Title: Engineered morphologic material structures
Description: Morphologies include the study of shape, size and structure for materials from atomic scale to macroscales. Properties/functions of material structures in general are dependent on morphologies, and tunable properties in chemical and physical can be realized through changing morphologies on surfaces and in bulk systems of materials. For low-dimensional materials, atomic modifications and changes in lattice morphologies can introduce varieties of fascinating phenomena and unconventional intrinsic properties in electric, mechanics chemistry and etc. The reason behind such controllability is that morphological undulation usually is consistent with the mapping of strain, which is related to atomic structures of materials. For micro/macro scale materials, interactions of surface tension, mechanical deformation, etc. dominate the morphological evolution. Structural designs and morphological control can achieve desirable functionalities, for example mechanical flexibility and liquid wettability for practical applications.

Herein, strain-engineering strategies including mechanical loading and atomic displacement were applied to modify and control morphologies in materials with different length scales. We firstly investigated the fundamental mechanism of morphological evolution through various load strategies, and relationship between morphologies and the properties of material structures across from nanoscale, microscale to macroscale, including graphene, phosphorene, core-shell microparticles and soft materials/bilayers, etc. Furthermore, we demonstrated to two applications of utilizing designed morphologies, which targeted to figures out challenges in the field of energy conversion and storage to close energy loop. Therefore, we mainly focus on the relation of engineered strategy-morphology-mechanism/property-functional devices in this thesis. Firstly, engineered morphologies in nanomaterials of graphene and phosphorene were investigated through strain-localization, gradient strain, bending/pressing. The effects of surface morphologies on fundamental properties including thermal conductivities, mechanics, electrics, surface energy and chemical reactivities were studied through molecular dynamics (MD) simulations and first-principle calculations combined with experimental verifications: Increased applications of nanoporous graphene in nanoelectronics and membrane separations require ordered and precise perforation of graphene, whose scalablility and time/cost effectiveness represent a significant challenge in existing nanoperforation methods, such as catalytical etching and lithography.

We reported a strain-guided perforation of graphene through oxidative etching, where nanopores nucleate selectively at the bulges induced by the pre-patterned nano-protrusions underneath. Using reactive molecular dynamics and theoretical models, we uncover the perforation mechanisms through the relationship between bulge-induced strain and enhanced etching reactivity. Parallel experiments of CVD graphene on SiO2 NPs/ SiO2 substrate verify the feasibility of such strain-guided perforation and evolution of pore size by exposure durations to oxygen plasma. When a nanodroplet is placed on a lattice surface, an inhomogeneous surface strain field perturbs the balance of van der Waals force between the nanodroplet and surface, thus providing a net driving force for nanodroplet motion. Using molecular dynamics and theoretical analysis, we studied the effect of strain gradient on modulating the movement of a nanodroplet. Both modeling and simulation showed that the driving force is opposite to the direction of strain gradient, with a magnitude that is proportional to the strain gradient as well as nanodroplet size.

Two representative surfaces, graphene and copper (111) plane, were exemplified to demonstrate the controllable motion of nanodroplet. When the substrate underwent various types of reversible deformations, multiple motion modes of nanodroplets could be feasibly achieved, including acceleration, deceleration and turning, becoming a facile strategy to manipulate nanodroplets along a designed 2D pathway. Using molecular dynamics (MD) simulations, we explored the structural stability and mechanical integrity of phosphorene nanotubes (PNTs), where the intrinsic strain in the tubular PNT structure plays an important role. It was proposed that the atomic structure of larger-diameter armchair PNTs (armPNTs) could remain stable at higher temperature, but the high intrinsic strain in the hoop direction renders zigzag PNTs (zigPNTs) less favorable. The mechanical properties of PNTs, including the Young’s modulus and fracture strength, are sensitive to the diameter, showing a size dependence. A simple model is proposed to express the Young’s modulus as a function of the intrinsic axial strain which in turns depends on the diameter of PNTs.

A new phosphorous allotrope, closed-edged bilayer phosphorene nanoribbon, was proposed via radially deforming armchair phosphorene nanotubes. Using molecular dynamics simulations, the transformation pathway from round phosphorene nanotubes falls into two types of collapsed structures: arc-like and sigmoidal bilayer nanoribbons, dependent on the number of phosphorene unit cells. The fabricated nanoribbions are energetically more stable than their parent nanotubes. It was also found via ab initio calculations that the band structure along tube axis substantially changes with the structural transformation. The direct-to-indirect transition of band gap was highlighted when collapsing into the arc-like nanoribbons but not the sigmoidal ones. Furthermore, the band gaps of these two types of nanoribbons showed significant size-dependence of the nanoribbon width, indicative of wider tunability of their electrical properties. Secondly, we studied fundamental mechanisms of generating fascinating surface morphologies on the micro materials/structures of core/shell microsphere driven by surface instability, which is not different those in nanoscale.

