Akihiro Kushima

In situ observation of the electrochemical lithiation of a single SnO2 nanowire electrode.

Fragile Tin Oxide Electrodes While tin oxide has a high energy density, and would thus make an attractive anode material for a Li-ion battery, it undergoes significant volume changes when Li is intercalated. The large strains cause cracking, pulverization, and a resultant loss of electrical conduction. Huang et al. (p. 1515; see the Perspective by Chiang) used in situ transmission electron microscopy on a single tin oxide nanowire to identify the physical changes that occur during intercalation and observed a moving cloud of dislocations that separated the reacted and unreacted sections. Upon completion of the electrochemical charging, the nanowire showed up to 90% elongation and a 35% increase in diameter. Transmission electron microscopy reveals dimensional changes in a tin oxide nanowire as it intercalates lithium. We report the creation of a nanoscale electrochemical device inside a transmission electron microscope—consisting of a single tin dioxide (SnO2) nanowire anode, an ionic liquid electrolyte, and a bulk lithium cobalt dioxide (LiCoO2) cathode—and the in situ observation of the lithiation of the SnO2 nanowire during electrochemical charging. Upon charging, a reaction front propagated progressively along the nanowire, causing the nanowire to swell, elongate, and spiral. The reaction front is a “Medusa zone” containing a high density of mobile dislocations, which are continuously nucleated and absorbed at the moving front. This dislocation cloud indicates large in-plane misfit stresses and is a structural precursor to electrochemically driven solid-state amorphization. Because lithiation-induced volume expansion, plasticity, and pulverization of electrode materials are the major mechanical effects that plague the performance and lifetime of high-capacity anodes in lithium-ion batteries, our observations provide important mechanistic insight for the design of advanced batteries.

Anisotropic Swelling and Fracture of Silicon Nanowires during Lithiation

We report direct observation of an unexpected anisotropic swelling of Si nanowires during lithiation against either a solid electrolyte with a lithium counter-electrode or a liquid electrolyte with a LiCoO(2) counter-electrode. Such anisotropic expansion is attributed to the interfacial processes of accommodating large volumetric strains at the lithiation reaction front that depend sensitively on the crystallographic orientation. This anisotropic swelling results in lithiated Si nanowires with a remarkable dumbbell-shaped cross section, which develops due to plastic flow and an ensuing necking instability that is induced by the tensile hoop stress buildup in the lithiated shell. The plasticity-driven morphological instabilities often lead to fracture in lithiated nanowires, now captured in video. These results provide important insight into the battery degradation mechanisms.

A realistic molecular model of cement hydrates

Despite decades of studies of calcium-silicate-hydrate (C-S-H), the structurally complex binder phase of concrete, the interplay between chemical composition and density remains essentially unexplored. Together these characteristics of C-S-H define and modulate the physical and mechanical properties of this “liquid stone” gel phase. With the recent determination of the calcium/silicon (C/S = 1.7) ratio and the density of the C-S-H particle (2.6 g/cm3) by neutron scattering measurements, there is new urgency to the challenge of explaining these essential properties. Here we propose a molecular model of C-S-H based on a bottom-up atomistic simulation approach that considers only the chemical specificity of the system as the overriding constraint. By allowing for short silica chains distributed as monomers, dimers, and pentamers, this C-S-H archetype of a molecular description of interacting CaO, SiO2, and H2O units provides not only realistic values of the C/S ratio and the density computed by grand canonical Monte Carlo simulation of water adsorption at 300 K. The model, with a chemical composition of (CaO)1.65(SiO2)(H2O)1.75, also predicts other essential structural features and fundamental physical properties amenable to experimental validation, which suggest that the C-S-H gel structure includes both glass-like short-range order and crystalline features of the mineral tobermorite. Additionally, we probe the mechanical stiffness, strength, and hydrolytic shear response of our molecular model, as compared to experimentally measured properties of C-S-H. The latter results illustrate the prospect of treating cement on equal footing with metals and ceramics in the current application of mechanism-based models and multiscale simulations to study inelastic deformation and cracking.

Oxygen ion diffusivity in strained yttria stabilized zirconia: where is the fastest strain?

