ITC/USA 2007 Conference Proceedings / The Forty-Third Annual International Telemetering Conference and Technical Exhibition / October 22-25, 2007 / Riviera Hotel & Convention Center, Las Vegas, Nevada / As technological advances continue to be made in the commercial sectors of portable and wireless communication products, additional advancements in battery technology have also been made. These advancements have allowed for the rapid growth of a large variety of commercially available batteries which have the capability to meet or even exceed the current power and size requirements for numerous ballistic telemetry systems. The replacement of a custom built battery with a COTS battery would provide immediate advantages such as lower cost, shorter lead times and higher availability. The overall objective of this paper is to provide ballistic telemetry systems engineers and designers with multiple low cost, readily available alternatives to traditional custom made power sources.

>Magister Scientiae - MSc / Spinel lithium manganese oxide (LiMn2O4), for its low cost, easy preparation and nontoxicity, is regarded as a promising cathode material for lithium-ion batteries. However, a key problem prohibiting it from large scale commercialization is its severe capacity fading during cycling. The improvement of electrochemical cycling stability is greatly attributed to the suppression of Jahn-Teller distortion (Robertson et al., 1997) at the surface of the spinel LiMn2O4 particles. These side reactions result in Mn2+ dissolution mainly at the surface of the cathode during cycling, therefore surface modification of the cathode is deemed an effective way to reduce side reactions. The utilization of a nanocomposite which comprises of metallic Cu and Au were of interest because their oxidation gives rise to a variety of catalytically active configurations which advances the electrochemical property of Li-ion battery. In this research study, an experimental strategy based on doping the LiMn2O4 with small amounts of Cu-Au nanocomposite cations for substituting the Mn3+ ions, responsible for disproportionation, was employed in order to increase conductivity, improve structural stability and cycle life during successive charge and discharge cycles. The spinel cathode material was synthesized by coprecipitation method from a reaction of lithium hydroxide and manganese acetate using 1:2 ratio. The Cu-Au nanocomposite was synthesized via a chemical reduction method using copper acetate and gold acetate in a 1:3 ratio. Powder samples of LiMxMn2O4 (M = Cu-Au nanocomposite) was prepared from a mixture of stoichiometric amounts of Cu-Au nanocomposite and LiMn2O4 precursor. The novel LiMxMn2O4 material has a larger surface area which increases the Li+ diffusion coefficient and reduces the volumetric changes and lattice stresses caused by repeated Li+ insertion and expulsion. Structural and morphological sample analysis revealed that the modified cathode material have good crystallinity and well dispersed particles. These results corroborated the electrochemical behaviour of LiMxMn2O4 examined by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The diffusion coefficients for LiMn2O4 and LiMxMn2-xO4 obtained are 1.90 x10-3 cm2 / s and 6.09 x10-3 cm2 / s respectively which proved that the Cu-Au nanocomposite with energy band gap of 2.28 eV, effectively improved the electrochemical property. The charge / discharge value obtained from integrating the area under the curve of the oxidation peak and reduction peak for LiMxMn2-xO4 was 263.16 and 153.61 mAh / g compared to 239.16 mAh / g and 120 mAh / g for LiMn2O4. It is demonstrated that the presence of Cu-Au nanocomposite reduced side reactions and effectively improved the electrochemical performance of LiMn2O4.

International Telemetering Conference Proceedings / October 25-28, 1999 / Riviera Hotel and Convention Center, Las Vegas, Nevada / The rapid growth in portable and wireless communication products has brought valuable advancements in battery technology. No longer is a battery restricted to a metal container in cylindrical or prismatic format. Today’s batteries (both primary and secondary) can be constructed in thin sheets and sealed in foil/plastic laminate packages. Along with improvements in energy density, temperature performance, and environmentally friendly materials, these batteries offer greater packaging options at a significantly lower development cost. Under the Hardened Subminiature Telemetry and Sensor System (HSTSS) program these battery technologies have been further developed for high-g telemetry applications. Both rechargeable solid state lithium-ion polymer and primary lithium manganese dioxide batteries are being developed in conjunction with Ultralife Batteries Inc. Prototypes of both chemistries have been successfully tested in a ballistic environment while providing high constant rates of discharge, which is essential to these types of applications. Electrical performance and environmental data are reported.

