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The insertion and removal of Li+ions into Li-ion battery electrodes can lead to severe mechanical fatigue because of the repeated expansion and compression of the host lattice during electrochemical cycling. In particular, the lithium manganese oxide spinel (LiMn2O4, LMO) experiences a significant surface stress contribution to electrode chemomechanics upon delithiation that is asynchronous with the potentials where bulk phase transitions occur. In this work, we probe the stress evolution and resulting mechanical fracture from LMO delithation using an integrated approach consisting of cyclic voltammetry, electron microscopy, and density functional theory (DFT) calculations. High-rate electrochemical cycling is used to exacerbate the mechanical deficiencies of the LMO electrode and demonstrates that mechanical degradation leads to slowing of delithiation and lithiation kinetics. These observations are further supported through the identification of significant fracturing in LMO using scanning electron microscopy. DFT calculations are used to model the mechanical response of LMO surfaces to electrochemical delithiation and suggest that particle fracture is unlikely in the [001] direction because of tensile stresses from delithiation near the (001) surface. Transmission electron microscopy and electron backscatter diffraction of the as-cycled LMO particles further support the computational analyses, indicating that particle fracture instead tends to preferentially occur along the {111} planes. This joint computational and experimental analysis provides molecular-level details of the chemomechanical response of the LMO electrode to electrochemical delithiation and how surface stresses may lead to particle fracture in Li-ion battery electrodes.

Metal fluorides usually have a large electronegativity and are promising electrode materials for high-power lithium-ion batteries. However, like other conversion-reaction-based materials, large volumetric expansions and large capacity losses in cycling are the major issues for metal fluorides. Here, we explore substitution of Ni with Cu for binary NiF2and its effects on the electrochemical properties. By in situ transmission electron microscopy, the structural evolutions of several ternary metal fluorides with different Cu/Ni ratios are observed and correlated with their electrochemical properties. With increased Cu substitution from 0 to 25 wt %, the areal expansion during the first lithiation is reduced. Meanwhile, the fluorine loss (due to reaction irreversibility) in the delithiation cycle is also reduced. This provides an explanation for the advantage of Cu substitution for improved cycling stability and capacity. We believe that our observations provide insight into the development of better ternary metal fluorides as cathodes for high power density lithium-ion batteries.

It is well known that metastable and transient structures in bulk can be stabilized in thin films via epitaxial strain (heteroepitaxy) and appropriate growth conditions that are often far from equilibrium. However, the mechanism of heteroepitaxy, particularly how the nominally unstable or metastable phase gets stabilized, remains largely unclear. This is especially intriguing for thin-film Ga2O3, where multiple crystal phases may exist under varied growth conditions with spatial and dimensional constraints. Herein, the development and distribution of epitaxial strain at the Ga2O3/Al2O3film–substrate interfaces is revealed down to the atomic resolution along different orientations, with an aberration-corrected scanning transmission electron microscope. Just a few layers of metastable α-Ga2O3structure were found to accommodate the misfit strain in direct contact with the substrate. Following an epitaxial α-Ga2O3structure of about couple unit cells, several layers (4–5) of transient phase appear as the intermediate structure to release the misfit strain. Subsequent to this transient crystal phase, the nominally unstable κ-Ga2O3phase is stabilized as the major thin-film phase form. We show that the epitaxial strain is gracefully accommodated by rearrangement of the oxygen polyhedra. When the structure is under large compressive strain, Ga3+ions occupy only the oxygen octahedral sites to form a dense structure. With gradual release of the compressive strain, more and more Ga3+ions occupy the oxygen tetrahedral sites, leading to volumetric expansion and the phase transformation. The structure of the transition phase is identified by high-resolution electron microscopy observation, complemented by the density functional theory calculations. This study provides insights from the atomic scale and their implications for the design of functional thin-film materials using epitaxial engineering.

