Jiangwei Wang

Two-Phase Electrochemical Lithiation in Amorphous Silicon

Lithium-ion batteries have revolutionized portable electronics and will be a key to electrifying transport vehicles and delivering renewable electricity. Amorphous silicon (a-Si) is being intensively studied as a high-capacity anode material for next-generation lithium-ion batteries. Its lithiation has been widely thought to occur through a single-phase mechanism with gentle Li profiles, thus offering a significant potential for mitigating pulverization and capacity fade. Here, we discover a surprising two-phase process of electrochemical lithiation in a-Si by using in situ transmission electron microscopy. The lithiation occurs by the movement of a sharp phase boundary between the a-Si reactant and an amorphous Li(x)Si (a-Li(x)Si, x ~ 2.5) product. Such a striking amorphous-amorphous interface exists until the remaining a-Si is consumed. Then a second step of lithiation sets in without a visible interface, resulting in the final product of a-Li(x)Si (x ~ 3.75). We show that the two-phase lithiation can be the fundamental mechanism underpinning the anomalous morphological change of microfabricated a-Si electrodes, i.e., from a disk shape to a dome shape. Our results represent a significant step toward the understanding of the electrochemically driven reaction and degradation in amorphous materials, which is critical to the development of microstructurally stable electrodes for high-performance lithium-ion batteries.

Nanoscale origins of the damage tolerance of the high-entropy alloy CrMnFeCoNi

Damage tolerance can be an elusive characteristic of structural materials requiring both high strength and ductility, properties that are often mutually exclusive. High-entropy alloys are of interest in this regard. Specifically, the single-phase CrMnFeCoNi alloy displays tensile strength levels of ∼1 GPa, excellent ductility (∼60–70%) and exceptional fracture toughness (KJIc>200 MPa√m). Here through the use of in situ straining in an aberration-corrected transmission electron microscope, we report on the salient atomistic to micro-scale mechanisms underlying the origin of these properties. We identify a synergy of multiple deformation mechanisms, rarely achieved in metallic alloys, which generates high strength, work hardening and ductility, including the easy motion of Shockley partials, their interactions to form stacking-fault parallelepipeds, and arrest at planar slip bands of undissociated dislocations. We further show that crack propagation is impeded by twinned, nanoscale bridges that form between the near-tip crack faces and delay fracture by shielding the crack tip.

In Situ Transmission Electron Microscopy Study of Electrochemical Sodiation and Potassiation of Carbon Nanofibers

Carbonaceous materials have great potential for applications as anodes of alkali-metal ion batteries, such as Na-ion batteries and K-ion batteries (NIB and KIBs). We conduct an in situ study of the electrochemically driven sodiation and potassiation of individual carbon nanofibers (CNFs) by transmission electron microscopy (TEM). The CNFs are hollow and consist of a bilayer wall with an outer layer of disordered-carbon (d-C) enclosing an inner layer of crystalline-carbon (c-C). The d-C exhibits about three times volume expansion of the c-C after full sodiation or potassiation, thus suggesting a much higher storage capacity of Na or K ions in d-C than c-C. For the bilayer CNF-based electrode, a steady sodium capacity of 245 mAh/g is measured with a Coulombic efficiency approaching 98% after a few initial cycles. The in situ TEM experiments also reveal the mechanical degradation of CNFs through formation of longitudinal cracks near the c-C/d-C interface during sodiation and potassiation. Geometrical changes of the tube are explained by a chemomechanical model using the anisotropic sodiation/potassiation strains in c-C and d-C. Our results provide mechanistic insights into the electrochemical reaction, microstructure evolution and mechanical degradation of carbon-based anodes during sodiation and potassiation, shedding light onto the development of carbon-based electrodes for NIBs and KIBs.

Near-ideal theoretical strength in gold nanowires containing angstrom scale twins

Although nanoscale twinning is an effective means to enhance yield strength and tensile ductility in metals, nanotwinned metals generally fail well below their theoretical strength limit due to heterogeneous dislocation nucleation from boundaries or surface imperfections. Here we show that Au nanowires containing angstrom-scaled twins (0.7 nm in thickness) exhibit tensile strengths up to 3.12 GPa, near the ideal limit, with a remarkable ductile-to-brittle transition with decreasing twin size. This is opposite to the behaviour of metallic nanowires with lower-density twins reported thus far. Ultrahigh-density twins (twin thickness<2.8 nm) are shown to give rise to homogeneous dislocation nucleation and plastic shear localization, contrasting with the heterogeneous slip mechanism observed in single-crystalline or low-density-twinned nanowires. The twin size dependent dislocation nucleation and deformation represent a new type of size effect distinct from the sample size effects described previously.

High damage tolerance of electrochemically lithiated silicon

Mechanical degradation and resultant capacity fade in high-capacity electrode materials critically hinder their use in high-performance rechargeable batteries. Despite tremendous efforts devoted to the study of the electro–chemo–mechanical behaviours of high-capacity electrode materials, their fracture properties and mechanisms remain largely unknown. Here we report a nanomechanical study on the damage tolerance of electrochemically lithiated silicon. Our in situ transmission electron microscopy experiments reveal a striking contrast of brittle fracture in pristine silicon versus ductile tensile deformation in fully lithiated silicon. Quantitative fracture toughness measurements by nanoindentation show a rapid brittle-to-ductile transition of fracture as the lithium-to-silicon molar ratio is increased to above 1.5. Molecular dynamics simulations elucidate the mechanistic underpinnings of the brittle-to-ductile transition governed by atomic bonding and lithiation-induced toughening. Our results reveal the high damage tolerance in amorphous lithium-rich silicon alloys and have important implications for the development of durable rechargeable batteries.