>Magister Scientiae - MSc / Lithium iron manganese phosphate (LiFe0.5Mn0.5PO4), is a promising, low cost and high energy density (700 Wh/kg) cathode material with high theoretical capacity and high operating voltage of 4.1 V vs. Li/Li+, which falls within the electrochemical stability window of conventional electrolyte solutions. However, a key problem prohibiting it from large scale commercialization is its severe capacity fading during cycling. The improvement of its electrochemical cycling stability is greatly attributed to the suppression of Jahn-Teller distortion at the surface of the LiFe0.5Mn0.5PO4 particles. Nanostructured materials offered advantages of a large surface to volume ratio, efficient electron conducting pathways and facile strain relaxation. The LiFe0.5Mn0.5PO4 nanoparticles were synthesized via a simple-facile microwave method followed by coating with multi-walled carbon nanotubes (MWCNTs) nanoparticles to enhance electrical and thermal conductivity. The pristine LiFe0.5Mn0.5PO4 and LiFe0.5Mn0.5PO4-MWCNTs composite were examined using a combination of spectroscopic and microscopic techniques along with electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Microscopic results revealed that the LiFe0.5Mn0.5PO4-MWCNTs composite contains well crystallized particles and regular morphological structures with narrow size distributions. The composite cathode exhibits better reversibility and kinetics than the pristine LiFe0.5Mn0.5PO4 due to the presence of the conductive additives in the LiFe0.5Mn0.5PO4-MWCNTs composite. For the composite cathode, D = 2.0 x 10-9 cm2/s while for pristine LiFe0.5Mn0.5PO4 D = 4.81 x 10-10 cm2/s. The charge capacity and the discharge capacity for LiFe0.5Mn0.5PO4-MWCNTs composite were 259.9 mAh/g and 177.6 mAh/g, respectively, at 0.01 V/s. The corresponding values for pristine LiFe0.5Mn0.5PO4 were 115 mAh/g and 44.75 mAh/g, respectively. This was corroborated by EIS measurements. LiFe0.5Mn0.5PO4-MWCNTs composite showed to have better conductivity which corresponded to faster electron transfer and therefore better electrochemical performance than pristine LiFe0.5Mn0.5PO4. The composite cathode material (LiFe0.5Mn0.5PO4-MWCNTs) with improved electronic conductivity holds great promise for enhancing electrochemical performances and the suppression of the reductive decomposition of the electrolyte solution on the LiFe0.5Mn0.5PO4 surface. This study proposes an easy to scale-up and cost-effective technique for producing novel high-performance nanostructured LiFe0.5Mn0.5PO4 nano-powder cathode material. / 2023-12-01

Doctor Educationis / Energy storage technologies are rapidly being developed due to the increased awareness of global warming and growing reliance of society on renewable energy sources. Among various electrochemical energy storage technologies, high power supercapacitors and lithium ion batteries with excellent energy density stand out in terms of their flexibility and scalability. However, supercapacitors are handicapped by low energy density and batteries lag behind in power. Supercapatteries have emerged as hybrid devices which synergize the merits of supercapacitors and batteries with the likelihood of becoming the ultimate power sources for multi-function electronic equipment and electric/hybrid vehicles in the future. But the need for new and advanced electrodes is key to enhancing the performance of supercapatteries. Leading edge technologies in material design such as nanoarchitectonics become very relevant in this regard. This work involves the preparation of vanadium pentoxide (V2O5), pristine and zinc doped lithium manganese silicate (Li2MnSiO4) nanoarchitectures as well as their composites with hydroxylated graphene (G-ol) and carbon nanotubes (CNT). / 2023-12-02

