Tu, Zhengyuan; Zachman, Michael J.; Choudhury, Snehashis; Khan, Kasim A.; Zhao, Qing; Kourkoutis, Lena F.; Archer, Lynden A.(Chemistry of Materials, American Chemical Society (ACS), 2018-07-25)[Article]
Approaches for regulating electrochemical stability of liquid electrolytes in contact with solid-state electrodes are a requirement for efficient and reversible electrical energy storage in batteries. Such methods are particularly needed in electrochemical cells in which the working potentials of the electrodes lie well outside the thermodynamic stability limits of the liquid electrolyte. Here we study electrochemical stability of liquids at electrolyte/electrode interfaces protected by a nanometer-thick, high-electrical band gap ceramic phase. We report that well-designed ceramic interphases extend the oxi-dative stability limits for both protic and aprotic liquid electrolytes, in some cases by as much as 1.5V. It is shown further that such interphases facilitate stable electrodeposition of reactive metals such as lithium at high Coulombic efficiency and in electrochemical cells subject to extended galvanostatic cycling at a high current density of 3 mA cm-2 and at capacities as high as 3 mAh cm-2. High-resolution cryo-FIB-SEM characterization reveals that solid/compact Li electrodeposits anchored by the ceramic interphase are the source of the enhanced Li deposition stability. The results enable a proof-of-concept ‘an-ode-free’ Li metal rechargeable battery in which Li initially provided in the cathode is the only source of lithium in the cell.
Nevers, Douglas R.; Williamson, Curtis B.; Savitzky, Benjamin H; Hadar, Ido; Banin, Uri; Kourkoutis, Lena F.; Hanrath, Tobias; Robinson, Richard D.(Journal of the American Chemical Society, American Chemical Society (ACS), 2018-01-27)[Article]
Magic-sized clusters (MSCs) are renowned for their identical size and closed-shell stability that inhibit conventional nanoparticle (NP) growth processes. Though MSCs have been of increasing interest, understanding the reaction pathways toward their nucleation and stabilization is an outstanding issue. In this work, we demonstrate that high concentration synthesis (1000 mM) promotes a well-defined reaction pathway to form high-purity MSCs (>99.9%). The MSCs are resistant to typical growth and dissolution processes. Based on insights from in-situ X-ray scattering analysis, we attribute this stability to the accompanying production of a large, hexagonal organic-inorganic mesophase (>100 nm grain size) that arrests growth of the MSCs and prevents NP growth. At intermediate concentrations (500 mM), the MSC mesophase forms, but is unstable, resulting in NP growth at the expense of the assemblies. These results provide an alternate explanation for the high stability of MSCs. Whereas the conventional mantra has been that the stability of MSCs derives from the precise arrangement of the inorganic structures (i.e., closed-shell atomic packing), we demonstrate that anisotropic clusters can also be stabilized by self-forming fibrous mesophase assemblies. At lower concentration (<200 mM or >16 acid-to-metal), MSCs are further destabilized and NPs formation dominates that of MSCs. Overall, the high concentration approach intensifies and showcases inherent concentration-dependent surfactant phase behavior that is not accessible in conventional (i.e., dilute) conditions. This work provides not only a robust method to synthesize, stabilize, and study identical MSC products, but also uncovers an underappreciated stabilizing interaction between surfactants and clusters.
Yao, Chuanjin; Zhao, Yushi; Lei, Guanglun; Steenhuis, Tammo S.; Cathles, Lawrence M.(Industrial & Engineering Chemistry Research, American Chemical Society (ACS), 2017-06-15)[Article]
Knowledge of preferential flow in heterogeneous environments is essential for enhanced hydrocarbon recovery, geothermal energy extraction, and successful sequestration of chemical waste and carbon dioxide. Dual tracer tests using nanoparticles with a chemical tracer could indicate the preferential flow. A dual-permeability model with a high permeable core channel surrounded by a low permeable annulus was constructed and used to determine the viability of an inert carbon nanoparticle tracer for this application. A series of column experiments were conducted to demonstrate how this nanoparticle tracer can be used to implement the dual tracer tests in heterogeneous environments. The results indicate that, with the injection rate selected and controlled appropriately, nanoparticles together with a chemical tracer can assess the preferential flow in heterogeneous environments. The results also implement the dual tracer tests in heterogeneous environments by simultaneously injecting chemical and nanoparticle tracers.
Odent, Jérémy; Raquez, Jean-Marie; Samuel, Cédric; Barrau, Sophie; Enotiadis, Apostolos; Dubois, Philippe; Giannelis, Emmanuel P.(Macromolecules, American Chemical Society (ACS), 2017-03-27)[Article]
Commercial polylactide (PLA) was converted and endowed with shape-memory properties by synthesizing ionic hybrids based on blends of PLA with imidazolium-terminated PLA and poly[ε-caprolactone-co-d,l-lactide] (P[CL-co-LA]) and surface-modified silica nanoparticles. The electrostatic interactions assist with the silica nanoparticle dispersion in the polymer matrix. Since nanoparticle dispersion in polymers is a perennial challenge and has prevented nanocomposites from reaching their full potential in terms of performance we expect this new design will be exploited in other polymers systems to synthesize well-dispersed nanocomposites. Rheological measurements of the ionic hybrids are consistent with the formation of a network. The ionic hybrids are also much more deformable compared to the neat PLA. More importantly, they exhibit shape-memory behavior with fixity ratio Rf ≈ 100% and recovery ratio Rr = 79%, for the blend containing 25 wt % im-PLA and 25 wt % im-P[CL-co-LA] and 5 wt % of SiO2–SO3Na. Dielectric spectroscopy and dynamic mechanical analysis show a second, low-frequency relaxation attributed to strongly immobilized polymer chains on silica due to electrostatic interactions. Creep compliance tests further suggest that the ionic interactions prevent permanent slippage in the hybrids which is most likely responsible for the significant shape-memory behavior observed.
Moore, David T.; Sai, Hiroaki; Tan, Kwan W.; Smilgies, Detlef-M.; Zhang, Wei; Snaith, Henry J.; Wiesner, Ulrich; Estroff, Lara A.(Journal of the American Chemical Society, American Chemical Society (ACS), 2015-02-09)[Article]
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