SIMES Publications

Abstract

The bilayer Hubbard model with electron-hole doping is an ideal platform to study excitonic orders due to suppressed recombination via spatial separation of electrons and holes. However, suffering from the sign problem, previous quantum Monte Carlo studies could not arrive at an unequivocal conclusion regarding the presence of phases with clear signatures of excitonic condensation in bilayer Hubbard models. Here, we develop a determinant quantum Monte Carlo algorithm for the bilayer Hubbard model that is sign-problem-free for equal and opposite doping in the two layers and study excitonic order and charge and spin density modulations as a function of chemical potential difference between the two layers, on-site Coulomb repulsion, and interlayer interaction. In the intermediate coupling regime and in proximity to the SU(4)-symmetric point, we find a biexcitonic condensate phase at finite electron-hole doping, as well as a competing (π, π) charge density wave state. We extract the Berezinskii-Kosterlitz-Thouless transition temperature from superfluid density and a finite-size scaling analysis of the correlation functions and explain our results in terms of an effective biexcitonic hard-core boson model.

Abstract

A common characteristic of many “overdoped” cuprates prepared with high-pressure oxygen is T_c values ≥ 50 K that often exceed that of optimally doped parent compounds, despite O stoichiometries that place the materials at the edge or outside of the conventional boundary between superconducting and normal Fermi liquid states. X-ray absorptionfine-structure (XAFS) measurements at 52 K on samples of high-pressure oxygen (HPO) YSr₂Cu_2.75 Mo_0.25 O_7.54, T_c= 84 K show that the Mo is in the (VI) valence in an unusually undistorted octahedral geometry with predominantly Mo neighbors that is consistent with its assigned substitution for Cu in the chain sites of the structure. Perturbations of the Cu environments are minimal, although the Cu X-ray absorption near-edge structure (XANES) differs from that in other cuprates. The primary deviation from the crystal structure is therefore nanophase separation into Mo- and Cu-enriched domains. There are, however, indications that the dynamical attributes of the structure are altered relative to YBa₂Cu₃O₇, including a shift of the Cu-apical O two-site distribution from the chain to the plane Cu sites. Another effect that would influence T_c is the possibility of multiple bands at the Fermi surface caused by the presence of the second phase and the lowering of the Fermi level.

Abstract

The local structure of the highly “overdoped” 95 K superconductor Sr₂CuO_3.3 determined by Cu K X-ray absorption fine structure (XAFS) at 62 K in magnetically oriented samples shows that 1) the magnetization is perpendicular to the c axis; 2) at these levels of precision the Cu sublattice is tetragonal in agreement with the crystal structure; the O sublattice has 3) continuous -Cu-O- chains that orient perpendicular to an applied magnetic field; 4) approximately half-filled -Cu-O- chains that orient parallel to this field; 5) a substantial number of apical O vacancies; 6) O ions at some apical positions with expanded Cu-O distances; and 7) interstitial positions that imply highly displaced Sr ions. These results contradict the universally accepted features of cuprates that require intact CuO₂ planes, magnetization along the c axis, and a termination of the superconductivity when the excess charge on the CuO₂ Cu ions exceeds 0.27. These radical differences in charge and structure demonstrate that this compound constitutes a separate class of Cu-O–based superconductors in which the superconductivity originates in a different, more complicated structural unit than CuO₂ planes while retaining exceptionally high transition temperatures.

Abstract

To achieve good rate capability of lithium metal anodes for high-energy-density batteries, one fundamental challenge is the slow lithium diffusion at the interface. Here we report an interpenetrated, three-dimensional lithium metal/lithium tin alloy nanocomposite foil realized by a simple calendering and folding process of lithium and tin foils, and spontaneous alloying reactions. The strong affinity between the metallic lithium and lithium tin alloy as mixed electronic and ionic conducting networks, and their abundant interfaces enable ultrafast charger diffusion across the entire electrode. We demonstrate that a lithium/lithium tin alloy foil electrode sustains stable lithium stripping/plating under 30 mA cm⁻² and 5 mAh cm⁻² with a very low overpotential of 20 mV for 200 cycles in a commercial carbonate electrolyte. Cycled under 6 C (6.6 mA cm⁻²), a 1.0 mAh cm⁻² LiNi_0.6Co_0.2Mn_0.2O₂ electrode maintains a substantial 74% of its capacity by pairing with such anode.

Abstract

The oxygen redox (OR) activity is conventionally considered detrimental to the stability and kinetics of batteries. However, OR reactions are often confused by irreversible oxygen oxidation. Here, based on high-efficiency mapping of resonant inelastic x-ray scattering of both the transition metal and oxygen, we distinguish the lattice OR in Na_0.6[Li_0.2Mn_0.8]O₂ and compare it with Na_2/3[Mg_1/3 Mn_2/3]O₂. Both systems display strong lattice OR activities but with distinct electrochemical stability. The comparison shows that the substantial capacity drop in Na_0.6[Li_0.2Mn_0.8]O₂ stems from non-lattice oxygen oxidations, and its voltage decay from an increasing Mn redox contribution upon cycling, contrasting those in Na_2/3[Mg_1/3 Mn_2/3]O₂. We conclude that lattice OR is not the ringleader of the stability issue. Instead, irreversible oxygen oxidation and the changing cationic reactions lead to the capacity and voltage fade. We argue that lattice OR and other oxygen activities should/could be studied and treated separately to achieve viable OR-based electrodes.

