Functional data analysis (FDA) studies data in the form of measurements over a domain as whole entities. Our first focus is on the post-hoc analysis with pairwise and contrast comparisons of the popular functional ANOVA model comparing groups of functional data. Existing contrast tests assume independent functional observations within group. In reality, this assumption may not be satisfactory since functional data are often collected continually overtime on a subject. In this work, we introduce a new linear contrast test that accounts for time dependency among functional group members. For a significant contrast test, it can be beneficial to identify the region of significant difference. In the second part, we propose a non-parametric regression procedure to obtain a locally sparse estimate of functional contrast. Our work is motivated by a biomedical study using Raman spectroscopy to monitor hemodialysis treatment near real-time. With contrast test and sparse estimation, practitioners can monitor the progress of the hemodialysis within session and identify important chemicals for dialysis adequacy monitoring. In the third part, we propose a functional data model for degradation analysis of functional data. Motivated by degradation analysis application of rechargeable Li-ion batteries, we combine state-of-the-art functional linear models to produce fully functional prediction for curves on heterogenous domains. Simulation studies and data analysis demonstrate the advantage of the proposed method in predicting degradation measure than existing method using aggregation method. / Doctor of Philosophy / Functional data analysis (FDA) studies complex data structure in the form of curves and shapes. Our work is motivated by two applications concerning data from Raman spectroscopy and battery degradation study. Raman spectra of a liquid sample are curves with measurements over a domain of wavelengths that can identify chemical composition and whose values signify the constituent concentrations in the sample. We first propose a statistical procedure to test the significance of a functional contrast formed by spectra collected at beginning and at later time points during a dialysis session. Then a follow-up procedure is developed to produce a sparse representation of the contrast functional contrast with clearly identified zero and nonzero regions. The use of this method on contrast formed by Raman spectra of used dialysate collected at different time points during hemodialysis sessions can be adapted for evaluating the treatment efficacy in real time. In a third project, we apply state-of-the-art methodologies from FDA to a degradation study of rechargeable Li-ion batteries. Our proposed methods produce fully functional prediction of voltage discharge curves allowing flexibility in monitoring battery health.

Formula SAE (FSAE) vehicle systems are very complex. Understanding how subsystems effect the overall vehicle is essential for making design trade-offs. FSAE is a competitive environment. Teams need to have reliable and high performing vehicles to do well in competition. The Virginia Tech (VT) FSAE team has produced a prototype electric powertrain (EPT) vehicle, VTM16e, and will take their first EPT vehicle, VTM17e, to competition in 2017. The use of model-based design (MBD) for an EPT FSAE vehicle is investigated through this thesis. The goal of the research is to build the framework of a full vehicle simulation to take knowledge gained from the VTM16e prototype vehicle, and apply it to the VTM17e competition vehicle. A top-down, bottom-up approach is taken to build a full vehicle model of an EPT FSAE vehicle. A full vehicle simulation is built with subsystems to establish an overall structure and subsystem interactions. Individual subsystems are then focused on for testing and validation. Breaking the vehicle down into subsystems allows the overall model to be incrementally improved. The battery subsystem is focused on in this thesis. Extensive testing is performed on the batteries to characterize their performance. Computer models are generated from empirical data through parameter estimation techniques. Validation of the battery models is performed and the resulting model is incorporated into the overall vehicle model. Performance limits of the vehicle are determined through model exploration, and design modifications to increase the reliability and performance for the VTM17e vehicle are proposed. / Master of Science

Lithium-ion batteries (LIBs) play a pivotal role in advancing transportation electrification, offering a crucial solution to address climate change and fossil fuel depletion, but the current energy density of LIBs remains unsatisfying, limiting electric transportation range. To address this limitation, extensive efforts focus on developing novel electrode materials, including high-voltage cathodes and high-specific-capacity electrodes. However, the pursuit of higher energy densities introduces safety concerns due to the higher possibility of thermal runaway and flammable nature of conventional liquid electrolytes. In this doctoral thesis, I will present several innovative strategies for high-performance lithium battery systems aimed at enhancing the mileage of electric transportation without compromising or even enhancing safety. The first part (Chapter 3) discusses a novel design for structural batteries. Structural batteries are the energy storage devices with enhanced mechanical properties integrated as structural components in vehicles to reduce vehicle weights and increase mileage. Through the development of a scalable and feasible tree-root-like lamination at the electrode/separator interface, an 