Spontaneous incorporation of gold in palladium-based ternary nanoparticles makes durable electrocatalysts for oxygen reduction reaction.

Replacing platinum by a less precious metal such as palladium, is highly desirable for lowering the cost of fuel-cell electrocatalysts. However, the instability of palladium in the harsh environment of fuel-cell cathodes renders its commercial future bleak. Here we show that by incorporating trace amounts of gold in palladium-based ternary (Pd6CoCu) nanocatalysts, the durability of the catalysts improves markedly. Using aberration-corrected analytical transmission electron microscopy in conjunction with synchrotron X-ray absorption spectroscopy, we show that gold not only galvanically replaces cobalt and copper on the surface, but also penetrates through the Pd-Co-Cu lattice and distributes uniformly within the particles. The uniform incorporation of Au provides a stability boost to the entire host particle, from the surface to the interior. The spontaneous replacement method we have developed is scalable and commercially viable. This work may provide new insight for the large-scale production of non-platinum electrocatalysts for fuel-cell applications.

Operando X-ray scattering and spectroscopic analysis of germanium nanowire anodes in lithium ion batteries.

X-ray diffraction (XRD) and Fourier transform extended X-ray absorption fine structure (EXAFS) analysis of X-ray absorption spectroscopy (XAS) measurements have been employed to determine structural and bonding changes, as a function of the lithium content/state of charge, of germanium nanowires used as the active anode material within lithium ion batteries (LIBs). Our data, collected throughout the course of battery cycling (operando), indicate that lithium incorporation within the nanostructured germanium occurs heterogeneously, preferentially into amorphous regions over crystalline domains. Maintenance of the molecular structural integrity within the germanium nanowire is dependent on the depth of discharge. Discharging to a shallower cutoff voltage preserves partial crystallinity for several cycles.

High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance.

Pseudocapacitance is commonly associated with surface or near-surface reversible redox reactions, as observed with RuO2·xH2O in an acidic electrolyte. However, we recently demonstrated that a pseudocapacitive mechanism occurs when lithium ions are inserted into mesoporous and nanocrystal films of orthorhombic Nb2O5 (T-Nb2O5; refs 1,2). Here, we quantify the kinetics of charge storage in T-Nb2O5: currents that vary inversely with time, charge-storage capacity that is mostly independent of rate, and redox peaks that exhibit small voltage offsets even at high rates. We also define the structural characteristics necessary for this process, termed intercalation pseudocapacitance, which are a crystalline network that offers two-dimensional transport pathways and little structural change on intercalation. The principal benefit realized from intercalation pseudocapacitance is that high levels of charge storage are achieved within short periods of time because there are no limitations from solid-state diffusion. Thick electrodes (up to 40 µm thick) prepared with T-Nb2O5 offer the promise of exploiting intercalation pseudocapacitance to obtain high-rate charge-storage devices.

Poly(2,5-dimercapto-1,3,4-thiadiazole) as a cathode for rechargeable lithium batteries with dramatically improved performance.

Organosulfur compounds with multiple thiol groups are promising for high gravimetric energy density electrochemical energy storage. We have synthesized a poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT)/poly(3,4-ethylenedioxythiophene) (PEDOT) composite cathode for lithium-ion batteries with a new method and investigated its electrochemical behavior by charge/discharge cycles and cyclic voltammetry (CV) in an ether-based electrolyte. Based on a comparison of the electrochemical performance with a carbonate-based electrolyte, we found a much higher discharge capacity, but also a very attractive cycling performance of PDMcT by using a tetra(ethylene glycol) dimethyl ether (TEGDME)-based electrolyte. The first discharge capacity of the as-synthesized PDMcT/PEDOT composite approached 210 mAh g(-1) in the TEGDME-based electrolyte. CV results clearly show that the redox reactions of PDMcT are highly reversible in this TEGDME-based electrolyte. The reversible capacity remained around 120 mAh g(-1) after 20 charge/discharge cycles. With improved cycling performance and very low cost, PDMcT could become a very promising cathode material when combined with a TEGDME-based electrolyte. The poor capacity in the carbonate-based electrolyte is a consequence of the irreversible reaction of the DMcT monomer and dimer with the solvent, emphasizing the importance of electrolyte chemistry when studying molecular-based battery materials.

