SIMES Publications

Abstract

Practical applications of Li-S batteries are hindered by the dissolution/diffusion loss of sulfur-related active materials in cathode and dendrite growth in Li metal anode. Here we present an integrated sulfur cathode design on tortuosity and sulfur-binding affinity parameters for mitigating diffusion loss of sulfur-based active materials. The high sulfur-philicity property (from oxygen functional groups, 16% in concentration) in reduced graphene oxide (rGO) host favors bonding with sulfur species to mitigate their diffusion/dissolution loss, while the high tortuosity (13.24, from horizontal arrangement of rGO sheets) can localize the soluble active materials within the host rather than outward diffusion loss with subsequent uneven redeposition. With this integrated concept, we achieved ultrahigh cathode areal capacities of 21 mAh cm⁻² with 98.1% retention after 160 cycles, surpassing those electrodes with lower tortuosity and sulfur-philicity. In addition, same rGO host suppresses dendrite growth in Li anode, enabling 278% prolonged cycle life in the full cell.

Abstract

Diamond anvil cell techniques have been improved to allow access to the multimegabar ultrahigh-pressure region for exploring novel phenomena in condensed matter. However, the only way to determine crystal structures of materials above 100 GPa, namely, X-ray diffraction (XRD), especially for low Z materials, remains nontrivial in the ultrahigh-pressure region, even with the availability of brilliant synchrotron X-ray sources. In this work, we perform a systematic study, choosing hydrogen (the lowest X-ray scatterer) as the subject, to understand how to better perform XRD measurements of low Z materials at multimegabar pressures. The techniques that we have developed have been proved to be effective in measuring the crystal structure of solid hydrogen up to 254 GPa at room temperature [C. Ji et al., Nature 573, 558–562 (2019)]. We present our discoveries and experiences with regard to several aspects of this work, namely, diamond anvil selection, sample configuration for ultrahigh-pressure XRD studies, XRD diagnostics for low Z materials, and related issues in data interpretation and pressure calibration. We believe that these methods can be readily extended to other low Z materials and can pave the way for studying the crystal structure of hydrogen at higher pressures, eventually testing structural models of metallic hydrogen.

Abstract

Compelling evidence indicates that the solid Earth consists of two physicochemically distinct zones separated radially in the middle of the lower mantle at ∼1800 km depth. The inner zone is governed by pressure-induced physics and chemistry dramatically different from the conventional behavior in the outer zone. These differences generate large physical and chemical potentials between the two zones that provide fundamental driving forces for triggering major events in Earth’s history. One of the main chemical carriers between the two zones is H₂O in hydrous minerals that subducts into the inner zone, releases hydrogen, and leaves oxygen to create superoxides and form oxygen-rich piles at the core–mantle boundary, resulting in localized net oxygen gain in the inner zone. Accumulation of oxygen-rich piles at the base of the mantle could eventually reach a supercritical level that triggers eruptions, injecting materials that cause chemical mantle convection, superplumes, large igneous provinces, extreme climate changes, atmospheric oxygen fluctuations, and mass extinctions. Interdisciplinary research will be the key for advancing a unified theory of the four-dimensional Earth system.

Abstract

The spin-1/2 kagome antiferromagnet is considered an ideal host for a quantum spin liquid (QSL) ground state. We find that when the bonds of the kagome lattice are modulated with a periodic pattern, new quantum ground states emerge. Newly synthesized crystalline barlowite (Cu₄(OH)₆FBr) and Zn-substituted barlowite demonstrate the delicate interplay between singlet states and spin order on the spin-1/2 kagome lattice. Comprehensive structural measurements demonstrate that our new variant of barlowite maintains hexagonal symmetry at low temperatures with an arrangement of distorted and undistorted kagome triangles, for which numerical simulations predict a pinwheel valence bond crystal (VBC) state instead of a QSL. The presence of interlayer spins eventually leads to an interesting pinwheel q=0 magnetic order. Partially Zn-substituted barlowite (Cu_3.44Zn_0.56(OH)₆FBr) has an ideal kagome lattice and shows QSL behavior, indicating a surprising robustness of the QSL against interlayer impurities. The magnetic susceptibility is similar to that of herbertsmithite, even though the Cu²⁺ impurities are above the percolation threshold for the interlayer lattice and they couple more strongly to the nearest kagome moment. This system is a unique playground displaying QSL, VBC, and spin order, furthering our understanding of these highly competitive quantum states.

Abstract

Metallic lithium (Li) anodes are crucial for the development of high specific energy batteries yet are plagued by their poor cycling efficiency. Electrode architecture engineering is vital for maintaining a stable anode volume and suppressing Li corrosion during cycling. In this paper, a reduced graphene oxide “host” framework for Li metal anodes is further optimized by embedding silicon (Si) nanoparticles between the graphene layers. They serve as Li nucleation seeds to promote Li deposition within the framework even without prestored Li. Meanwhile, the Li_xSi alloy particles serve as supporting “pillars” between the graphene layers, enabling a minimized thickness shrinkage after full stripping of metallic Li. Combined with a Li compatible electrolyte, a 99.4% Coulombic efficiency over ∼600 cycles is achieved, and stable cycling of a Li||NMC532 full cell for ∼380 cycles with negligible capacity decay is realized.

