Quasi-binary thiophosphate-based solid electrolytes (SEs) are attracting substantial interest for lithium batteries due to their outstanding room temperature ionic conductivities. This work describes ...reactions occurring at the solid electrolyte (SE)/Au interface during Li deposition and stripping for two exemplary SE materials: β-Li3PS4 (β-LPS) and Li10GeP2S12 (LGPS). We used in situ Raman spectroscopy, along with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) to evaluate potential-dependent changes in the chemistry of these materials at active electrode interfaces. For β-LPS, a partially reversible conversion of PS4 3– to P2S6 4– was found along with the formation of Li2S during Li deposition and stripping. In contrast, LGPS exhibited only irreversible changes at potentials below 0.7 V vs Li+/Li. The different behaviors likely relate to differences in the structures of the two SE materials and the availability of easily bridged anion components in close proximity. The work shows that SE integrity at interfaces can be altered by applied potential and illustrates important speciations for the interfacial structures that mediate their electrochemical activities.
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IJS, KILJ, NUK, PNG, UL, UM
The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit ...promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites.
We report that substrate doping-induced charge carrier density modulation leads to the tunable wettability and adhesion of graphene. Graphene’s water contact angle changes by as much as 13° as a ...result of a 300 meV change in doping level. Upon either n- or p-type doping with subsurface polyelectrolytes, graphene exhibits increased hydrophilicity. Adhesion force measurements using a hydrophobic self-assembled monolayer-coated atomic force microscopy probe reveal enhanced attraction toward undoped graphene, consistent with wettability modulation. This doping-induced wettability modulation is also achieved via a lateral metal–graphene heterojunction or subsurface metal doping. Combined first-principles and atomistic calculations show that doping modulates the binding energy between water and graphene and thus increases its hydrophilicity. Our study suggests for the first time that the doping-induced modulation of the charge carrier density in graphene influences its wettability and adhesion. This opens up unique and new opportunities for the tunable wettability and adhesion of graphene for advanced coating materials and transducers.
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We report on angular-resolved x-ray photoelectron spectroscopy (XPS) studies of magnetron sputtered CNx thin films, first in situ (without air exposure), then after air exposure (for time periods ...ranging from minutes to several years), and finally after Ar ion etching using ion energies ranging from 500 eV to 4 keV. The as-deposited films typically exhibit two strong N1s peaks corresponding to pyridine-like, and graphite-like, at ∼398.2 eV and ∼400.7 eV, respectively. Comparison between in situ and air-exposed samples suggests that the peak component at ∼402–403 eV is due only to quaternary nitrogen and not oxidized nitrogen. Furthermore, peak components in the ∼399–400 eV range cannot only be ascribed to nitriles or pyrrolic nitrogen as is commonly done. We propose that it can also be due to a polarization shift in pyridinic N, induced by surface water or hydroxides. Argon ion etching readily removes surface oxygen, but results also in a strong preferential sputtering of nitrogen and can cause amorphization of the film surface. The best methods for evaluating and interpreting the CNx film structure and composition with ex-situ XPS are discussed.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
Electrochemical conversion of CO2 holds promise for utilization of CO2 as a carbon feedstock and for storage of intermittent renewable energy. Presently Cu is the only metallic electrocatalyst known ...to reduce CO2 to appreciable amounts of hydrocarbons, but often a wide range of products such as CO, HCOO–, and H2 are formed as well. Better catalysts that exhibit high activity and especially high selectivity for specific products are needed. Here a range of bimetallic Cu–Pd catalysts with ordered, disordered, and phase-separated atomic arrangements (Cuat:Pdat = 1:1), as well as two additional disordered arrangements (Cu3Pd and CuPd3 with Cuat:Pdat = 3:1 and 1:3), are studied to determine key factors needed to achieve high selectivity for C1 or C2 chemicals in CO2 reduction. When compared with the disordered and phase-separated CuPd catalysts, the ordered CuPd catalyst exhibits the highest selectivity for C1 products (>80%). The phase-separated CuPd and Cu3Pd achieve higher selectivity (>60%) for C2 chemicals than CuPd3 and ordered CuPd, which suggests that the probability of dimerization of C1 intermediates is higher on surfaces with neighboring Cu atoms. Based on surface valence band spectra, geometric effects rather than electronic effects seem to be key in determining the selectivity of bimetallic Cu–Pd catalysts. These results imply that selectivities to different products can be tuned by geometric arrangements. This insight may benefit the design of catalytic surfaces that further improve activity and selectivity for CO2 reduction.
