Dynamic in Situ Electrochemical Neutron Reflectivity Measurements

Abstract

We report the first dynamic in situ electrochemical neutron reflectivity (NR) measurements on electroactive films. By using a boxcar integration strategy within a cyclic voltammetric experiment, it is possible to acquire neutron reflectivity data associated with narrow, defined windows of potential. Accumulation of data from repetitive cycles allows one to build up potential- (time-) resolved profiles. The effective time resolution is now on the order of seconds, as compared to ca. 1 h using conventional methodology, making in situ NR a practical technique for dynamic electrochemical studies. Illustrative data for polyvinylferrocene films reveal hysteresis in (de)swelling, incomplete desolvation upon reduction, and transient salt retention, all of which respond to time-scale variations.

Neutron Reflectometry for Studying Corrosion and Corrosion Inhibition

“…There have been a number of related NR studies with in situ electrochemistry addressing an interesting range of challenges such as battery electrodes [107][108][109][110][111], solid electrolyte interface SEI formation [84], electroactive polymer films [112][113][114] and other double layer capacitance systems, such as ionic liquids at surfaces [56,115,116], as well as the formation and properties of passivating oxide layers [68,91,100].…”

“…These include measuring over a limited Q-range that can be collected quickly (a range with the greatest expected change is chosen) [101] or, perhaps more elegantly, by taking stroboscopic measurements [112,114], in which the potential is cycled and the reflected counts are binned into small time slices. Only a few counts are collected per cycle, but by repeating the process many times, the narrow time slices can yield good statistical data.…”

Introduction à la réflectivité de neutrons : potentialités pour les études de surfaces de systèmes magnétiques et en matière molle

“…Enfin, des mesures d'électrochimie « in situ » sont décrites par exemple dans la référence [20] ou la mesure de la pénétration de solvants dans des films électro-polymérisés a été possible. Quelques mesures de fluides complexes confinés entre des surfaces de quartz et de saphir séparées par ∼100 nm sont décrites dans la référence [21].…”

Effect of Annealing Treatment on the Electrochemical Properties of Polyoxomolybdate K₄[SiMo₁₂O₄₀] as Cathode Material of Lithium Battery

“…[3][4][5][6][7][8][9] The charge-discharge mechanism of these organic radical cathodes is nevertheless quite different from that of the lithium (de-)insertion electrodes widely used in lithium battery. The redox active part included in organic materials, which is independent from the crystal structure, is oxidized or reduced during the charging and discharging process, accompanied with the lithium desorption or adsorption to the cathode surface, respectively.…”