Abstract

Recently, quantum anomalous Hall effect with spontaneous ferromagnetism was observed in twisted bilayer graphenes (TBG) near 3/4 filling. Importantly, it was observed that an extremely small current can switch the direction of the magnetization. This offers the prospect of realizing low energy dissipation magnetic memories. However, the mechanism of the current-driven magnetization switching is poorly understood as the charge currents in graphenes are generally believed to be non-magnetic. In this work, we demonstrate that in TBG, the twisting and substrate induced symmetry breaking allow an out of plane orbital magnetization to be generated by a charge current. Moreover, the large Berry curvatures of the flat bands give the Bloch electrons large orbital magnetic moments so that a small current can generate a large orbital magnetization. We further demonstrate how the charge current can switch the magnetization of the ferromagnetic TBG near 3/4 filling as observed in the experiments.

Abstract

Due to their outstanding properties, diverse geometry, and ability to be manipulated and functionalized, diamondoids have gained interest as highly attractive targets as molecular building blocks for applications in biomedicine, materials science, and nanotechnology, in addition to the field of petroleum engineering (Clay et al., 2009; Mcintosh et al., 2004; Sasagawa & Shen, 2008; Willey et al., 2006; Zhang et al., 2016). Diamondoid molecules are also a useful system for basic science studies. They display atomic‐level uniformity and a systematic series of sizes and geometries, making them ideal materials for exploring how different parameters can be used to tune properties. In this chapter, the pressure‐induced structural modifications in a range of diamondoids are reported. In section 27.2, the critical role of molecular geometry in determining the phase transition pressures and bulk moduli of diamondoids is discussed, followed by the sensitivity of diamondoids to hydrostaticity and deviatoric stress under compression. Section 27.3 examines recent work investigating functionalized diamondoids at high pressure and concludes with a perspective for future work and exciting potential directions for studying diamondoids at extreme conditions.

Abstract

We determine the work functions of the iron arsenic compounds AFe₂As₂ (A=Ca,Ba,Cs) using photoemission spectroscopy to be 2.7 eV for CaFe₂As₂, 1.8 eV for BaFe₂As₂, and 1.3 eV for CsFe₂As₂. The work functions of these 122 iron-based superconductors track those of the elementary metal A but are substantially smaller. The most likely explanation of this observation is that the cleaving surface exposes only half an A-layer. The low work function and good photoemission cross section of BaFe₂As₂ and CsFe₂As₂ enable photoemission even from a common white LED light.

Abstract

Studies of two-dimensional electron systems in a strong magnetic field revealed the quantum Hall effect¹, a topological state of matter featuring a finite Chern number C and chiral edge states^2,3. Haldane⁴ later theorized that Chern insulators with integer quantum Hall effects could appear in lattice models with complex hopping parameters even at zero magnetic field. The ABC-trilayer graphene/hexagonal boron nitride (ABC-TLG/hBN) moiré superlattice provides an attractive platform with which to explore Chern insulators because it features nearly flat moiré minibands with a valley-dependent, electrically tunable Chern number^5,6. Here we report the experimental observation of a correlated Chern insulator in an ABC-TLG/hBN moiré superlattice. We show that reversing the direction of the applied vertical electric field switches the moiré minibands of ABC-TLG/hBN between zero and finite Chern numbers, as revealed by large changes in magneto-transport behaviour. For topological hole minibands tuned to have a finite Chern number, we focus on quarter filling, corresponding to one hole per moiré unit cell. The Hall resistance is well quantized at h/2e² (where h is Planck’s constant and e is the charge on the electron), which implies C = 2, for a magnetic field exceeding 0.4 tesla. The correlated Chern insulator is ferromagnetic, exhibiting substantial magnetic hysteresis and a large anomalous Hall signal at zero magnetic field. Our discovery of a C = 2 Chern insulator at zero magnetic field should open up opportunities for discovering correlated topological states, possibly with topological excitations⁷, in nearly flat and topologically nontrivial moiré minibands.

Correction to: Naturehttps://doi.org/10.1038/s41586-020-2049-7Published online 4 March 2020

Abstract

Carbon-based nanomaterials have exceptional properties that make them attractive for a variety of technological applications. Here, we report on the use of diamondoids (diamond-like, saturated hydrocarbons) as promising precursors for laser-induced high-pressure, high-temperature diamond synthesis. The lowest pressure and temperature (P-T) conditions that yielded diamond were 12 GPa (at ~2000 K) and 900 K (at ~20 GPa), respectively. This represents a substantially reduced transformation barrier compared with diamond synthesis from conventional (hydro)carbon allotropes, owing to the similarities in the structure and full sp3 hybridization of diamondoids and bulk diamond. At 20 GPa, diamondoid-to-diamond conversion occurs rapidly within <19 μs. Molecular dynamics simulations indicate that once dehydrogenated, the remaining diamondoid carbon cages reconstruct themselves into diamond-like structures at high P-T. This study is the first successful mapping of the P-Tconditions and onset timing of the diamondoid-to-diamond conversion and elucidates the physical and chemical factors that facilitate diamond synthesis.