11-fold enhancement in the flexural modulus of pouch cells is achieved, and the underlying mechanism is revealed by finite element simulations. This lamination has a minimal impact on the electrochemical performance of LIBs and the smallest reported specific energy reduction of ~3% in structural batteries. The prototype "electric wings" showcases stable flight for an aircraft model, highlighting the effectiveness and scalability of engineering interfacial adhesion in developing structural batteries with superior mechanical and electrochemical properties. The second part (Chapter 4) presents a design rule for polymer electrolytes to enhance lithium metal battery safety. Lithium metal batteries are attractive for electric transportation due to their high energy densities, but their application is hindered by the safety concerns from dendrite growth. In this work, we observe that if the compositions of polyethylene oxide (PEO) electrolytes are near the boundary between amorphous and polymer-rich regions, concentration polarization in electrolytes will induce a phase transformation and create a PEO-rich phase at the electrode surface. This new phase is mechanically rigid with a Young’s modulus of ∼1-3 GPa so that it can suppress lithium dendrites, which allows Li/PEO/LiFePO₄ cells with such a phase transformation demonstrate superior lithium reversibility without dendrites for 100 cycles. The third part (Chapter 5) proposes an innovative cathode design for all-solid-state Li-S batteries (ASSLSBs) which have ultra-high energy densities and enhanced battery safety. However, conventional cathode designs of filling sulfur in carbon hosts suffer from accelerated decomposition of electrolytes and sulfur detachment, leading to significant capacity loss. As a solution, I propose that nonconductive polar hosts allow long cycling life of ASSLSBs via stabilizing the adjacent electrolytes and bonding sulfur/Li₂S steadily to avoid detachment. By using a mesoporous SiO₂host filled with 70 wt.% sulfur as the cathode, we demonstrate steady cycling in ASSLSBs with a capacity reversibility of 95.1% in the initial cycle and a discharge capacity of 1446 mAh g-1 after 500 cycles at C/5.

Energy storage is a necessity for the electrification of the modern world and the progression towards renewable energy. Designing new and innovative energy storage alternatives is one of the many challenges taken on by the Nuckolls group at Columbia University. More precisely, organic materials for energy storage with facile synthesis methods, non-toxic materials, and compatibility with aqueous electrolytes are a focus of this research. For this purpose, Perylenediimide (PDI) is the chosen primary molecular building block, that has enabled design of redox active materials due to its versatility as a structural unit, as well as its remarkable electrochemical performance. In this thesis 3 classes of materials based on PDI - small molecules, polymer networks, and COF materials - are compared; providing insights into how their design impacts electrochemical performance. Chapter 1 provides an overview of existing organic materials for energy storage. In particular, explaining the limitations, challenges, current landscape, and future of organic materials for battery and pseudocapacitive applications. This research area confronts current traditional energy storage strategies, such as lithium-ion batteries, with new organic alternatives that offer opportunities that could be more eco-friendly alternatives to lithium-ion batteries in specific applications. Chapter 2 describes the synthesis and characterization of PHATN, the highest performing aqueous n-type pseudocapacitor based on the PDI molecular backbone integrated into a 3-dimensional polymer network, and the relationship between electrochemical performance and structural contortion generated because of the molecular design. This is accomplished by benchmarking against a non-contorted linear polymer and comparing their electrochemical properties. This work provides the foundation for chapters 3 and 4. Chapter 3 expands on the use of molecular contortion as a design principle for molecular electronics, associating molecular contortion to electrochemical performance by generating helical inspired PDI polymers. This design reveals that the helical motif allows for enhanced electronic communication between the redox moieties and leads to higher device performance. Chapter 4 utilizes linear PDI polymers as a non-contorted control in comparison to the helical inspired polymers described in chapter 3. This linear motif reveals the competing design principle of increased surface area for electrolyte access to redox sites which is shown to increase device performance. Chapter 5 discusses a COF inspired redox active 2-dimensional polymers (RA-2DP) based on PDI materials and how the structural motif and conductive linkers can improve electrochemical performance. This chapter validates the design criteria outlined in chapter 4 and explains how these RA-2DPs and similar structures can enhance energy storage in organic materials. Collectively, this work provides a structured story of PDI materials, their potential as energy storage materials, and the design principles that have led to increased performance. The work completed in this thesis points towards structured and porous redox active organic materials as next generation energy storage alternatives. With the consideration of renewable energy and challenges with existing energy storage options, it is our hope that organic materials will contribute to this ever evolving and growing research area to create a more sustainable and environmentally friendly future.