Abstract

Fully understanding the mechanism of lithium metal deposition is critical for the development of rechargeable lithium battery anodes. The heterogeneous electron transfer kinetics are an important aspect of lithium electrodeposition, but they have been difficult to measure and understand. Here, we use transient voltammetry with ultramicroelectrodes to explicitly investigate the electron transfer kinetics of lithium electrodeposition. The results deviate from the Butler–Volmer model of electrode kinetics; instead, a Marcus model accurately describes the electron transfer. Measuring the kinetics in a series of electrolytes shows the mechanism of lithium deposition under electron transfer control is consistent with the general framework of Marcus theory. Comparison of the transient voltammetry results to electrochemical impedance spectra provides a strategy for understanding how the interplay of the electron transfer and mass transport resistances affect the morphology of lithium.

Abstract

Safety issues in lithium-ion batteries have raised serious concerns due to their ubiquitous utilization and close contact with the human body. Replacing flammable liquid electrolytes, solid-state electrolytes (SSEs) is thought to address this issue as well as provide unmatched energy densities in Li-based batteries. However, among the most intensively studied SSEs, polymeric solid electrolyte and polymer/ ceramic composites are usually flammable, leaving the safety issue unattended. Here, we report the first design of a fireproof, ultralightweight polymer−polymer SSE. The SSE is composed of a porous mechanic enforcer (polyimide, PI), a fire-retardant additive (decabromodiphenyl ethane, DBDPE), and a ionic conductive polymer electrolyte (poly(ethylene oxide)/lithium bis(trifluoromethanesulfonyl)imide). The whole SSE is made from organic materials, with a thin, tunable thickness (10−25 μm), which endorse the energy density comparable to conventional separator/liquid electrolytes. The PI/DBDPE film is thermally stable, nonflammable, and mechanically strong, preventing Li−Li symmetrical cells from short-circuiting after more than 300 h of cycling. LiFePO₄/Li half cells with our SSE show a high rate performance (131 mAh g⁻¹ at 1 C) as well as cycling performance (300 cycles at C/2 rate) at 60 °C. Most intriguingly, pouch cells made with our polymer− polymer SSE still functioned well even under flame abuse tests.

Abstract

Double-sided metal-oxide-semiconductor field-effect-transistor processing is demonstrated for the first time on an ultrathin crystalline silicon substrate of 6-20 μm in a 100 mm diameter wafer format without a carrier wafer, the thinnest free-standing silicon wafers ever fabricated. The compatibility of the flexible material with conventional semiconductor processing tools is enabled by supporting an interior ultrathin silicon with a surrounding thicker ring of silicon. Current-voltage characteristics of transistors on ultrathin silicon show performance as expected from bulk silicon, with electron mobility ~1500 cm² V⁻¹ second⁻¹. Mechanical measurements quantify the handleability.

Abstract

The traditional Zn/MnO₂ battery has attracted great interest due to its low cost, high safety, high output voltage, and environmental friendliness. However, it remains a big challenge to achieve long‐term stability, mainly owing to the poor reversibility of the cathode reaction. Different from previous studies where the cathode redox reaction of MnO₂/MnOOH is in solid state with limited reversibility, here a new aqueous rechargeable Zn/MnO₂ flow battery is constructed with dissolution–precipitation reactions in both cathodes (Mn²⁺/MnO₂) and anodes (Zn²⁺/Zn), which allow mixing of anolyte and catholyte into only one electrolyte and remove the requirement for an ion selective membrane for cost reduction. Impressively, this new battery exhibits a high discharge voltage of ≈1.78 V, good rate capability (10C discharge), and excellent cycling stability (1000 cycles without decay) at the areal capacity ranging from 0.5 to 2 mAh cm^‐2. More importantly, this battery can be readily enlarged to a bench scale flow cell of 1.2 Ah with good capacity retention of 89.7% at the 500th cycle, displaying great potential for large‐scale energy storage.

Abstract

Manipulating liquids with tunable shape and optical functionalities in real time is important for electroactive flow devices and optoelectronic devices, but remains a great challenge. Here, we demonstrate electrotunable liquid sulfur microdroplets in an electrochemical cell. We observe electrowetting and merging of sulfur droplets under different potentiostatic conditions, and successfully control these processes via selective design of sulfiphilic/sulfiphobic substrates. Moreover, we employ the electrowetting phenomena to create a microlens based on the liquid sulfur microdroplets and tune its characteristics in real time through changing the shape of the liquid microdroplets in a fast, repeatable, and controlled manner. These studies demonstrate a powerful in situ optical battery platform for unraveling the complex reaction mechanism of sulfur chemistries and for exploring the rich material properties of the liquid sulfur, which shed light on the applications of liquid sulfur droplets in devices such as microlenses, and potentially other electrotunable and optoelectronic devices.