraction. J. Synchrotron Rad. 18, 938–941.Google Scholar
Rowles, M. R., Styles, M. J., Madsen, I. C., Scarlett, N. V. Y., McGregor, K., Riley, D. P., Snook, G. A., Urban, A. J., Connolley, T. & Reinhard, C. (2012). Quantification of passivation layer growth in inert anodes for molten salt electrochemistry by in situ energy-dispersive diffraction. J. Appl. Cryst. 45, 28–37.Google Scholar
Styles, M. J., Rowles, M. R., Madsen, I. C., McGregor, K., Urban, A. J., Snook, G. A., Scarlett, N. V. Y. & Riley, D. P. (2012). A furnace and environmental cell for the in situ investigation of molten salt electrolysis using high-energy X-ray diffraction. J. Synchrotron Rad. 19, 39–47.Google Scholar
Walton, R. I. & O'Hare, D. (2000). Watching solids crystallise using in situ powder diffraction. Chem. Commun. pp. 2283–2291.Google Scholar

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