Exploring the Role of an Electrolyte Additive in Suppressing Surface Reconstruction of a Ni-Rich NMC Cathode at Ultrahigh Voltage via Enhanced In Situ and Operando Characterization Methods.

Vinylene carbonate (VC) is a widely used electrolyte additive in lithium-ion batteries for enhanced solid electrolyte interphase formation on the anode side. However, the cathode electrolyte interphase (CEI) formation with VC has received a lot less attention. This study presents a comprehensive investigation employing advanced in situ/operando-based Raman and X-ray absorption spectroscopy (XAS) to explore the effect of electrolyte composition on the CEI formation and suppression of surface reconstruction of LixNiyMnzCo1-y-zO2 (NMC) cathodes. A novel chemical pathway via VC polymerization is proposed based on experimental results. In situ Raman spectra revealed a new peak at 995 cm-1, indicating the presence of C-O semi-carbonates resulting from the radical polymerization of VC. Operando Raman analysis unveiled the formation of NiO at 490 cm-1 in the baseline system under ultrahigh voltage (up to 5.2 V). However, this peak was conspicuously absent in the VC electrolyte, signifying the effectiveness of VC in suppressing surface reconstruction. Further investigation was carried out utilizing in situ XAS compared X-ray absorption near edge structure spectra from cells of 3 and 20 cycles in both electrolytes at different operating voltages. The observed shift at the Ni K-edge confirmed a more substantial reduction of Ni in the baseline electrolyte compared to that in the VC electrolyte, thus indicating less CEI protection in the former. A sophisticated extended X-ray absorption fine structure analysis quantitatively confirmed the effective suppression of rock-salt formation with the VC electrolyte during the charging process, consistent with the operando Raman results. The in situ XAS results thus provided additional support for the key findings of this study, establishing the crucial role of VC polymerization in enhancing CEI stability and mitigating surface reconstruction on NMC cathodes. This work clarifies the relationship between the enhanced CEI layer and NMC degradation and inspires rational electrolyte design for long-cycling NMC cathodes.

Synergistic Effects of In-Situ Exsolved Ni-Ru Bimetallic Catalyst on High-Performance and Durable Direct-Methane Solid Oxide Fuel Cells.

Direct-methane solid oxide fuel cells (CH4-SOFCs) have gained significant attention as methane, the primary component of natural gas (NG), is cheap and widely available and the natural gas infrastructures are relatively mature. However, at intermediate temperatures (e.g., 600-650 °C), current CH4-SOFCs suffer from low performance and poor durability under a low steam-to-carbon ratio (S/C ratio), which is ascribed to the Ni-based anode that is of low catalytic activity and prone to coking. Herein, with the guidance of density functional theory (DFT) studies, a highly active and coking tolerant steam methane reforming (SMR) catalyst, Sm-doped CeO2-supported Ni-Ru (SCNR), was developed. The synergy between Ni and Ru lowers the activation energy of the first C-H bond activation and promotes CHx decomposition. Additionally, Sm doping increases the oxygen vacancy concentration in CeO2, facilitating H2O adsorption and dissociation. The SCNR can therefore simultaneously activate both CH4 and H2O molecules while oxidizing the CH* and improving coking tolerance. We then applied SCNR as the CH4-SOFC anode catalytic reforming layer. A peak power density of 733 mW cm-2 was achieved at 650 °C, representing a 55% improvement compared to that of pristine CH4-SOFCs (473 mW cm-2). Moreover, long-term durability testing, with >2000 h continuous operation, was performed under almost dry methane (5% H2O). These results highlight that CH4-SOFCs with a SCNR catalytic layer can convert NG to electricity with high efficiency and resilience.

Nanocomposite Catalyst for High-Performance and Durable Intermediate-Temperature Methane-Fueled Metal-Supported Solid Oxide Fuel Cells.

