Proton transfer and regulation across chemical interfaces by small-molecule assemblies.

We report on measurements and control of proton gradient across interfaces of water and dichloroethane. Such interfaces are interesting as mimics of biological membranes. We use impedance spectroscopy to quantify interfacial proton gradient and identify proton transfer modes. We quantify proton movement using reciprocal of time constant (τ-1 ) acquired from electrochemical impedance modeling. We show that proton gradient across interfaces of water/dichloroethane and τ-1 correlate with the aqueous phase pH, changing from ca. 1 s-1 at pH 1 to 0.2 s-1 at pH 7. τ-1 changes in the presence of proton shuttling fat-soluble molecules. Dinitrophenol acts as a pH activated proton coupler which is active at around neutral pH and inert at pH <4. However, quinone type cofactors change the interfacial proton transport when activated by redox reactions with ferrocene type molecules, such as decamethyl ferrocence (DMFc). Quinone type cofactors show distinct features in their impedance response assigned to a proton coupled electron transfer (PCET) process, different from the uncoupled proton transfer activity of dinitrophenol. The observed PCET reaction significantly changes τ-1 . We use τ-1 as a proton transport descriptor. In particular, CoQ10 -DMFc shows a τ-1 of 3.5 s-1 at pH 7, indicating how small-molecule assemblies change proton availability.

Structural Evolution of Ultrathin SrFeO3-δ Films during Oxygen Evolution Reaction Revealed by In Situ Electrochemical Stress Measurements.

We report the electrochemical stress analysis of SrFeO3-δ (SFO) films deposited on Au substrates during oxygen evolution reactions (OERs). Our in situ analysis of Au reveals conversion reactions from Au to Au(OH)3, AuOOH, and AuOx during the OER. Au reactions cause a monotonic compressive stress on surfaces assigned to the formation of Au hydroxides and oxides. Electrochemical stress analysis of SrFeO3-δ/Au shows a dramatically different behavior during the OER, which we attribute to structural evolutions and conversion reactions, such as the conversion of SFO to iron (oxy)hydroxides. Interestingly, electrochemical stress analysis of SrFeO3-δ/Au shows a tensile trend, which evolves with cycling history. Electrochemical stress analysis of SFO films before the onset of the OER shows in situ changes, which cause tensile stresses when cycling to 1.2 V. We attribute these stresses to the formation of Fe2+δOδ(OH)2-δ (0 ≤ δ ≤ 1.5)-type materials where δ approaches 1.5 at higher potentials. At potentials higher than 1.2 V and during OER, surface stress response is rather stable, which we assign to the full conversion of SFO to iron (oxy)hydroxides. This analysis provides insight into the reaction mechanism and details of in situ structural changes of iron perovskites during the OER in alkaline environments.

In-situ Raman analysis of hydrogenation in well-defined ultrathin molybdenum diselenide deposits synthesized through vapor phase deposition.

We report on the synthesis, characterization and in-situ Raman spectroscopy analysis of hydrogenation in ultrathin crystalline MoSe2 deposits. We use a controllable vapor phase synthesis method using MoSe2 powder as the only precursor, to fabricate nano- to micro-size few layer thick MoSe2 deposits with tunable number densities on SiO2/Si substrates. We employ this controllable synthesis method to correlate characteristic Raman spectroscopy response of MoSe2 at ca. 242 cm-1 (A1g) and ca. 280 cm-1 (E2g1) with the thickness of the deposits acquired from atomic force microscopy (AFM). We also use this array of well-defined atomically thin MoSe2 deposits to study possible hydrogenation effects on select architectures using in-situ Raman spectroscopy. Interestingly, our analysis indicates that ultrathin MoSe2 deposits with exposed edges show a blue shift of 1-2 cm-1 when exposed to H2 flow at 150-250 sccm for 2-4 hours in a sealed reaction cell. Exposure to Ar flow under same condition reverses the observed shift in the A1g mode of the select MoSe2 deposits. Our measurements provide in-situ evidence for hydrogen adsorption on MoSe2 deposits at room temperature and insight into the possible active sites for hydrogen reactions on layered dichalcogenides at lower dimensions.

Electrochemical stiffness in lithium-ion batteries.

Although lithium-ion batteries are ubiquitous in portable electronics, increased charge rate and discharge power are required for more demanding applications such as electric vehicles. The high-rate exchange of lithium ions required for more power and faster charging generates significant stresses and strains in the electrodes that ultimately lead to performance degradation. To date, electrochemically induced stresses and strains in battery electrodes have been studied only individually. Here, a new technique is developed to probe the chemomechanical response of electrodes by calculating the electrochemical stiffness via coordinated in situ stress and strain measurements. We show that dramatic changes in electrochemical stiffness occur due to the formation of different graphite-lithium intercalation compounds during cycling. Our analysis reveals that stress scales proportionally with the lithiation/delithiation rate and strain scales proportionally with capacity (and inversely with rate). Electrochemical stiffness measurements provide new insights into the origin of rate-dependent chemomechanical degradation and the evaluation of advanced battery electrodes.

Identification of Li-Ion Battery SEI Compounds through (7)Li and (13)C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry.

Solid-state (7)Li and (13)C MAS NMR spectra of cycled graphitic Li-ion anodes demonstrate SEI compound formation upon lithiation that is followed by changes in the SEI upon delithiation. Solid-state (13)C DPMAS NMR shows changes in peaks associated with organic solvent compounds (ethylene carbonate and dimethyl carbonate, EC/DMC) upon electrochemical cycling due to the formation of and subsequent changes in the SEI compounds. Solid-state (13)C NMR spin-lattice (T1) relaxation time measurements of lithiated Li-ion anodes and reference poly(ethylene oxide) (PEO) powders, along with MALDI-TOF mass spectrometry results, indicate that large-molecular-weight polymers are formed in the SEI layers of the discharged anodes. MALDI-TOF MS and NMR spectroscopy results additionally indicate that delithiated anodes exhibit a larger number of SEI products than is found in lithiated anodes.

Defect evolution in graphene upon electrochemical lithiation.

Despite rapidly growing interest in the application of graphene in lithium ion batteries, the interaction of the graphene with lithium ions and electrolyte species during electrochemical cycling is not fully understood. In this work, we use Raman spectroscopy in a model system of monolayer graphene transferred on a Si(111) substrate and density functional theory (DFT) to investigate defect formation as a function of lithiation. This model system enables the early stages of defect formation to be probed in a manner previously not possible with commonly used reduced graphene oxide or multilayer graphene substrates. Using ex situ and Ar-atmosphere Raman spectroscopy, we detected a rapid increase in graphene defect level for small increments in the number of lithiation/delithiation cycles until the I(D)/I(G) ratio reaches ∼1.5-2.0 and the 2D peak intensity drops by ∼50%, after which the Raman spectra show minimal changes upon further cycling. Using DFT, the interplay between graphene topological defects and chemical functionalization is explored, thus providing insight into the experimental results. In particular, the DFT results show that defects can act as active sites for species that are present in the electrochemical environment such as Li, O, and F. Furthermore, chemical functionalization with these species lowers subsequent defect formation energies, thus accelerating graphene degradation upon cycling. This positive feedback loop continues until the defect concentration reaches a level where lithium diffusion through the graphene can occur in a relatively unimpeded manner, with minimal further degradation upon extended cycling. Overall, this study provides mechanistic insight into graphene defect formation during lithiation, thus informing ongoing efforts to employ graphene in lithium ion battery technology.