Many intermetallic materials deliver poor capacity retention when cycled vs. Li. Many authors have attributed this poor capacity retention to large volume expansions of the active material. Here we report the volume changes of continuous and patterned films of crystalline Al, crystalline Sn, amorphous Si ͑a-Si͒, and a-Si 0.64 Sn 0.36 as they reversibly react with Li measured by in situ atomic force microscopy ͑AFM͒. Although these materials all undergo large volume expansions, the amorphous phases undergo reversible shape and volume changes. The crystalline materials do not. We attribute this difference to the homogeneous expansion and contraction that occurs in the amorphous materials. Inhomogeneous expansion occurs in the crystalline materials due to the presence of coexisting phases with different Li concentrations. Thin films of a-Si and a-Si 0.64 Sn 0.36 show good capacity retention with cycle number.
A multitarget sputtering machine with a water-cooled rotating substrate table has been modified to produce films on 75 mm × 75 mm wafers which map large portions of ternary phase diagrams. The system is unconventional because the stoichiometries of the elements sputtered on the wafer vary linearly with position and in an orthogonal manner. Subsequent screening of film properties is therefore quite intuitive, since the compositional variations are simple. Depositions are made under continuous rotation, so either intimate mixing of the elements (fast rotation) or artificial layered structures (slow rotation) can be produced. Rotating subtables mounted on the main rotating table hold the 75 mm × 75 mm substrates. Stationary mask openings over the targets and mechanical actuators that rotate the subtables in a precise manner accomplish the linear and orthogonal stoichiometry variations. Deposition of a film spanning the range SiSn x Al y (0 < x, y < 1), with Sn content increasing parallel to one edge on the wafer and Al content increasing in a perpendicular direction, is given to illustrate the effectiveness of the method. Since the system was easily and inexpensively built, it has enabled our research program in combinatorial materials synthesis to begin without large scale funding.
LiFePO 4 /Li 4/3 Ti 5/3 O 4 Li-ion cells have been investigated by many groups and their behavior in standard electrolytes such as 1 M LiPF 6 ethylene carbonate: diethyl carbonate ͑EC:DEC͒ is well known. Here we report on the behavior of these cells with 2,5-ditertbutyl-1,4-dimethoxybenzene added to the electrolyte as a redox shuttle additive to prevent overcharge and overdischarge. We explore methods to increase the current-carrying capacity of the shuttle and explore the heating of practical cells during extended overcharge. The solubility of 2,5-ditertbutyl-1,4-dimethoxybenzene was determined as a function of salt concentration in lithium bis-oxolatoborate-͑LiBOB͒ and LiPF 6 -containing electrolytes based on propylene carbonate ͑PC͒, EC, DEC, and dimethyl carbonate ͑DMC͒ solvents. Concentrations of 2,5-ditertbutyl-1,4-dimethoxybenzene up to 0.4 M can be obtained in 0.5 M LiBOB PC:DEC ͑1:2 by volume͒. Coin-type test cells were tested for extended overcharge protection using an electrolyte containing 0.2 M 2,5-ditertbutyl-1,4-dimethoxybenzene in 0.5 M LiBOB PC:DEC. Sustained overcharge protection at a current density of 2.3 mA/cm 2 was possible and hundreds of 100% shuttle-protected overcharge cycles were achieved at current densities of about 1 mA/cm 2 . The diffusion coefficient of the shuttle molecule in this electrolyte was determined to be 1.6 ϫ 10 −6 cm 2 /s from cyclic voltammetry and also from measurements of the shuttle potential vs. current density. The power produced during overcharge was measured using isothermal microcalorimetry and found to be IV as expected, where I is the charging current and V is the cell terminal voltage during shuttle-protected overcharge. Calculations of the temperature of 18650-sized Li-ion cells as a function of time during extended shuttle-protected overcharge at various C-rates are presented. These show that Li-ion cells need external cooling during extended shuttle-protected overcharge if currents exceed about C/5 rates.
SUMMARYGraphite has been used as the negative electrode in lithium-ion batteries for more than a decade. To attain higher energy density batteries, silicon and tin, which can alloy reversibly with lithium, have been considered as a replacement for graphite. However, the volume expansion of these metal elements upon lithiation can result in poor capacity retention. Alloying the active metal element with an inactive material can limit the overall volume expansion and improve cycle life. This paper presents a summary of tin-based materials as negative electrodes. After reviewing attempts to improve and understand the electrochemical behaviour of metallic tin and its oxides, the focus turns to alloys of tin with a transition metal (TM) and, optionally, carbon. To do so, a combinatorial sputtering technique was used to simultaneously prepare many different compositions of Sn-TM-based materials. The structural and electrochemical results of these samples are presented and they show that cobalt is the preferred TM to give optimal performance. Finally, a comparison of a Sn-Co-C negative electrode material prepared by a rapid quenching method (sputtering) with a material prepared by an economical milling method (mechanical attrition) is presented and discussed.
Design, testing, and performance of a 64-channel combinatorial electrochemical cell are described. This cell is used for highthroughput screening of materials for use as Li-ion rechargeable battery electrodes. Our sealed cell has 64 separate positive electrodes and Li foil for the reference and counter electrodes. This combinatorial electrochemical cell was designed to complement our existing combinatorial materials science infrastructure. Using the combinatorial electrochemical cell decreases the time and labor associated with test cell assembly, improves the repeatability of our assembly procedure, and increases the number of compositions we can test in a given amount of time. In this paper, we demonstrate that the results from the combinatorial electrochemical cell and from conventional 2325 coin-type test cells, containing electrodes of sputtered films prepared in the same sputtering run, are identical for electrodes of the same composition.
We present an investigation into the influence of nanocrystal size on the reactivity of silicon nanocrystals (Si-NCs) in near-UV photochemical hydrosilylation. The size-dependent reactivity of Si-NCs with photoluminescence (PL) in the visible and near-infrared regions was evaluated using PL and Fourier-transform infrared (FTIR) spectroscopy, and small-angle X-ray scattering (SAXS). Under near-UV excitation, Si-NCs with PL in the visible spectral region react faster than Si-NCs with near-IR PL, allowing partial separation of a mixture of Si-NC sizes through hydrosilylation. This is attributed to quantum size effects in the exciton-mediated mechanisms proposed for this reaction.
A cationic and water‐soluble polythiophene [poly[3‐(6‐pyridiniumylhexyl)thiophene bromide] (P3PHT+Br−)] is synthesized and used in combination with anionic poly(3,4‐ethylenedioxythiophene):poly(p‐styrenesulfonate) (PEDOT:PSS)− to produce hybrid coatings on indium tin oxide (ITO). Two coating strategies are established: i) electrostatic layer‐by‐layer assembly with colloidal suspensions of (PEDOT:PSS)−, and ii) modification of an electrochemically prepared (PEDOT:PSS)− film on ITO. The coatings are found to modify the work function of ITO such that it could act as a cathode in inverted 2,5‐diyl‐poly(3‐hexylthiophene) (P3HT)/[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) polymer photovoltaic cells. The interfacial modifier created from the layer‐by‐layer assembly route is used to produce efficient inverted organic photovoltaic devices (power conversion efficiency ∼2%) with significant long‐term stability in excess of 500 h.
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