The island-like dot pattern on spherical substrate were investigated: Through strain-induced morphological instability, protruding patterns of roughly commensurate nanostructures are self-assembled on the surface of spherical core/shell systems. A three-dimensional (3D) phase field model was established for closed substrate. We investigated both numerically and analytically the kinetics of the morphological evolution, from grooves to separated islands which are sensitive to substrate curvature, misfit strain and modulus ratio between core and shell. The faster growth rate of surface undulation was associated with the core/shell system of harder substrate, larger radius or misfit strain. Based on a Ag core/SiO2 shell system, the self-assemblies of SiO2 nano-islands were explored experimentally. The numerical and experimental studies herein could guide the fabrication of ordered quantum structures via surface instability on closed and curved substrates. Up to macroscale material structures, the variety and controllability surface morphologies on soft materials and bilayer films were realized through pre-pattern defects of cavities and in-plane compression.

The checkboard and wrinkling surface patterns were observed in different systems through both finite element simulations and 3D printing technique: A rich diversity of surface topologies is controllably engineered by patterning cavities embedded beneath the surface of soft materials. Upon external compression, the surface undergoes the reversible transformation from the flat surface to various surface topographies, including the periodic checkerboard pattern with alternatively convex and concave features. To design the surface features, both 2D and 3D finite element based-simulations were performed. It was demonstrated that the periodic surface features with controllable morphology, such as 1D waves, checkerboard pattern and mutually perpendicular apexes, etc. can be realized through varying cavity geometries (e.g., relative inter-cavity distance, shapes and biaxial/uniaxial load). Based on 3D printed prototypes, we further conducted experiments to validate the simulation results of 2D morphologies.

The patterned cavities in soft materials made designing a variety of reversible surface features possible, offering an effective fabrication approach for wide application across multiple scales. Wrinkle formation followed by sharp strain localization is commonly observed in compressed stiff film/soft substrate systems. However, cavities or defects beneath the film may directly trigger the formation of local ridges and then folding configurations at a relatively small compressive strain, and a mixture of wrinkles and folds upon further compression. The morphological transition is different than those of defect-free substrates. Numerical simulations of continuously compressed bilayer with pre-patterned cavities were carried out to elucidate the transition mechanism of surface patterns. Parallel experiments of cavities-patterned bilayer prototypes by 3D-printing were also performed to validate the findings in simulations. A rich diversity of periodic surface topologies, including overall spreading waves, localizations, saw-like and co-existing features of folds and wrinkles can be obtained by varying the diameter, depth and spacing of cavities, which provides a potential approach to engineer various surface patterns for applications.

Since these discussed material structures are promising candidates for energy/environmental applications, two device-level functional systems/products here utilize intriguing morphologies in both nanoscale and macroscale. To close energy loop, the energy conversion reactor (chemical loop reduction of CO2) and the energy storage device (flexible lithium ion battery) were demonstrated: We reported an effective reduction method for splitting air-containing CO2 into CO for high-value chemicals, through a chemical looping redox scheme with Cu-doped LaFeO3 perovskites as efficient oxygen carriers for splitting CO2 with a high-concentration of O2 (e.g. 1:5 O2/CO2 molar ratio, mimicking 1:1 CO2/air mixture). Up to 2.28 mol/kg CO yield was achieved with good stability in the CO2 splitter, five times higher than that with the conventional pristine LaFeO3 perovskite. Through ab initio calculations, we uncovered that the exsolution of metallic Cu on the surface of reduced perovskite is capable of mitigating the competition between CO2 and O2 for the re-oxidation step.

This air-stable and scalable scheme can economically integrate with upstream DAC and downstream gas-to-liquids plants, exhibiting up to 94.5% and 42.8% reduction in net CO2 emission for valuable chemicals production (methanol and acetic acid) when compared with the coal gasifier-based route and this redox scheme using pure CO2, respectively. Flexible batteries, seamlessly compatible with flexible and wearable electronics, attract a great deal of research attention. Current designs of flexible batteries are unable to meet one of the most extreme yet common deformation scenarios in practice, folding, while retaining high energy density. Inspired by origami folding, we proposed a novel strategy to fabricate zigzag-like lithium ion batteries with superior foldability. The battery structure could approach zero-gap between two adjacent energy storage segments, achieving an energy density that is 96.4% of that in a conventional stacking cell. A foldable battery thus fabricated demonstrated an energy density of 275 Wh L-1 and was resilient to fatigue over 45,000 dynamic cycles with a folding angle of 130°, while retaining stable electrochemical performance.

Additionally, the power stability and resilience to nail shorting of the foldable battery were also examined.