Thesis (M.Sc. (Physics)) -- University of Limpopo, 2020. / This dissertation presents the results of the ab-initio based computational studies of spinel lithium manganese oxide (LiMn2O4) bulk, surfaces, and the adsorption of an organic electrolyte, ethylene carbonate. The spinel LiMn2O4 is one of the most promising cathode materials for Lithium-ion batteries because of its affordability, nontoxicity, and improved safety compared to commercially used LiCoO2. However, it also suffers from the irreversible capacity due to the electrolyte-cathode interactions which lead to manganese (Mn) dissolution. Using the spin-polarized density functional theory calculations with on site Coulomb interactions and long-range dispersion corrections [DFT+U−D3−(BJ)], we investigated the bulk properties, surface stability and surface reactivity towards the ethylene carbonate (EC) during charge/discharge processes. Firstly, we explored the structural, electronic, and vibrational bulk properties of the spinel LiMn2O4. It was found that the bulk structure is a stable face-centred cubic structure with a bandgap of 0.041 eV and pseudo-gap at the Fermi level indicating electronic stability. Calculated elastic constants show that the structure is mechanically stable since they obey the mechanical stability criteria. The plotted phonon curves show no imaginary vibrations, indicating vibrational stability. To study the charge/discharge surfaces, we modelled the fully lithiated and the partially delithiated slabs and studied their stability. For the fully lithiated slabs, Li-terminated (001) surface was found to be the most stable facet, which agrees with the reported experimental and theoretical data. However, upon surface delithiation, the surface energies increase, and eventually (111) surface becomes the most stable slab as shown by the reduction of the plane in the particle morphologies. Finally, we explored the surface reactivity towards the ethylene carbonate during charge/discharge processes. The ethylene carbonate adsorption on the fully lithiated and partly delithiated facets turn to enhance the stability of (111) surface. Besides the strong interaction with the (111) surfaces, a negligible charge transfer was calculated, and it was attributed by a large charge rearrangement that takes place within the surfactant upon adsorption. The wavenumbers of the C=O stretching showed a red shifting concerning the isolated EC molecule

<p>LiMn₂O₄ is ideal as a high-capacity Li-ion battery cathode material by virtue of its low toxicity, low cost, and the high natural abundance of Mn. Surface related reactions and bulk kinetics have been the major focus of this work. The main techniques exploited have been: electrochemical cycling, X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy and thermal analysis.</p><p>Interface formation between the LiMn₂O₄cathode and carbonate-based electrolytes has been followed under different pre-treatment conditions. The variables have been: number of charge/discharge cycles, storage time, potential, electrolyte salt and temperature. The formation of the surface layer was found not to be governed by electrochemical cycling. The species precipitating on the surface of the cathodes at ambient temperature have been determined to comprise a mixture of organic and inorganic compounds: LiF, Li_xPF_y (or Li_xBF_y, depending on the electrolyte salt used), Li_xPO_yF_z (or Li_xBO_yF_z) and poly(oxyethylene). Additional compounds were found at elevated temperatures: phosphorous oxides (or boron oxides) and polycarbonates. A model has been presented for the formation of these surface species at elevated temperatures. </p><p>The cathode surface structure was found to change towards a lithium-rich and Mn³⁺-rich compound under self-discharge. The reduction of LiMn₂O₄, in addition to the high operating potential, induces oxidation of the electrolyte at the cathode surface.</p><p>A novel <i>in situ</i> electrochemical/structural set-up has facilitated a study of the kinetics in the LiMn₂O₄ electrode. The results eliminate solid-phase diffusion as the rate-limiting factor in electrochemical cycling. The electrode preparation method used results in good utilisation of the electrode, even at high discharge rates.</p>

LiMn2O4 is ideal as a high-capacity Li-ion battery cathode material by virtue of its low toxicity, low cost, and the high natural abundance of Mn. Surface related reactions and bulk kinetics have been the major focus of this work. The main techniques exploited have been: electrochemical cycling, X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy and thermal analysis. Interface formation between the LiMn2O4 cathode and carbonate-based electrolytes has been followed under different pre-treatment conditions. The variables have been: number of charge/discharge cycles, storage time, potential, electrolyte salt and temperature. The formation of the surface layer was found not to be governed by electrochemical cycling. The species precipitating on the surface of the cathodes at ambient temperature have been determined to comprise a mixture of organic and inorganic compounds: LiF, LixPFy (or LixBFy, depending on the electrolyte salt used), LixPOyFz (or LixBOyFz) and poly(oxyethylene). Additional compounds were found at elevated temperatures: phosphorous oxides (or boron oxides) and polycarbonates. A model has been presented for the formation of these surface species at elevated temperatures. The cathode surface structure was found to change towards a lithium-rich and Mn3+-rich compound under self-discharge. The reduction of LiMn2O4, in addition to the high operating potential, induces oxidation of the electrolyte at the cathode surface. A novel in situ electrochemical/structural set-up has facilitated a study of the kinetics in the LiMn2O4 electrode. The results eliminate solid-phase diffusion as the rate-limiting factor in electrochemical cycling. The electrode preparation method used results in good utilisation of the electrode, even at high discharge rates.