Lithium–tellurium batteries based on tellurium/porous carbon composite

For the first time, lithiation/delithiation behavior of tellurium at room temperature was investigated using tellurium/porous carbon (Te/C) composite electrodes. The Te/C composite is synthesized by the infusion of liquid tellurium into a porous carbon host at the high temperature of 600 °C under vacuum. Owing to the physical confinement of Te by porous carbon matrix, the Te/C electrode is capable of delivering a reversible volumetric capacity as high as 1400 mAh cm−3 (224 mAh g−1) at 312 mA cm−3 (50 mA g−1) current and maintains 87% of its initial capacity after 1000 cycles. Even when the current increases to 12480 mA cm−3 (2000 mA g−1), the Te/C electrode can still provide a volumetric capacity of 500 mAh cm−3. The high volumetric capacity, long cycle life and good rate capability make Te/C composite a promising electrode for Li-ion batteries.

Size-Dependent Brittle-to-Ductile Transition in Silica Glass Nanofibers

Silica (SiO2) glass, an essential material in human civilization, possesses excellent formability near its glass-transition temperature (Tg > 1100 °C). However, bulk SiO2 glass is very brittle at room temperature. Here we show a surprising brittle-to-ductile transition of SiO2 glass nanofibers at room temperature as its diameter reduces below 18 nm, accompanied by ultrahigh fracture strength. Large tensile plastic elongation up to 18% can be achieved at low strain rate. The unexpected ductility is due to a free surface affected zone in the nanofibers, with enhanced ionic mobility compared to the bulk that improves ductility by producing more bond-switching events per irreversible bond loss under tensile stress. Our discovery is fundamentally important for understanding the damage tolerance of small-scale amorphous structures.

High rate and long cycle life porous carbon nanofiber paper anodes for potassium-ion batteries

Potassium-ion batteries (KIBs) are an emerging energy storage technology for low cost and large scale applications. However, they suffer from insufficient cycle life and poor rate capability caused by the large K ions. In this paper, these problems are circumvented by using free-standing porous carbon nanofiber (CNF) paper anodes. Excellent electrochemical performance was demonstrated with an extremely high rate capability retaining 100 mA h g−1 at the current rate of 7.7 A g−1, a high reversible capacity of 270 mA h g−1 and a very low decay rate of 0.01% per cycle over 1200 cycles, which are much better than those of previously reported anode materials in KIBs and even in most sodium-ion batteries. The superior performance is attributed to the unique structure of CNFs, in which the porous structure can effectively alleviate the volume expansion induced by the insertion of large K ions. Considering the abundance and widespread distribution of potassium in the Earths crust, the encouraging results make KIBs a strong competitor to Na-ion batteries as an alternative energy storage technology to Li-ion batteries.

Strong Hall–Petch Type Behavior in the Elastic Strain Limit of Nanotwinned Gold Nanowires

Pushing the limits of elastic deformation in nanowires subjected to stress is important for the design and performance of nanoscale devices from elastic strain engineering. Particularly, introducing nanoscale twins has proved effective in rising the tensile strength of metals. However, attaining ideal elastic strains in nanotwinned materials remains challenging, because nonuniform twin sizes locally affect the yielding behavior. Here, using in situ high-resolution transmission electron microscopy tensile testing of nanotwinned [111]-oriented gold nanowires, we report direct lattice-strain measurements that demonstrate a strong Hall-Petch type relationship in the elastic strain limit up to 5.3%, or near the ideal theoretical limit, as the twin size is decreased below 3 nm. It is found that the largest twin in nanowires with irregular twin sizes controls the slip nucleation and yielding processes in pure tension, which is in agreement with earlier atomistic simulations. Continuous hardening behavior without loss of strength or softening is observed in nanotwinned single-crystalline gold nanowires, which differs from the behaviors of bulk nanocrystalline and nanotwinned-nanocrystalline metals. These findings are of practical value for the use of nanotwinned metallic and semiconductor nanowires in strain-engineered functional microdevices.

Tuning the Outward to Inward Swelling in Lithiated Silicon Nanotubes via Surface Oxide Coating

Electrochemically induced mechanical degradation hinders the application of Si anodes in advanced lithium-ion batteries. Hollow structures and surface coatings have been often used to mitigate the degradation of Si-based anodes. However, the structural change and degradation mechanism during lithiation/delithiation of hollow Si structures with coatings remain unclear. Here, we combine in situ TEM experiment and chemomechanical modeling to study the electrochemically induced swelling of amorphous-Si (a-Si) nanotubes with different thicknesses of surface SiOx layers. Surprisingly, we find that no inward expansion occurs at the inner surface during lithiation of a-Si nanotubes with native oxides. In contrast, inward expansion can be induced by increasing the thickness of SiOx on the outer surface, thus reducing the overall outward swelling of the lithiated nanotube. Moreover, both the sandwich lithiation mechanism and the two-stage lithiation process in a-Si nanotubes remain unchanged with the increasing thickness of surface coatings. Our chemomechanical modeling reveals the mechanical confinement effects in lithiated a-Si nanotubes with and without SiOx coatings. This work not only provides insights into the degradation of nanotube anodes with surface coatings but also sheds light onto the optimal design of hollow anodes for high-performance lithium-ion batteries.