<p dir="ltr">This study investigates the electrochemical behavior of molybdenum disulfide (MoS₂) when utilized as an anode material in Li-ion batteries, particularly focusing on the intriguing phenomenon of extra capacity observed beyond theoretical expectations and the unique discharge curve of the first cycle. Employing a robust suite of advanced characterization methods such as in situ and ex situ X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), the research unravels the complex structural and chemical evolution of MoS₂ throughout its cycling process. A pivotal discovery of the research is the identification of a distinct lithium intercalation mechanism in MoS₂, which leads to the formation of reversible Li_xMoS₂. These phases play a crucial role in contributing to the extra capacity observed in the MoS₂ electrode. Additionally, density functional theory (DFT) calculations have been utilized to explore the potential for overlithiation within MoS₂, suggesting that Li₅MoS₂ could be the most energetically favorable phase during the lithiation-delithiation process. This study also explores the energetics of a Li-rich phase forming on the surface of Li₄MoS2, indicating that this configuration is energetically advantageous and could contribute further to the extra capacity. The incorporation of reduced graphene oxide (RGO) as a conductive additive in MoS₂ electrodes, demonstrating that RGO notably improves the electrochemical performance, rate capability, and durability of the electrodes. These findings are supported by experimental observations and are crucial for advancing the understanding of MoS₂ as a high-capacity anode material. The implications of this research are significant, offering a pathway to optimize the design and composition of electrode materials to exceed traditional performance and longevity limits in Li-ion batteries.</p>

This case study investigates the potential graphite circular economy within the lithium-ion battery industry, intending to create sustainable management of graphite waste streams. The improper handling of graphite as waste amplifies the carbon footprint and incurs additional costs for battery recyclers. Unlike cathode materials in batteries, graphite regeneration into battery-grade material has not beenindustrialized. Therefore, the study investigates recycling and other alternative approaches to obtain the circularity of graphite. The research explores downcycling, recycling, and upcycling business modelsfor graphite from lithium batteries. With the aim to maximize value and minimize efforts and associated costs. As per methods, an exploratory qualitative method was employed with the data mainly collected through interviews with actors in the graphite sector and recycling technologies. The findings showeconomic viability, feasibility, market dynamic, and regulatory aspects as crucial considerations for the decision-making of battery recyclers. Given the novelty of the material, evaluating technical feasibility through research and development requires coordination with potential partners. Several potential customer options, including graphene applications, steel and refineries, and refractory products, are proposed, each involving a respective business model. Furthermore, the study suggests diversifying partners and establishing partnerships with material receivers as a short-term strategy while awaiting advancements in recycling and upcycling technologies.

