Synthesis and electrochemical characterization of novel electroactive materials for lithium-ion batteries

Lithium-ion batteries (LIBs) have become ubiquitous as energy storage devices for mobile electronics, electric vehicles, and are beginning to be used for electric grid-scale energy storage. Lithium-ion batteries offer higher efficiencies, energy density, and longer life compared to incumbent technologies such as lead-acid and nickel metal hydride. Applications in which LIBs are used are continuing to demand better performing batteries at lower cost, which requires improvement in electroactive materials. This dissertation investigates the low temperature synthesis and modification of LiCoPO₄ as a potential high-voltage and therefore higher energy density polyanion cathode material for LIBs, as well as a new class of interdigitated metal foil anodes which promises to be an inexpensive, higher energy density, alternative to graphite. Chapter 1 is a brief introduction to lithium-ion batteries and the principle of operation of intercalation type electrochemical energy storage devices. The components of lithium ion batteries are introduced, specifically the anode, cathode, separator, and electrolyte. Some of the shortfalls of the current technologies are discussed and areas of research interest are highlighted. Chapter 2 is a brief overview of the various experimental methods that are generally applicable to more than one of the subsequent chapters. Methods which are specific to a given study are discussed in their respective chapters. Chapter 3 presents work on the low temperature microwave-assisted solovthermal synthesis (MW-ST) of three unique polymorphs of LiCoPO₄, specifically the polymorphs belonging to the Pnma, Cmcm, and Pn2₁a space groups. Prior to this work, only the Pnma polymorph had been reported via MW-ST method, and electrochemistry had not yet been reported for either the Pn2₁a or Cmcm polymorph. The dependence of the polymorphs on both the water content, and ammonium hydroxide content of the solvent was shown. Although, the electrochemistry of both the Pn2₁a and Cmcm polymorphs was found to be inferior to the Pnma polymorph, the ability to synthesize phase pure materials was crucial to conducting the work presented in chapters 4 and 5. Chapter 4 presents the aliovalent substitution of V³⁺ for Co²⁺ in LiCoPO₄ via a low-temperature MW-ST process. Substitution of up to 7% vanadium for cobalt was demonstrated and verified by changes in the lattice parameters with vanadium content. Both the ionic and electronic conductivity of LiCoPO₄ was enhanced with increasing vanadium substitution, which was attributed to the introduction of both charge carriers as well as inter-tunnel cobalt vacancies. Finally, the first cycle capacity was enhanced (from 69 mAh/g to 115 mAh/g) as well as the capacity retention over cycling. Chapter 5 demonstrates a novel technique of MW-ST assisted coating of a thin (2-5nm) conformal coating of LiFePO₄ on vanadium substituted LiCoPO₄. Although the vanadium substitution was able to independently increase the performance of LiCoPO₄, the materials still suffers from severe side reactions with the electrolyte. The coating of LiFePO₄ effectively raises the Fermi energy of the cathode material above the high occupied molecular orbital (HOMO) of the electrolyte preventing side reactions and increase the coulombic efficiency to nearly 100%. Chapter 6 introduces a novel method of producing high surface area, electrically conductive, metal nanofoams via a MW-ST process. Nickel, copper, and silver metal nanofoams are made via an inexpensive yet scalable process whereby metal acetates are reduced by polyglycol under microwave irradiation. The nanofoams were characterized via BET, SEM, XRD, EDS, and TEM. The nanofoams have potential uses in many clean energy applications, particularly lithium-ion batteries. Chapter 7 introduces a new framework for making a new class of high capacity, low-cost alloying anodes for lithium ion batteries. A novel interdigitated metal foil anode (IMFA) in which a nanosized active material, such as tin, is interdigitated with an electrically conductive matrix, such as aluminum, is presented. The foils are formed by the rolling of a eutectic Al-Sn alloy into a foil, which is an extremely cheap and scalable process. The anodes demonstrate an approximately 70% increase in capacity compared to graphite over 100 cycles, at reasonably fast rates (C/5), and high coulombic efficiency (>99%). Finally, Chapter 8 gives a brief overview of the results of the prior work and proposes areas for future research.Materials Science and Engineerin

Scalable Multi-Chain Coordination via the Hierarchical Longest Chain Rule

This paper introduces BlockReduce, a Proof-of-Work (PoW) based blockchain system which achieves high transaction throughput through a hierarchy of merged mined blockchains, each operating in parallel on a partition the overall application state. Most notably, the full PoW available within the network is applied to all blockchains in BlockReduce, and cross-blockchain state transitions are enabled seamlessly within the core protocol. This paper shows that, given a hierarchy of blockchains and its associated security model, the protocol scales superlinearly in transaction throughput with the number of blockchains operated by the protocol

