  Metal hydrides are critical materials in numerous technologies including
hydrogen storage, gas separation, and electrocatalysis. Here, using Pd-H as a
model metal hydride, we perform electrochemical insertion studies of hydrogen
via liquid and solid state electrolytes at 1 atm ambient pressure, and achieve
H:Pd ratios near unity, the theoretical solubility limit. We show that the
compositions achieved result from a dynamic balance between the rate of
hydrogen insertion and evolution from the Pd lattice, the combined kinetics of
which are sufficiently rapid that operando experiments are necessary to
characterize instantaneous PdHx composition. We use simultaneous
electrochemical insertion and X-ray diffraction measurements, combined with a
new calibration of lattice parameter versus hydrogen concentration, to enable
accurate quantification of the composition of electrochemically synthesized
PdHx. Furthermore, we show that the achievable hydrogen concentration is
severely limited by electrochemomechanical damage to the palladium and/or
substrate. The understanding embodied in these results helps to establish new
design rules for achieving high hydrogen concentrations in metal hydrides.