The invention of the lithium-ion battery has revolutionized the passenger transportation field in recent years, and it has emerged as one of the state-of-the-art solutions to address greenhouse gases emission and air pollution issues. Layered oxide lithium-ion battery cathode materials have become commercially successful in the past few decades due to their high energy density, high power density, long cycle life, and low cost. Yet, with the increasing demand for battery performance, it is crucial to understand the material fading mechanisms further to improve layered oxide materials' performance. A heterogeneous redox reaction is a dominant fading mechanism, which limits the utilization percentage of a battery materials' redox capability and leads to adverse effects such as detrimental interfacial reactions, lattice oxygen release, and chemomechanical breakdown. Crystallographic defects, such as dislocations and grain boundaries, are rich in battery materials. These crystallographic defects change the local lithium-ion diffusivity and have a dramatic effect on the redox reactions. To date, there is still a knowledge gap on how various crystallographic defects affect electrochemistry at the microscopic scale. Herein, we adopted synchrotron-based diffraction, imaging, and spectroscopic techniques to systematically study the correlation between crystallographic defects and redox chemistries in the nanodomain. Our studies shed light on design principles of next-generation battery materials. In Chapter 1, we first provide a comprehensive background introduction on the battery chemistry at various length scales. We then introduce the heterogeneous redox reactions in layered oxide cathode materials, including a discussion on the impacts of heterogeneous redox reactions. Finally, we present the different categories of crystallographic defects in layered oxide materials and how these crystallographic defects affect electrochemical performance. In Chapter 2, we use LiCoO2, a representative layered oxide cathode material, as the material platform to quantify the categories and densities of various crystallographic defects. We then focus on geometrically necessary dislocations as they represent a major class of crystallographic defects in LiCoO2. Combining synchrotron-based X-ray fluorescence mapping, micro-diffraction, and spectroscopic techniques, we reveal that geometrically necessary dislocations can facilitate the charging reactions in LiCoO2 grains. Our study illustrates that the heterogeneous redox chemistries can be potentially mitigated by precisely controlling the defects. In Chapter 3, we systematically investigated how grain boundaries affect redox reactions. We reveal that grain boundaries can guide redox reactions in LiNixMnyCo1-x-yO2 (NMC) materials. Specifically, NMC materials with radially aligned grains have a more uniform charge distribution, less stress mismatch, and better cycling performance. NMC materials with randomly orientated grains have a more heterogeneous redox reaction. These heterogeneous redox reactions are related to the lattice strain mismatch and worse cycling performance. Our study emphasizes the importance of tuning grain orientations to achieve improved performance. Chapter 4 systematically investigated how the grain boundaries and crystallographic orientations affect the thermal stability of layered oxide cathode materials. Combining diffraction, spectroscopic, and imaging techniques, we reveal that a cathode materials' microstructure plays a significant role in determining the lattice oxygen release behavior and, therefore, determines cathode materials' thermal stability. Our study provides a fundamental understanding of how the grain boundaries and crystallographic orientations can be tuned to develop better cathode materials for the next-generation Li-ion batteries. Chapter 5 summarizes the contributions of our work and provides our perspective on future research directions. / Doctor of Philosophy / Lithium-ion battery technology has revolutionized the portable electronic device and electric vehicle markets in recent years. Yet, the performance of current lithium-ion batteries still cannot satisfy customer demands. To further improve battery performance, we need a deeper understanding of why battery materials degrade over long-term cycling. One of the fading mechanisms in lithium-ion batteries is heterogeneous redox reactions, i.e., charge or discharge reactions do not proceed at the same pace at different locations in the electrode materials. Herein, we utilize layered oxide cathode materials as an example to systematically investigate how crystallographic defects in the cathode materials lead to heterogeneous redox reactions. Our study indicates that crystallographic defects, such as geometrically necessary dislocations, contribute positively to the charging reaction of the cathode materials. We also unveil that the grain crystallographic orientations of the primary particles affect the redox reactions directly. By aligning the single grains in the radial direction, the volumetric-change-induced stress can be effectively mitigated to ensure prolonged cycling performance. Our study also points out that the single grain orientations are related to the thermal stability of the battery materials. To summarize, our studies provide new insights into the heterogeneous redox reactions in battery materials and offer critical material design criteria to improve battery performance further.

