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Metal oxide pseudocapacitors are limited by low electrical and ionic conductivities. The present work integrates defect engineering and architectural design to exhibit, for the first time, intercalation pseudocapacitance in CeO

Metal oxide pseudocapacitors are limited by low electrical and ionic conductivities. The present work integrates defect engineering and architectural design to exhibit, for the first time, intercalation pseudocapacitance in CeO2–x. An engineered chronoamperometric electrochemical deposition is used to synthesize 2D CeO2–x nanoflakes as thin as ~12 nm. Through simultaneous regulation of intrinsic and extrinsic defect concentrations, charge transfer and charge–discharge kinetics with redox and intercalation capacitances together are optimized, where reduction increases the gravimetric capacitance by 77% to 583 F g–1, exceeding the theoretical capacitance (562 F g–1). Mo ion implantation and reduction processes increase the specific capacitance by 133%, while the capacitance retention increases from 89 to 95%. The role of ion-implanted Mo6+ is critical through its interstitial solid solubility, which is not to alter the energy band diagram but to facilitate the generation of electrons and to establish the midgap states for color centers, which facilitate electron transfer across the band gap, thus enhancing n-type semiconductivity. Critically, density functional theory simulations reveal, for the first time, that the reduction causes the formation of ordered oxygen vacancies that provide an atomic channel for ion intercalation. These channels enable intercalation pseudocapacitance but also increase electrical and ionic conductivities. In addition, the associated increased active site density enhances the redox such that the 10% of the Ce3+ available for redox (surface only) increases to 35% by oxygen vacancy channels. These findings are critical for any oxide system used for energy storage systems, as they offer both architectural design and structural engineering of materials to maximize the capacitance performance by achieving accumulative surface redox and intercalation-based redox reactions during the charge/discharge process.

Glass-ceramics (GCs) based on titanate pyrochlores have attracted recent attention as candidate waste forms for actinide immobilization. As zirconate pyrochlore has a superior radiation resistance, it is anticipated that Zr substitution of Ti in titanate pyrochlore GCs would increase their potential for waste form applications. The concept was primarily addressed via the preparation of Gd2Ti2-xZrxO7 (x = 0.1–0.3) GCs to determine the effects of sintering temperature, Zr substitution, and pyrochlore content (50–70 wt%) on the properties of the resultant GCs. XRD and SEM analyses were used to reveal the phase assemblages and microstructures while TEM and Raman spectroscopy were used to analyze the local structures. XRD results confirmed the formation of the targeted pyrochlore as the major phase, with Gd9.33(SiO4)6O2 oxyapatite present as a minor phase. SEM analyses revealed that up to 0.2 formula units of Ti could be substituted by Zr under the processing conditions. The pyrochlore crystallite sizes were largely controlled by the sintering temperature and cooling rate and showed little sensitivity to the glass contents. This work has demonstrated successful substitutions of Ti with Zr in Gd2Ti2O7 GCs as potential waste forms for actinide wastes owing to their superior radiation resistance.