We present the mechanism and the extent of increase in the oxygen anion diffusivity in Y2O3 stabilized ZrO2 (YSZ) under biaxial lattice strain. The oxygen vacancy migration paths and barriers in YSZ as a function of lattice strain was assessed computationally using density functional theory (DFT) and nudged elastic band (NEB) method. Two competing and non-linear processes acting in parallel were identified to alter the migration barrier upon applied strain: (1) the change in the space, or electronic density, along the migration path, and (2) the change in the strength of the interatomic bonds between the migrating oxygen and the nearest neighbor cations that keep the oxygen from migrating. The increase of the migration space and the weakening of the local oxygen–cation bonds correspond to a decrease of the migration barrier, and vice versa. The contribution of the bond strength to the changes in the migration barrier is more significant than that of the opening of migration space in strained YSZ. A database of migration barrier energies as a function of lattice strain for a set of representative defect distributions in the vicinity of the migration path in YSZ was constructed. This database was used in kinetic Monte Carlo (KMC) simulations to estimate the effective oxygen diffusivity in strained YSZ. The oxygen diffusivity exhibits an exponential increase up to a critical value of tensile strain, or the fastest strain. This increase is more significant at the lower temperatures. At the strain states higher than the critical strain, the diffusivity decreases. This is attributed to the local relaxations at large strain states beyond a limit of elastic bond strain, resulting in the strengthening of the local oxygen–cation bonds that increases the migration barrier. The highest enhancement of diffusivity in 9%-YSZ compared to its unstrained state is 6.8 × 103 times at 4% strain and at 400 K. The results indicate that inducing an optimal strain state by direct mechanical load or by creating a coherent hetero-interface with lattice mismatch can enable desirably high ionic conductivity in YSZ at reduced temperatures. The insights gained here particularly on the nonlinear and competing consequences of lattice strain on the local bonding structure and charge transport process are of importance for tuning the ionic transport properties in a variety of solid-state conducting material applications, including but not limited to fuel cells.

Probing the failure mechanism of SnO2 nanowires for sodium-ion batteries.

Nonlithium metals such as sodium have attracted wide attention as a potential charge carrying ion for rechargeable batteries. Using in situ transmission electron microscopy in combination with density functional theory calculations, we probed the structural and chemical evolution of SnO2 nanowire anodes in Na-ion batteries and compared them quantitatively with results from Li-ion batteries (Huang, J. Y.; et al. Science 2010, 330, 1515 - 1520). Upon Na insertion into SnO2, a displacement reaction occurs, leading to the formation of amorphous NaxSn nanoparticles dispersed in Na2O matrix. With further Na insertion, the NaxSn crystallized into Na15Sn4 (x = 3.75). Upon extraction of Na (desodiation), the NaxSn transforms to Sn nanoparticles. Associated with the dealloying, pores are found to form, leading to a structure of Sn particles confined in a hollow matrix of Na2O. These pores greatly increase electrical impedance, therefore accounting for the poor cyclability of SnO2. DFT calculations indicate that Na(+) diffuses 30 times slower than Li(+) in SnO2, in agreement with in situ TEM measurement. Insertion of Na can chemomechanically soften the reaction product to a greater extent than in lithiation. Therefore, in contrast to the lithiation of SnO2 significantly less dislocation plasticity was seen ahead of the sodiation front. This direct comparison of the results from Na and Li highlights the critical role of ionic size and electronic structure of different ionic species on the charge/discharge rate and failure mechanisms in these batteries.

Slurryless Li2S/Reduced Graphene Oxide Cathode Paper for High-Performance Lithium Sulfur Battery

Lithium sulfide (Li2S) is a promising cathode material for Li-S batteries with high capacity (theoretically 1166 mAh g(-1)) and can be paired with nonlithium-metal anodes to avoid potential safety issues. However, the cycle life of coarse Li2S particles suffers from poor electronic conductivity and polysulfide shuttling. Here, we develop a flexible slurryless nano-Li2S/reduced graphene oxide cathode paper (nano-Li2S/rGO paper) by simple drop-coating. The Li2S/rGO paper can be directly used as a free-standing and binder-free cathode without metal substrate, which leads to significant weight savings. It shows excellent rate capability (up to 7 C) and cycle life in coin cell tests due to the high electron conductivity, flexibility, and strong solvent absorbency of rGO paper. The Li2S particles that precipitate out of the solvent on rGO have diameters 25-50 nm, which is in contrast to the 3-5 μm coarse Li2S particles without rGO.

Leapfrog Cracking and Nanoamorphization of ZnO Nanowires during In Situ Electrochemical Lithiation

The lithiation reaction of single ZnO nanowire (NW) electrode in a Li-ion nanobattery configuration was observed by in situ transmission electron microscopy. Upon first charge, the single-crystalline NW was transformed into a nanoglass with multiple glassy nanodomains (Gleiter, H. MRS Bulletin2009, 34, 456) by an intriguing reaction mechanism. First, partial lithiation of crystalline NW induced multiple nanocracks ∼70 nm ahead of the main lithiation front, which traversed the NW cross-section and divided the NW into multiple segments. This was followed by rapid surface diffusion of Li(+) and solid-state amorphization along the open crack surfaces. Finally the crack surfaces merged, leaving behind a glass-glass interface (GGI). Such reaction front instability also repeated in the interior of each divided segment, further subdividing the NW into different nanoglass domains (nanoamorphization). Instead of the profuse dislocation plasticity seen in SnO(2) NWs (Science2010, 330, 1515), no dislocation was seen and the aforementioned nanocracking was the main precursor to the electrochemically driven solid-state amorphization in ZnO. Ab initio tensile decohesion calculations verified dramatic lithium embrittlement effect in ZnO, but not in SnO(2). This is attributed to the aliovalency of Sn cation (Sn(IV), Sn(II)) in contrast to the electronically more rigid Zn(II) cation.