The present thesis demonstrates and discusses polymeric ion and mixed ion-electron conductors for rechargeable batteries based on lithium viz. lithium-ion and lithium-sulphur batteries. The proposed polymer ion conductors in the thesis are discussed primarily as potential alternatives to conventional liquid and solid-crystalline electrolytes in lithium-ion batteries. These discussions are part of Chapters 2-4. On the other hand, the polymer based mixed ion-electron conductor is demonstrated as a novel electrode for lithium-Sulphur battery in Chapter 5. Possibility of application of polymer ion conductors is discussed in the context of Li-S battery in Chapter 6. A distinct correlation between the physical properties and electrochemical performance of the proposed conductors is highlighted in detail in this thesis. Systematic investigation of the ion transport mechanism in the polymeric ion conductors has been carried out using various spectroscopic techniques at different time and length scales. Such detailed investigations demonstrate the key structural and physical parameters for design of alternative polymer conductors for rechargeable batteries. Though the thesis discusses the various polymeric conductors in the context of lithium-based batteries, it is strongly felt that the design strategies are equally likely to be beneficial for different battery chemistries as well as for other electrochemical generation and storage devices. A brief discussion of the contents and highlights of the individual chapters are described below: The thesis comprises of six Chapters. Chapter 1 briefly reviews the important developments and materials of lithium-based batteries, with specific focus on Li-ion and Li-S batteries. It starts with discussions on different types of liquid, solid crystalline and solid-like electrolytes. Their materials characteristics, advantages and disadvantages are discussed in the context of secondary batteries such as lithium-ion and lithium-sulphur batteries. As prospective alternative electrolytes polymer based soft matter electrolytes are discussed in detail. Special emphasis is given to the recent developments in polymer electrolytes and their ion conduction mechanism, which are central themes to this thesis. The importance of investigation of charge transport, typically ion, on electrochemical processes is also briefly discussed in Chapter 1. A brief discussion about the characteristics, materials and non-trivialities of the electrochemical storage process in Li-S battery is also reviewed. Chapter 2A demonstrates a binary polymer physical network based gel (PN-x) electrolyte, comprising of an ionic liquid confined inside a binary polymer system for electrochemical devices such as secondary batteries. The synthesis, physical property and electrochemical performances are studied as a function of content of one of the polymers in this Chapter. A physical network of two polymers with different functional groups leads to multiple interesting consequences. The polymer physical network characteristics determine all physical properties including electrochemical property of the ionic liquid integrated PN based GPE. The conductivities of the proposed gel are nearly an order in magnitude higher than the unconfined ionic liquid electrolyte and displays good dimensional stability and electrochemical performance in a separator-free battery configuration. The ac-impedance spectroscopy, steady shear viscosity measurement, dynamic rheology are employed to study physical properties of the proposed gel polymer electrolyte. Chapter 2B discusses the detailed investigations of the ion transport mechanism of the gel polymer electrolyte, as discussed in Chapter 2A. Ion conduction mechanism is investigated in the light of ion diffusion and solvent dynamics of the entrapped ionic liquid inside the polymer. The studies reveal a heavy influence of network characteristics on the ion conduction mechanism. The influence of solvent dynamics on the ion transport is drastically altered by polymer physical network. Consequently, a drastic change in the ion mobility and nature of predominant charge carrier is observed in the polymer physical network based gel electrolyte. A clear transformation from dual ion conductivity to a predominantly anion conductivity is observed on going from single polymer to a dual polymer network. The spectroscopic tools such as pulsed field gradient nuclear magnetic resonance (PFG–NMR), Brillouin light scattering spectroscopy, ac-impedance spectroscopy, FT-Raman and FTIR spectroscopy were used to elucidate the ion transport mechanism in the Chapter. Chapter 3 demonstrates a simple design strategy of gel polymer electrolyte comprising of a lithium salt (lithium bis(trifluoromethanesulfonyl) imide, LiTFSI) solvated by two plastic crystalline solvents, one a solid (succinonitrile, abbreviated as SN) and another a (room temperature) ionic liquid (1-butyl-1-methyl-pyrrolidinium bis(trifluoromethane sulfonyl) imide, (abbreviated as IL) confined inside a linear network of poly(methyl methacrylate) (PMMA). The concentration of