Design and Performance of a Full Functional Electrochemical Cell for Lab Scale in-Situ GI-XRD Instruments
Authors: Kubicek Sabine , Artner Werner , Eder Andreas , Eisenmenger-Sittner Christoph , Larisegger Silvia , Nelhiebel Michael , Fafilek Guenter 
Published: December 2020

In-situ XRD may support electrochemical measurements by delivering analytical information about electrochemical processes. Since structural changes at the electrode/electrolyte interface are of specific interest, measurements are done usually in small angle reflection mode geometry. The surface sensitive grazing incidence – XRD (GI-XRD) in-situ technique allows the detection of short-lived electrode reaction products or products sensitive to ambient atmosphere exposure. This method finds applications for quite a number of investigations of electrochemical processes including corrosion, film growth and deposition, reconstruction of superficial regions, ion insertion battery materials, etc. The common cell designs for lab scale XRD equipment use thin electrolyte layers to avoid unacceptable beam intensity loss through water. The use of synchrotron radiation would reduce this shortcoming to some extent but is much less accessible.
In 1986, Fleischmann et al. presented an in-situ XRD thin layer cell in reflection as well as in transmission mode, where a X-ray transparent Mylar foil was used as window material [1]. However, this geometry restricts the positioning of counter and reference electrodes and therefore has unfavorable current density distribution, has very small electrolyte volume, is vulnerable to side reactions with gas evolution and does not allow high flow rates for the solution. Thus, the general applicability is limited.
In our proposed in-situ cell design for GI-XRD, the electrochemical cell is fully functional, avoiding all of the above mentioned drawbacks [2]. The solution of this issue is the "backside-illumination" (or "inverse" illumination) of a thin film working electrode applied on a thin polymer foil as a support by the X-ray beam at a small incident angle. On the opposite side a conventional electrochemical cell with reference electrode and counter electrode and sufficient solution volume can be used. The big advantage of this design is that the X-ray only has to penetrate the foil and the thin layer of electrode material resulting in high signals from the region of interest. It is used with a conventional laboratory X-ray source and does not need high intensity synchrotron radiation. With this cell design, problems with bulk solution resistance, inhomogeneous current-density distribution, insufficient bath agitation or gas evolution as side reaction are eliminated.
In this contribution, details of the cell design, analysis of current density distribution within the thin current collector and the electrochemical cell, results of calibration measurements and measurements on copper as an example for a galvanic deposition/dissolution process are presented.
[1] M. Fleischmann, A. Oliver, and J. Robinson, ‘In Situ X-ray diffraction studies of electrode solution interfaces’, Electrochimica Acta, vol. 31, no. 8, pp. 899–906, (1986)
[2] S. Reither, W. Artner, A. Eder, S. Larisegger, M. Nelhiebel, C. Eisenmenger-Sittner, G. Fafilek, ‘On the In-Situ Grazing Incidence X-Ray Diffraction of Electrochemically Formed Thin Films’, ECS Transactions, 80 (10) 1231-1238, (2017) 10.1149/08010.1231ecst

Figure 1