Shuman Xia

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.

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.

Atomic-scale mechanisms of sliding along an interdiffused Li-Si-Cu interface.

We perform ab initio calculations on the shear deformation response of the interdiffused Li-Si-Cu phase structure existing between a lithiated Si electrode and a Cu current collector. We show that the formation of well-delineated and weakly bonded Si-Cu and Li-Cu crystalline atomic layers within this phase structure facilitates interface sliding. However, sliding can be terminated by the formation of LiSi3 compounds across these atomic layers, which causes the abrupt capacity fade of the electrode after repeated cycling.

Brittle-to-ductile transition of lithiated silicon electrodes: Crazing to stable nanopore growth

Using first principle calculations, we uncover the underlying mechanisms explaining the brittle-to-ductile transition of LixSi electrodes in lithium ion batteries with increasing Li content. We show that plasticity initiates at x = ∼ 0.5 with the formation of a craze-like network of nanopores separated by Si-Si bonds, while subsequent failure is still brittle-like with the breaking of Si-Si bonds. Transition to ductile behavior occurs at x ⩾ 1 due to the increased density of highly stretchable Li-Li bonds, which delays nanopore formation and stabilizes nanopore growth. Collapse of the nanopores during unloading of the LixSi alloys leads to significant strain recovery.

Nanoscale Deformation Analysis With High-Resolution Transmission Electron Microscopy and Digital Image Correlation

We present an application of the digital image correlation (DIC) method to high-resolution transmission electron microscopy (HRTEM) images for nanoscale deformation analysis. The combination of DIC and HRTEM offers both the ultrahigh spatial resolution and high displacement detection sensitivity that are not possible with other microscope-based DIC techniques. We demonstrate the accuracy and utility of the HRTEM-DIC technique through displacement and strain analysis on amorphous silicon. Two types of error sources resulting from the transmission electron microscopy (TEM) image noise and electromagnetic-lens distortions are quantitatively investigated via rigid-body translation experiments. The local and global DIC approaches are applied for the analysis of diffusion- and reaction-induced deformation fields in electrochemically lithiated amorphous silicon. As a result, the DIC technique coupled with HRTEM provides a new avenue for the deformation analysis of materials at the nanometer length scales.