CH4-fueled metal-supported solid oxide fuel cells (CH4-MS-SOFCs) are propitious as CH4 is low-priced and readily available, and its renewable production is possible, such as biomethane. However, the current CH4-MS-SOFCs suffer from either poor power density or short durable operation, which is ascribed to the low catalytic activity and poor coking tolerance of the metallic anode support. Herein, we have deliberately designed and synthesized a highly active nanocomposite catalyst, Sm-doped CeO2-supported Ni, as the internal steam methane reforming catalyst, to optimize CH4-MS-SOFCs. Both power densities and durability of optimized CH4-MS-SOFCs have been dramatically enhanced compared to the pristine CH4-MS-SOFCs. The optimized CH4-MS-SOFCs deliver the highest performances among all zirconia-based CH4-MS-SOFCs. Furthermore, the operating temperature has been reduced to 600 °C. At 600 °C, a viable peak power density of >350 mW/cm2 is achieved, which is more than three times as high as the pristine CH4-MS-SOFCs. Furthermore, the optimized CH4-MS-SOFC achieves >1000 h of stable operation.

High-Performance, Thermal Cycling Stable, Coking-Tolerant Solid Oxide Fuel Cells with Nanostructured Electrodes.

Solid oxide fuel cells (SOFCs) are a promising solution to a sustainable energy future. However, cell performance and stability remain a challenge. Durable, nanostructured electrodes fabricated via a simple, cost-effective method are an effective way to address these problems. In this work, both the nanostructured PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF) cathode and Ni-Ce0.8Sm0.2O1.9 (SDC) anode are fabricated on a porous yttria-stabilized zirconia (YSZ) backbone via solution infiltration. Symmetrical cells with a configuration of PBSCF|YSZ|PBSCF show a low interfacial polarization resistance of 0.03 Ω cm2 with minimal degradation at 700 °C for 600 h. Ni-SDC|YSZ|PBSCF single cells exhibit a peak power density of 0.62 W cm-2 at 650 °C operated on H2 with good thermal cycling stability for 110 h. Single cells also show excellent coking tolerance with stable operation on CH4 for over 120 h. This work offers a promising pathway toward the development of high-performance and durable SOFCs to be powered by natural gas.

Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid.

Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (E(p), 1.10 ≤ E(p) ≤ 1.50 V), polarization time (t(p), 10(0) ≤ t(p) ≤ 10(4) s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (d(ox)). Because X1 > d(ox) for the entire range of E(p), t(p), and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Pt(δ+)-O(δ-) surface dipole (µ(PtO)), and the potential drop (V(ox)) and electric field (E(ox)) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide.

Platinum supported on titanium-ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles.

We report a unique and highly stable electrocatalyst-platinum (Pt) supported on titanium-ruthenium oxide (TRO)-for hydrogen fuel cell vehicles. The Pt/TRO electrocatalyst was exposed to stringent accelerated test protocols designed to induce degradation and failure mechanisms identical to those seen during extended normal operation of a fuel cell automobile-namely, support corrosion during vehicle startup and shutdown, and platinum dissolution during vehicle acceleration and deceleration. These experiments were performed both ex situ (on supports and catalysts deposited onto a glassy carbon rotating disk electrode) and in situ (in a membrane electrode assembly). The Pt/TRO was compared against a state-of-the-art benchmark catalyst-Pt supported on high surface-area carbon (Pt/HSAC). In ex situ tests, Pt/TRO lost only 18% of its initial oxygen reduction reaction mass activity and 3% of its oxygen reduction reaction-specific activity, whereas the corresponding losses for Pt/HSAC were 52% and 22%. In in situ-accelerated degradation tests performed on membrane electrode assemblies, the loss in cell voltage at 1 A · cm(-2) at 100% RH was a negligible 15 mV for Pt/TRO, whereas the loss was too high to permit operation at 1 A · cm(-2) for Pt/HSAC. We clearly show that electrocatalyst support corrosion induced during fuel cell startup and shutdown is a far more potent failure mode than platinum dissolution during fuel cell operation. Hence, we posit that the need for a highly stable support (such as TRO) is paramount. Finally, we demonstrate that the corrosion of carbon present in the gas diffusion layer of the fuel cell is only of minor concern.