Capacitive deionization, CDI, has emerged as an attractive alternative for water desalination. Electrodes based on Hierarchically porous carbons, HPCs, consistently show promising electrosorption performance. However, the typically low mesopore fraction and broad pore size distribution limit their utilization in practical applications. Here we report the CDI performance of a series of HPCs synthesized via ice templation possessing a high fraction of mesopore volume (85–93% of total porosity) and tight control over the amount and the size of mesopores (∼6 nm). Electrochemical measurements indicate high rate capability (82% salt retention) and outstanding cycling stability performance (100% capacitance retention over 600 cycles at 0.76 A g−1). In the CDI experiments, the HPCs display high salt capacity (up to ∼ 13 mg g−1) and consistently outperform other high surface areas commercial carbons. The existence of high fraction of mesoporosities enables better utilization of the accessible surfaces of HPCs where the introduction of micropores leads to more than 80% increase in the salt capacity. The HPCs reported here can serve as model electrode systems in studies to delineate the impact of mesoporosity (pore size and volume) on CDI performance and they may pave the way for practical CDI applications.
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.
Carefully designed solid-electrolyte interphases are required for stable, reversible and efficient electrochemical energy storage in batteries. We report that hybrid battery anodes created by depositing an electrochemically active metal (for example, Sn, In or Si) on a reactive alkali metal electrode by a facile ion-exchange chemistry lead to very high exchange currents and stable long-term performance of electrochemical cells based on Li and Na electrodes. By means of direct visualization and ex situ electrodeposition studies, Sn–Li anodes are shown to be stable at 3 mA cm−2 and 3 mAh cm−2. Prototype full cells in which the hybrid anodes are paired with high-loading LiNi0.8Co0.15Al0.05O2(NCA) cathodes are also reported. As a second demonstration, we create and study Sn–Na hybrid anodes and show that they can be cycled stably for more than 1,700 hours with minimal voltage divergence. Charge storage at the hybrid anodes is reported to involve a combination of alloying and electrodeposition reactions.
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.
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.
Rechargeable batteries based on metallic anodes are of interest for fundamental and application-focused studies of chemical and physical kinetics of liquids at solid interfaces. Approaches that allow facile creation of uniform coatings on these metals to prevent physical contact with liquid electrolytes, while enabling fast ion transport, are essential to address chemical instability of the anodes. Here, we report a simple electroless ion-exchange chemistry for creating coatings of indium on lithium. By means of joint density functional theory and interfacial characterization experiments, we show that In coatings stabilize Li by multiple processes, including exceptionally fast surface diffusion of lithium ions and high chemical resistance to liquid electrolytes. Indium coatings also undergo reversible alloying reactions with lithium ions, facilitating design of high-capacity hybrid In-Li anodes that use both alloying and plating approaches for charge storage. By means of direct visualization, we further show that the coatings enable remarkably compact and uniform electrodeposition. The resultant In-Li anodes are shown to exhibit minimal capacity fade in extended galvanostatic cycling when paired with commercial-grade cathodes.
Tu, Zhengyuan; Choudhury, Snehashis; Zachman, Michael J.; Wei, Shuya; Zhang, Kaihang; Kourkoutis, Lena F.; Archer, Lynden A.(Joule, Elsevier BV, 2017-09-21)[Article]
Substrates able to rectify transport of ions based on charge and/or size are ubiquitous in biological systems. Electrolytes and interphases that selectively transport electrochemically active ions are likewise of broad interest in all electrical energy storage technologies. In lithium-ion batteries, electrolytes with single- or near-single-ion conductivity reduce losses caused by ion polarization. In emergent lithium or sodium metal batteries, they maintain high conductivity at the anode and stabilize metal deposition by fundamental mechanisms. We report that 20- to 300-nm-thick, single-ion-conducting membranes deposited at the anode enable electrolytes with the highest combination of cation transference number, ionic conductivity, and electrochemical stability reported. By means of direct visualization we find that single-ion membranes also reduce dendritic deposition of Li in liquids. Galvanostatic measurements further show that the electrolytes facilitate long (3 mAh) recharge of full Li/LiNi0.8Co0.15Al0.05O2 (NCA) cells with high cathode loadings (3 mAh cm−2/19.9 mg cm−2) and at high current densities (3 mA cm−2).
Kosma, Vasiliki; Hayrapetyan, Suren; Diamanti, Evmorfia; Dhawale, Ajay; Giannelis, Emmanuel P.(Construction and Building Materials, Elsevier BV, 2017-11-29)[Article]
Bitumen-clay nanocomposite binders with styrene-butadienestyrene triblock copolymer, SBS, and combinations of SBS and crumb rubber (CR) with different CR/SBS ratios have been synthesized and characterized. In addition to the binder, samples containing the binder and concrete sand (with a weight ratio 1:9) were prepared. The modified binders were studied in terms of filler dispersion, storage stability, mechanical performance and water susceptibility. We demonstrate that the samples containing nanoclays consistently outperform those based only on the polymer additives. We also find that nanocomposite samples based on a combination of SBS and CR are best, since in addition to other improvements they show excellent storage stability. Our work shows that substituting CR with SBS as a bitumen additive and combining it with inexpensive nanoclays leads to new materials with enhanced performance and improved stability for practical asphalt applications.
Yao, Chuanjin; Zhao, Yushi; Lei, Guanglun; Steenhuis, Tammo S.; Cathles, Lawrence M.(Industrial & Engineering Chemistry Research, American Chemical Society (ACS), 2017-06-07)[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.
Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid–electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.
The export option will allow you to export the current search results of the entered query to a file. Different
formats are available for download. To export the items, click on the button corresponding with the preferred download format.
By default, clicking on the export buttons will result in a download of the allowed maximum amount of items.
For anonymous users the allowed maximum amount is 50 search results.
To select a subset of the search results, click "Selective Export" button and make a selection of the items you want to export.
The amount of items that can be exported at once is similarly restricted as the full export.
After making a selection, click one of the export format buttons. The amount of items that will be exported is indicated in the bubble next to export format.