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All-solid-state Li-ion batteries afford possibilities to enhance battery safety while improving their energy and power densities. Current challenges for achieving high-performance all-solid-state ...batteries with long cycle life include shorting resulting predominantly from Li dendrite formation and infiltration through the solid electrolyte (SE) and increases in cell impedance induced by SE decomposition at the SE/electrode interface. In this work, we evaluate the electrochemical properties of two interlayer materials, Si and Li x Al(2–x/3)O3 (LiAlO), at the Li7P3S11 (LPS)/Li interface. Compared to the Li/LPS/Li symmetric cells in absence of interlayers, the presence of Si and LiAlO both significantly enhance the cycle number and total charge passing through the interface before failures resulting from cell shorting. In both cases, the noted improvements were accompanied by cell impedances that had increased substantially. The data reveal that both interlayers prevent the direct exposure of LPS to the metallic Li and therefore eliminate the intrinsic LPS decomposition that occurs at Li surfaces before electrochemical cycling. After cycling, a reduction of LPS to Li2S occurs at the interface when a Si interlayer is present; LiAlO, which functions to drop the potential between Li and LPS, suppresses LPS decomposition processes. The relative propensities toward SE decomposition follows from the electrochemical potentials at the interface, which are dictated by the identities of the interlayer materials. This work provides new insights into the phase dynamics associated with specific choices for SE/electrode interlayer materials and the requirements they impose for realizing high efficiency, long lasting all-solid-state batteries.
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IJS, KILJ, NUK, PNG, UL, UM
The electrochemical nitrate reduction reaction (NO3 –RR) offers two-fold advantagesrestoring balance to the global nitrogen cycle and a less energy intensive pathway to the production of ammonia. We ...report the results of voltammetric and spectroscopic measurements examining NO3 –RR on Cu and Cu-alloyed electrodes (CuAg, CuSn, and CuPt) in an alkaline medium. Electrochemical results demonstrate that the overpotential for the NO3 –RR is ∼120 mV less on the CuAg catalyst as compared to the Cu-only catalyst. In situ surface enhanced Raman spectroscopy (SERS) obtained from these two Cu samples shows that the presence of dilute Ag maintains the Cu surface in a more reduced state (Cu(I)) during the course of NO3 –RR, while the neat Cu surface is heavily oxidized during NO3 –RR in an alkaline medium. Consistent with this behavior, the CuSn alloy also stabilizes Cu(I) on the electrode surface and results in increased NO3 –RR rates. Alternatively, the CuPt alloy does not yield a stabilized Cu(I) component and consequently results in NO3 –RR rates lower than those for neat Cu. These results indicate that alloying Cu with different metals can tune the nitrate reduction activity by making the Cu atoms more resistant to oxidation to Cu(II) and stabilizing the Cu atoms in lower oxidation states.
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This work utilizes in situ electrochemical and analytical characterization during cycling of LiMn2O4 (LMO) equilibrated at different potentials in an ultrahigh vacuum (UHV) environment. The LMO ...reacts with organic molecules in the vacuum to form a high surface concentration of Li2CO3 (≈50% C) during initial charging to 4.05 V. Charging to higher potentials reduces the overall Li2CO3 concentration (≈15% C). Discharging to 3.0 V increases the Li2CO3 concentration (≈30% C) and over discharging to 0.1 V again reduces its concentration (≈15% C). This behavior is reproducible over 5 cycles. The model geometry utilized suggests that oxygen from LMO can participate in redox of carbon, where LMO contributes oxygen to form the carbonate in the solid electrolyte interphase (SEI). Similar results were obtained from samples cycled ex situ, suggesting that the model in situ geometry provides reasonably representative information about surface chemistry evolution. Carbon redox at LMO and the inherent voltage instability of the Li2CO3 likely contributes significantly to its capacity fade.
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Lithiated ternary oxides containing nickel, cobalt, and manganese are intercalation compounds that are used as positive electrodes in high-energy lithium-ion batteries. These oxides undergo changes, ...when they are stored in humid air or exposed to moisture, that adversely affect their electrochemical performance. There is a new urgency to better understanding of these "weathering" mechanisms as manufacturing moves toward a more environmentally benign aqueous processing of the positive electrode. Delithiation of the oxide and the formation of lithium salts (such as hydroxides and carbonates) coating the surface, are known to occur during moisture exposure. The redox reactions which follow this delithiation are believed to trigger all the other transformations. In this article we suggest another possibility: namely, the proton - lithium exchange. We argue that this hypothesis provides a simple, comprehensive rationale for our observations, which include contraction of the c-axis (unit cell) lattice parameter, rock salt phase formation in the subsurface regions, presence of amorphous surface films, and the partial recovery of oxide capacity during electrochemical relithiation. The detrimental effects of water exposure need to be mitigated before aqueous processing of the positive electrode can find widespread adoption during cell manufacturing.
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