Electrocatalysis of 2,5-dimercapto-1,3,5-thiadiazole by 3,4-ethylenedioxy-substituted conducting polymers.

The electronic properties of electropolymerized films of the 3,4-ethylenedioxy-substituted conducting polymers (CP) poly(3,4-ethylenedioxythiophene) (PEDOT), poly(3,4-ethylenedioxypyrrole) (PEDOP) and poly(3,4-ethylenedioxyselenophene) (PEDOS) have been investigated, along with their electrocatalytic activity toward 2,5-dimercapto-1,3,4-thiadiazole (DMcT). For the electropolymerized films, the conductivity onset potential was most negative for PEDOP (-1.50 V), followed by PEDOS (-1.35 V) and with PEDOT possessing the most positive onset (-1.15 V). The heterogeneous charge transfer rate constant for DMcT in solution at polymer-film-modified glassy carbon electrodes (GCEs) was studied. It was found that compared to PEDOP, both PEDOS and PEDOT performed better as electrocatalysts, with PEDOS having a heterogeneous charge transfer rate constant of 1.8 × 10(-3) cm/s. The film morphology of the electropolymerized films was investigated via SEM, and some film characteristics could be correlated with electrocatalytic activity. The potential use of CP/DMcT composites for lithium ion batteries (LIBs) is discussed.

Electrochemistry of individual monolayer graphene sheets.

We report on the fabrication and measurement of devices designed to study the electrochemical behavior of individual monolayer graphene sheets as electrodes. We have examined both mechanically exfoliated and chemical vapor deposited (CVD) graphene. The effective device areas, determined from cyclic voltammetric measurements, show good agreement with the geometric area of the graphene sheets, indicating that the redox reactions occur on clean graphene surfaces. The electron transfer rates of ferrocenemethanol at both types of graphene electrodes were found to be more than 10-fold faster than at the basal plane of bulk graphite, which we ascribe to corrugations in the graphene sheets. We further describe an electrochemical investigation of adsorptive phenomena on graphene surfaces. Our results show that electrochemistry can provide a powerful means of investigating the interactions between molecules and the surfaces of graphene sheets as electrodes.

X-ray fluorescence investigation of ordered intermetallic phases as electrocatalysts towards the oxidation of small organic molecules.

The composition of ordered intermetallic nanoparticles (PtBi and PtPb) has been quantitatively studied by in situ X-ray fluorescence (XRF) during active electrochemical control in solutions of supporting electrolyte and small organic molecules (SOMs). Because the Pt L(ß1,2) lines and the Bi L(α1,2) lines are only separated by 200 eV, an energy-dispersive detector and a multiple-channel analyzer (MCA) were used to record the major fluorescent emission lines from these two elements. The molar ratios of platinum to the less-noble elements (Bi, Pb) in the nanoparticles dramatically changed as a function of the applied upper limit potentials (E(ulp)) in cyclic voltammetric (CV) characterization. Similar to previous investigations for bulk intermetallic surfaces, the less-noble elements leached out from the surfaces of the intermetallic nanoparticles. For PtBi nanoparticles, the ratios of fluorescence intensities of Pt/Bi in the samples were 0.42, 0.96, and 1.36 for E(ulp)=+0.40, +0.80, and 1.20 V, respectively, while cycling the potential from -0.20 V to the E(ulp) value for 10 cycles. The leaching-out process of the less-noble elements occurred at more negative E(ulp) values than expected. After cycling to relatively positive E(ulp) values, nonuniform PtM (M=Bi of Pb) nanoparticles formed with a Pt-rich shell and intermetallic PtM core. When the supporting solutions contained active fuel molecules in addition to the intermetallic nanoparticles (formic acid for PtBi, formic acid and methanol for PtPb), kinetic stabilization effects were observed for E(ulp)=+0.80 V, in a way similar to the response of the bulk materials. It was of great importance to quantitatively explore the change in composition and structure of the intermetallic nanoparticles under active electrochemical control. More importantly, this approach represents a simple, universal, and multifunctional method for the study of multi-element nanoparticles as electrocatalysts. This is, to our knowledge, the first report of nondestructive, quantitative characterization of bimetallic or multi-elemental nanoparticles electrocatalysts under active electrochemical control.