Coordination Polymers Derived General Synthesis of Multishelled Mixed Metal-Oxide Particles for Hybrid Supercapacitors

Metal-organic frameworks (MOFs) or coordination polymers (CPs) have been used as precursors for synthesis of materials. Unlike crystalline MOF, amorphous CP is nonspecific to metal cation species, therefore its composition can be tuned easily. Here, it is shown that amorphous CP can be used as general synthesis precursors of highly complex mixed metal oxide shells. As a proof of concept, NiCo coordination polymer spheres are first synthesized and subsequently transformed into seven-layered NiCo oxide onions by rapid thermal oxidation. This approach is very versatile and can be applied to produce ternary and quaternary metal oxide onions with tunable size and composition. The NiCo oxide onions exhibit exceptional charge storage capability in aqueous electrolyte with high specific capacitance (≈1900 F g-1 at 2 A g-1 ), good rate capability, and ultrahigh cycling stability (93.6% retention over 20 000 cycles). A hybrid supercapacitor against graphene/multishelled mesoporous carbon sphere shows a high energy density of 52.6 Wh kg-1 at a power density of 1604 W kg-1 (based on active materials weight), as well as remarkable cycling stability.

Computing the viscosity of supercooled liquids

We describe an atomistic method for computing the viscosity of highly viscous liquids based on activated state kinetics. A basin-filling algorithm allowing the system to climb out of deep energy minima through a series of activation and relaxation is proposed and first benchmarked on the problem of adatom diffusion on a metal surface. It is then used to generate transition state pathway trajectories in the potential energy landscape of a binary Lennard-Jones system. Analysis of a sampled trajectory shows the system moves from one deep minimum to another by a process that involves high activation energy and the crossing of many local minima and saddle points. To use the trajectory data to compute the viscosity we derive a Markov Network model within the Green-Kubo formalism and show that it is capable of producing the temperature dependence in the low-viscosity regime described by molecular dynamics simulation, and in the high-viscosity regime (10(2)-10(12) Pa s) shown by experiments on fragile glass-forming liquids. We also derive a mean-field-like description involving a coarse-grained temperature-dependent activation barrier, and show it can account qualitatively for the fragile behavior. From the standpoint of molecular studies of transport phenomena this work provides access to long relaxation time processes beyond the reach of current molecular dynamics capabilities. In a companion paper we report a similar study of silica, a representative strong liquid. A comparison of the two systems gives insight into the fundamental difference between strong and fragile temperature variations.

Self-healing SEI enables full-cell cycling of a silicon-majority anode with a coulombic efficiency exceeding 99.9%

Despite active developments, full-cell cycling of Li-battery anodes with >50 wt% Si (a Si-majority anode, SiMA) is rare. The main challenge lies in the solid electrolyte interphase (SEI), which when formed naturally (nSEI), is fragile and cannot tolerate the large volume changes of Si during lithiation/delithiation. An artificial SEI (aSEI) with a specific set of mechanical characteristics is henceforth designed; we enclose Si within a TiO2 shell thinner than 15 nm, which may or may not be completely hermetic at the beginning. In situ TEM experiments show that the TiO2 shell exhibits 5× greater strength than an amorphous carbon shell. Void-padded compartmentalization of Si can survive the huge volume changes and electrolyte ingression, with a self-healing aSEI + nSEI. The half-cell capacity exceeds 990 mA h g−1 after 1500 cycles. To improve the volumetric capacity, we further compress SiMA 3-fold from its tap density (0.4 g cm−3) to 1.4 g cm−3, and then run the full-cell battery tests against a 3 mA h cm−2 LiCoO2 cathode. Despite some TiO2 enclosures being inevitably broken, 2× the volumetric capacity (1100 mA h cm−3) and 2× the gravimetric capacity (762 mA h g−1) of commercial graphite anode is achieved in stable full-cell battery cycling, with a stabilized areal capacity of 1.6 mA h cm−2 at the 100th cycle. The initial lithium loss, characterized by the coulombic inefficiency (CI), is carefully tallied on a logarithmic scale and compared with the actual full-cell capacity loss. It is shown that a strong, non-adherent aSEI, even if partially cracked, facilitates an adaptive self-repair mechanism that enables full-cell cycling of a SiMA, leading to a stabilized coulombic efficiency exceeding 99.9%.