the IL component determines the physical properties of the unconfined electrolyte and when confined inside the polymer network in gel polymer electrolyte. Intrinsic dynamics of one plastic crystal influences the conduction mechanism of gel polymer electrolytes. The enhanced disordering in the plastic phase of succinonitrile by IL doping alters both the local ion environment and viscosity. The proposed plastic crystal electrolytes show predominantly anion conduction (tTFSI ≈ 0.5) however, lithium transference number (tLi ≈ 0.2) is nearly an order higher than the ionic liquid electrolyte (IL-LiTFSI) (tLi ≈ 0.02-0.06), discussed in Chapter 2. The gel polymer electrolyte displayed high mechanical compliability, stable Li-electrode | electrolyte interface, low rate of Al corrosion and stable cyclability. The promising electrochemical performance further justifies simple strategy of employing mixed physical state plasticizers to tune the physical properties of polymer electrolytes requisite for application in rechargeable batteries. Chapter 4A proposes a novel liquid dendrimer–based single ion conducting liquid electrolyte as potential alternative to conventional molecular liquid solvent–salt solutions and conventional solid polymer electrolytes for rechargeable batteries, sensors and actuators. The physical properties are investigated as a function of peripheral functionalities in the first generation poly(propyl ether imine) (G1-PETIM)–lithium salt complexes. The change in peripheral group simultaneously affects the effective physical properties viz. viscosity, ionic conductivity, ion diffusion coefficients, transference numbers and also the electrochemical response. The specific change from ester (–COOR) to cyano (–CN) terminated peripheral group resulted in a remarkable switch over from a high cation (tLi+ = 0.9 for –COOR) to a high anion (tPF6- = 0.8 for –CN) transference number. Chapter 4B presents an analysis of the frequency dependent ionic conductivity of single ion dendrimer conductors by using time temperature scaling principles (TTSPs) and dielectric modeling of the electrode polarization. The TTSP provides information on the salt dissociation and number density of mobile charges and hence provides direct insights into the ion conduction mechanism. Summerfield and Baranovskii–Cordes scaling laws, which are well known TTSPs, have been applied to analyze the ion conductivity. The electrode polarization, which quantifies the number density of mobile charges and ionic mobility, is studied using Macdonald-Coelho model of electrode polarization. The combination of these two theoretical investigations of the experimental data emanating from one technique i.e. ac– impedance spectroscopy, predicts independently the contributions of the effect of mobile ion charges and ionic mobility to ion conduction mechanism. In Chapter 5 focus shifts from polymer ion conductors to polymer mixed ion-electron conductor. The polymer mixed ion-electron conductor is demonstrated as a novel electrode material for Li-S battery. A simple strategy to overcome the challenges towards practical realization of a stable high performance Li–S battery is discussed. A soft mixed conducting polymeric network is utilized to configure sulphur nanoparticle. The soft matter network provides efficient and distinct pathways for lithium and electron conduction simultaneously. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li–S batteries. The S-MIEC is characterized by several methods: powder-X-ray diffraction (PXRD), thermo gravimetric analysis (TGA), fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), ac-impedance spectroscopy and dc current-voltage measurements are performed to evaluate conductivity of S-MIEC cathode. Electrochemical studies such as cyclic voltammetry, galvanostatic charge-discharge cycling, galvanostatic intermittent titration (GITT) are performed to demonstrate feasibility of S-MIEC in the Li–S battery performance. Chapter 6 provides a brief summary of the work carried out as part of this thesis and also demonstrates the future perspective of the present work. Potential of the polymer physical network based gel polymer electrolytes, which are discussed in Chapter 2A-B for lithium-ion batteries, are demonstrated in Li-S battery. The proposed polymer physical network confines higher order lithium polysulfides (typically Li2S8) dissolved in tetraethylene glycol dimethyl ether (TEGDME) based electrolyte (TEGDME-1M LiTFSI). The three dimensional polymer network is proposed to be formed by physical blending of the poly(acrylonitrile) (PAN) with the copolymer of AN and poly(ethylene glycol) methyl ether methacrylate (PEGMA), [ P(AN–co–PEGMA)]. We extend here the similar synthetic approaches as described in Chapter 2A. The approach proposed and demonstrated in this concluding Chapter is expected to mitigate some of the major issues of Li-S chemistry. The proposed Li2S8 confined gel electrolyte exhibits moderately high values of ionic conductivity, 2 × 10-3 Ω-1cm-1 and shows a stable capacity of 350 mAhg-1 over 30 days in a separator free Li-S battery.