Traumatic Urethral Injury without Pelvic Fracture in an Adult Female

A 23-year-old female was involved in a motor vehicle collision with multiple injuries, including a right acetabular fracture, but no pelvic fracture. Urology consultation was obtained due to difficulty placing a urethral catheter. Examination revealed a longitudinal urethral tear with vaginal laceration extending 2 cm from the urethral meatus proximally toward the bladder neck. The longitudinal urethral tear was repaired primarily. Traumatic female urethral injury in the absence of a pelvic fracture is an exceedingly rare occurrence

Intravesical Dimethyl Sulfoxide Inhibits Acute and Chronic Bladder Inflammation in Transgenic Experimental Autoimmune Cystitis Models

New animal models are greatly needed in interstitial cystitis/painful bladder syndrome (IC/PBS) research. We recently developed a novel transgenic cystitis model (URO-OVA mice) that mimics certain key aspects of IC/PBS pathophysiology. This paper aimed to determine whether URO-OVA cystitis model was responsive to intravesical dimethyl sulfoxide (DMSO) and if so identify the mechanisms of DMSO action. URO-OVA mice developed acute cystitis upon adoptive transfer of OVA-specific OT-I splenocytes. Compared to PBS-treated bladders, the bladders treated with 50% DMSO exhibited markedly reduced bladder histopathology and expression of various inflammatory factor mRNAs. Intravesical DMSO treatment also effectively inhibited bladder inflammation in a spontaneous chronic cystitis model (URO-OVA/OT-I mice). Studies further revealed that DMSO could impair effector T cells in a dose-dependent manner in vitro. Taken together, our results suggest that intravesical DMSO improves the bladder histopathology of IC/PBS patients because of its ability to interfere with multiple inflammatory and bladder cell types

Does urethral competence affect urodynamic voiding parameters in women with prolapse?

Aims To (1) compare voiding parameters and (2) correlate symptoms and urodynamic findings in women with pelvic organ prolapse (POP) and varying degrees of urethral competence. Methods We compared three groups of women with stages II–IV POP. Groups 1 and 2 were symptomatically stress continent women participating in the Colpopexy and Urinary Reduction Efforts (CARE) trial; during prolapse reduction before sacrocolpopexy, Group 1 (n = 67) did not have and Group 2 (n = 84) had urodynamic stress incontinence (USI) during prolapse reduction. Group 3 participants (n = 74), recruited specifically for this study, had stress urinary incontinence (SUI) symptoms and planned sacrocolpopexy. Participants completed standardized uroflowmetry, pressure voiding studies, and validated symptom questionnaires. Results Subjects' median age was 61 years, median parity 3 and 87% had stage III or IV POP. Fourteen percent of women in Group 3 demonstrated USI without, and 70% with, prolapse reduction. Women in Groups 2 and 3 had more detrusor overactivity (DO) than Group 1 (17 and 24% vs. 6%, P  = 0.02) and detrusor overactivity incontinence (DOI) (15 and 8% vs. 0%, P  = 0.004). Based on the Blaivis–Groutz nomogram, 60% of all women were obstructed. Post-void residual volume (PVR), peak flow rate, detrusor pressure at peak flow, voiding mechanisms, voiding patterns, obstruction and urinary retention did not differ among groups. Women in Group 3 had higher irritative and obstructive symptom scores than Group 1 or 2; neither score differed by presence of DO nor obstruction, respectively. Conclusion Women with POP have significant rates of urodynamic obstruction and retention, independent of their continence status. Symptoms of obstruction and retention correlate poorly with urodynamic findings. Neurourol. Urodynam. 26:1030–1035, 2007. © 2007 Wiley-Liss, Inc.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/57365/1/20436_ftp.pd

Bowel function, sexual function, and symptoms of pelvic organ prolapse in women with and without urinary incontinence

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/146399/1/nau23587_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/146399/2/nau23587.pd

A multicentered comparison of measurements obtained with microtip and external water pressure transducers

This study compared simultaneous intravesical pressure readings obtained with catheter-mounted microtip transducers and external water pressure transducer catheters during filling cystometry. Women undergoing multichannel urodynamic testing were randomly assigned to one of three groups: two microtip catheters, two external water pressure transducer catheters, or one of each type. Intravesical pressure was measured simultaneously for each transducer combination in each subject for minimal and maximal Valsalva effort and minimal, moderate, and maximal cough effort at two sequential bladder volumes (150 and 300 ml). Paired t tests were used to compare the means of the intravesical pressure obtained by the two types of catheters. The largest mean differences were observed when comparing microtip and water pressure transducers. Correlations of maximum pressure were consistently high between two microtip transducers and two water pressure transducers but lower for the microtip–water combination. Excellent reproducibility was demonstrated with transducers of similar types for intravesical pressures recorded during Valsalva and cough in women without prolapse. However, considerable variability was seen in pressures recorded by different transducers, particularly dependent on the water catheter manufacturer, indicating that intravesical pressure recordings from microtip and water-based systems are not interchangeable.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/45850/1/192_2005_Article_27.pd