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, pp. 192-193

Section Cells for electrochemistry

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: Cells for electrochemistry

| top | pdf |

With ever-increasing standards of living, the world is becoming more and more dependent on energy. As natural resources (coal, gas and petrol) are limited, there has been a large impetus towards developing alternative ways of producing and storing energy, while also taking into account environmental issues. Despite many decades of research and tremendous progress in this field, in situ diffraction was only adapted for electrochemical research in the 1990s. Nevertheless, this field now has the largest variety of cells. It is impossible to give a comprehensive overview of this complex subject here, and therefore the reader is referred to the articles by Brant et al. (2013[link]), De Marco & Veder (2010[link]) and Morcrette et al. (2002[link]), which describe how to design and reference most existing miniaturized in situ cells. The recent work by Johnsen & Norby (2013[link]), who have developed a capillary-based micro-battery cell, is not included in these reviews. The main advantage of this cell is that it allows diffraction data to be obtained from a single electrode. The recent work on electrochemical cells using conventional diffractometers (Shen et al., 2014[link]) and high-throughput cells for synchrotron applications (Herklotz et al., 2013[link], 2016[link]) is also relevant. When planning experiments on central facilities, not only appropriate cells but also dedicated ancillary equipment (e.g. a glove box) for cell loading owing to air sensitivity of the electrode material (e.g. lithium) are essential. In centralized facilities, this may lead to conflicts due to the incompatibility of liquid electrolytes with samples from other users, and dedicated electrochemistry glove boxes have started to appear. As an example of the use of an electrochemical cell, Morcrette et al. (2002[link]) managed to perform structural Rietveld refinement during delithiation of an LiCoO2 electrode. In order to obtain reliable intensities, five diffraction images at six different positions in the cell were averaged for each point in the charge cycle. Owing to the amount and quality of the data, six different structural phases could be determined, including lattice parameters, space group, atomic positions and R factors (see Fig. 2.9.5[link]). As the potentiostat or galvanostat is driving and measuring the performance of the battery, the structure–activity relationship is obtained automatically. This is a similar concept to the operando methodology in catalysis research that uses a mass spectrometer to measure activity.

[Figure 2.9.5]

Figure 2.9.5 | top | pdf |

(a) In situ synchrotron diffraction patterns (selected region) of an LiCoO2/Li cell collected during cell charging. Below: overview of a Bellcore flat three-electrode plastic Li-ion cell (b) with an enlargement (c) of the assembly steps during which all the separated laminates are brought together by a thermal fusion process via a laminator. The thicknesses of the plastic Li-ion cells assembled for in situ X-ray experiments were about 0.4/0.5 mm. A derived version of the Bellcore plastic Li-ion battery with a beryllium window thermally glued to the packing envelope on one side is shown in (d). Adapted from Morcrette et al. (2002[link]) with permission from Elsevier.

In analogy with microcapillary cells, miniaturized electrochemistry cells are extremely efficient for studying many aspects of an operational battery despite the fact that a fundamental understanding of electrochemical systems is inherently challenging. All the components of a cell influence each other at the interfaces during the cyclic charge-transfer process. It is also crucial to be able to establish the critical factors that determine the lifetime of the battery. To make efficient use of beamtime, it is common practice to construct many cells within one frame, all operating in parallel. The whole batch of cells is then mounted on translation stages on a diffractometer and measurements are taken periodically. However, miniature cells will never provide a complete picture, and there will always be a need to study large prototype or production cells (Rijssenbeek et al., 2011[link]) of the types discussed in Sections[link] and[link].


Brant, W. R., Schmid, S., Du, G., Gu, Q. & Sharma, N. (2013). A simple electrochemical cell for in-situ fundamental structural analysis using synchrotron X-ray powder diffraction. J. Power Sources, 244, 109–114.Google Scholar
De Marco, R. & Veder, J.-P. (2010). In situ structural characterization of electrochemical systems using synchrotron-radiation techniques. TrAC Trends Anal. Chem. 29, 528–537.Google Scholar
Herklotz, M., Scheiba, F., Hinterstein, M., Nikolowski, K., Knapp, M., Dippel, A.-C., Giebeler, L., Eckert, J. & Ehrenberg, H. (2013). Advances in in situ powder diffraction of battery materials: a case study of the new beamline P02.1 at DESY, Hamburg. J. Appl. Cryst. 46, 1117–1127.Google Scholar
Herklotz, M., Weiss, J., Ahrens, E., Yavuz, M., Mereacre, L., Kiziltas-Yavuz, N., Dräger, C., Ehrenberg, H., Eckert, J., Fauth, F., Giebeler, L. & Knapp, M. (2016). A novel high-throughput setup for in situ powder diffraction on coin cell batteries. J. Appl. Cryst. 49, 340–345.Google Scholar
Johnsen, R. E. & Norby, P. (2013). Capillary-based micro-battery cell for in situ X-ray powder diffraction studies of working batteries: a study of the initial intercalation and deintercalation of lithium into graphite. J. Appl. Cryst. 46, 1537–1543.Google Scholar
Morcrette, M., Chabre, Y., Vaughan, G., Amatucci, G., Leriche, J.-B., Patoux, S., Masquelier, C. & Tarascon, J.-M. (2002). In situ X-ray diffraction techniques as a powerful tool to study battery electrode materials. Electrochim. Acta, 47, 3137–3149.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
Shen, Y., Pedersen, E. E., Christensen, M. & Iversen, B. B. (2014). An electrochemical cell for in operando studies of lithium/sodium batteries using a conventional X-ray powder diffractometer. Rev. Sci. Instrum. 85, 084101.Google Scholar

to end of page
to top of page