Lithium alloys with metallic or semi-metallic elements are attractive candidate materials for the next-generation rechargeable Li-ion battery anodes, thanks to their large specific and volumetric capacities. The key challenge, however, has been the large volume changes, and the associated stress buildup and failure during cycling. The chemo-mechanics of alloy-based electrode materials entail interactions among diffusion, chemical reactions, plastic flow, and material property evolutions. In this study, a continuum theory of two-way coupling between diffusion and deformation is formulated and numerically implemented. Analyses based on this framework reveal three major conclusions. First, the stress-to-diffusion coupling in Li/Si is much stronger than what has been known in other electrode materials. Practically, since the beneficial effect of stress-enhanced diffusion is more pronounced at intermediate or higher concentrations, lower charging rates should be used during the initial stages of charging. Second, when plastic deformation and lithiation-induced softening take place, the effect of stress-enhanced diffusion is neutralized. Because the mechanical driving forces tend to retard diffusion when constraints are strong, even in terms of operational charging rate alone, Li/Si nano-particles are superior to Li/Si thin films or bulk materials. Third, the diffusion of the host atoms can lead to significant stress relaxation even when the stress levels are below the yield threshold of the material, a beneficial effect that can be leveraged to reduce stresses because the host diffusivity in Li/Si can be non-negligible at higher Li concentrations. A theory of coupled chemo-mechanical fracture driving forces is formulated in order to capture the effect of deformation-diffusion coupling and lithiation-induced softening on fracture. It is shown that under tensile loading, Li accumulates in front of crack tips, leading to an anti-shielding effect on the energy release rate. For a pre-cracked Li/Si thin-film electrode, it is found that the driving force for fracture is significantly lower when the electrode is operated at higher Li concentrations -- a result of more effective stress relaxation via global yielding. The results indicate that operation at higher concentrations is an effective means to minimize failure of thin-film Li/Si alloy electrodes.

Three-dimensional macroporous structures (‘opals’ and ‘inverse opals’) can be produced by colloidal crystal templating, one of the most intensively studied areas in materials science today. There are several potential advantages of lithium-ion battery electrodes based on inverse opal structures. High electrode surface, easier electrolyte access to the bulk of electrode and reduced lithium diffusion lengths allow higher discharge rates. Highly open structures provide for better mechanical stability to volume swings during cycling. Silicon is one of the most promising anode materials for lithium-ion batteries. Its theoretical capacity exceeds capacities of all other materials besides metallic lithium. Silicon is abundant, cheap, and its use would allow for incorporation of microbattery production into the semiconductor manufacturing. Performance of silicon is restricted mainly by large volume changes during cycling. The objective of this work was to investigate how the inverse opal structures influence the performance of silicon electrodes. Several types of silicon-based inverse opal films were synthesised, and their electrochemical performance was studied. Amorphous silicon inverse opals were fabricated via chemical vapour deposition and characterised by various techniques. Galvanostatic cycling of these materials confirmed the feasibility of the approach taken, since the electrodes demonstrated high capacities and decent capacity retentions. The rate performance of amorphous silicon inverse opals was unsatisfactory due to low conductivity of silicon. The conductivity of silicon inverse opals was improved by crystallisation. Nanocrystalline silicon inverse opals demonstrated much better rate capabilities, but the capacities faded to zero after several cycles. Silicon-carbon composite inverse opal materials were synthesised by depositing a thin layer of carbon via pyrolysis of a sucrose-based precursor onto the silicon inverse opals in an attempt to further increase conductivity and achieve mechanical stabilisation of the structures. The amount of carbon deposited proved to be insufficient to stabilise the structures, and silicon-carbon composites demonstrated unsatisfactory electrochemical behaviour. Carbon inverse opals were coated with amorphous silicon producing another type of macroporous composites. These electrodes demonstrated significant improvement both in capacity retentions and in rate capabilities. The inner carbon matrix not only increased the material conductivity, but also resulted in lower silicon pulverisation during cycling.