Ultrafast synthesis of high-quality transition-metal dichalcogenide nanocrystals, such as molybdenum disulfide (MoS2), is technologically relevant for large-scale production of electronic and optoelectronic devices. Here, we report a rapid solid-state synthesis route for MoS2using the chemically homogeneous molecular precursor, (NH4)2Mo3S13·H2O, resulting in nanoparticles with estimated size down to 25 nm only in 10 s at 1000 °C. Despite the extreme nonequilibrium conditions, the resulting porous MoS2nanoparticles remain aggregated to preserve the form of the original rod shape bulk morphology of the molecular precursor. This ultrafast synthesis proceeds through the rapid decomposition of the precursor and rearrangement of Mo and S atoms coupled with simultaneous efficient release of massive gaseous species, to create nanoscale porosity in the resulting isomorphic pseudocrystals, which are composed of the MoS2nanoparticles. Despite the very rapid escape of massive amounts of NH3, H2O, H2S, and S gases from the (NH4)2Mo3S13·H2O mm sized crystals, they retain their original shape as they convert to MoS2rather than undergo explosive destruction from the rapid escape process of the gases. The obtained pseudocrystals are made of aggregated MoS2nanocrystals exhibit a Brunauer–Emmett–Teller surface area of ∼35 m2/g with an adsorption average pore width of ∼160 Å. The nanoporous MoS2crystals are solution processable by dispersing in ethanol and water and can be cast into large-area uniform composite films. Photodetectors fabricated from these films show more than 2 orders of magnitude higher conductivity (∼6.25 × 10–6S/cm) and photoconductive gain (20 mA/W) than previous reports of MoS2composite films. The optoelectronic properties of this nanoporous MoS2imply that the shallow defects that originate from the ultrafast synthesis act as sensitizing centers that increase the photocurrent gain via two-level recombination kinetics.

Spinel-type lithium manganese oxide (LiMn2O4) cathodes suffer from severe manganese dissolution in the electrolyte, compromising the cyclic stability of LMO-based Li-ion batteries (LIBs). In addition to causing structural and morphological deterioration to the cathode, dissolved Mn ions can migrate through the electrolyte to deposit on the anode, accelerating capacity fade. Here, we examine single-crystal epitaxial LiMn2O4(111) thin-films using synchrotron in situX-ray diffraction and reflectivity to study the structural and interfacial evolution during cycling. Cyclic voltammetry is performed in a wide range (2.5–4.3 V vsLi/Li+) to promote Mn3+formation, which enhances dissolution, for two different electrolyte systems: an imidazolium ionic liquid containing lithium bis-(trifluoromethylsulfonyl)imide (LiTFSI) and a conventional carbonate liquid electrolyte containing lithium hexafluorophosphate (LiPF6). We find exceptional stability in this voltage range for the ionic liquid electrolyte compared to the conventional electrolyte, which is attributed to the absence of Mn dissolution in the ionic liquid. X-ray reflectivity shows a negligible loss of cathode material for the films cycled in the ionic liquid electrolyte, further confirmed by inductively coupled plasma mass spectrometry and transmission electron microscopy. Conversely, a substantial loss of Mn is found when the film is cycled in the conventional electrolyte. These findings show the significant advantages of ionic liquids in suppressing Mn dissolution in LiMn2O4LIB cathodes.

Nanolayered structures present significantly enhanced electrochemical performance by facilitating the surface-dependent electrochemical reaction processes for supercapacitors, which, however, causes capacitance fade upon cycling due to their poor chemical stability. In this work, we report a simple and effective approach to develop a stable, high performance electrode material by integrating 2D transition metal hydroxide and reduced graphene oxide sheets at nanometer scale. Specifically, a hybrid nanolayer of Ni–Co hydroxide @reduced graphene oxide (Ni,Co–OH/rGO) with an average thickness of 1.37 nm is synthesized through an easy one-pot hydrothermal method. Benefiting from the face to face contact model between Ni–Co hydroxide and rGO sheets, such unique structure presents superior specific capacitance and cycling performance as compared to the pure Ni–Co hydroxide nanolayers. An asymmetric supercapacitor based on Ni,Co–OH/rGO and three-dimensional (3D) hierarchical porous carbon is developed, exhibiting a high energy density of 56.1 Wh kg–1along with remarkable cycling stability (80% retention after 17 000 cycles), which holds great promise for practical applications in energy storage devices.