>Magister Scientiae - MSc / In the wide search for advanced materials for next generation lithium-ion batteries, lithium manganese orthosilicate, Li₂MnSiO₄ is increasingly gaining attention as a potential cathode material by virtue of its ability to facilitate the extraction of two lithium ions per formula unit, resulting in a two-electron redox process involving Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺ redox couples. This property confers on it, a higher theoretical specific capacity of 333 mAhg⁻¹ which is superior to the conventional layered LiCoO₂ at 274 mAhg⁻¹ and the commercially available olivine LiFePO₄ at 170 mAhg⁻¹. Its iron analogue, Li₂FeSiO₄ has only 166 mAhg⁻¹ capacity as the Fe⁴⁺ oxidation state is difficult to access. However, the capacity of Li₂MnSiO₄ is not fully exploited in practical galvanostatic charge-discharge tests due to the instability of the delithiated material which causes excessive polarization during cycling and its low intrinsic electronic conductivity. By reducing the particle size, the electrochemical performance of this material can be enhanced since it increases the surface contact between the electrode and electrolyte and further reduces the diffusion pathway of lithium ions. In this study, a versatile hydrothermal synthetic pathway was employed to produce nanoparticles of Li₂MnSiO₄, by carefully tuning the reaction temperature and the concentration of the metal precursors. The nanostructured cathode material was further coated with a thin film of aluminium oxide in order to modify its structural and electronic properties. The synthesized materials were characterized by microscopic (HRSEM and HRTEM), spectroscopic (FTIR, XRD, SS-NMR, XPS) and electrochemical techniques (CV, SWV and EIS). Microscopic techniques revealed spherical morphologies with particle sizes in the range of 21-90 nm. Elemental distribution maps obtained from HRSEM for the novel cathode material showed an even distribution of elements which will facilitate the removal/insertion of Li-ions and electrons out/into the cathode material. Spectroscopic results (FTIR) revealed the vibration of the Si-Mn-O linkage, ascertaining the complete insertion of Mn ions into the SiO₄⁴⁻ tetrahedra. XRD and ⁷Li MAS NMR studies confirmed a Pmn21 orthorhombic crystal pattern for the pristine Li₂MnSiO₄ and novel Li₂MnSiO₄/Al₂O₃ which is reported to provide the simplest migratory pathway for Li-ions due to the high symmetrical equivalence of all Li sites in the unit cell, thus leading to high electrochemical reversibility and an enhancement in the overall performance of the cathode materials. The divalent state of manganese present in Li₂Mn²⁺SiO₄ was confirmed by XPS surface analysis. Scan rate studies performed on the novel cathode material showed a quasi-reversible electron transfer process. The novel cathode material demonstrated superior electrochemical performance over the pristine material. Charge/discharge capacity values calculated from the cyclic voltammograms of the novel and pristine cathode materials showed a higher charge and discharge capacity of 209 mAh/g and 107 mAh/g for the novel cathode material compared to 159 mAh/g and 68 mAh/g for the pristine material. The diffusion coefficient was one order of magnitude higher for the novel cathode material (3.06 x10⁻⁶ cm2s⁻¹) than that of the pristine material (6.79 x 10⁻⁷ cm2s⁻¹), with a charge transfer resistance of 1389 Ω and time constant (τ) of 1414.4 s rad⁻¹ for the novel cathode material compared to 1549 Ω and 1584.4 s rad-1 for the pristine material. The higher electrochemical performance of the novel Li₂MnSiO₄/All₂O₃ cathode material over the pristine Li₂MnSiO₄ material can be attributed to the alumina nanoparticle surface coating which considerably reduced the structural instability intrinsic to the pristine Li₂MnSiO₄ cathode material and improved the charge transfer kinetics.

<p>Proton exchange membrane fuel cells and lithium polymer batteries are important as future power sources in electronic devices, vehicles and stationary applications. The development of these power sources involves finding and characterising materials that are well suited r the application.</p><p>The materials investigated in this thesis are the perfluorosulphonic ionomer Nafion^TM(DuPont) and metal oxides incorporated into the membrane form of this material. The ionomer is used as polymer electrolyte in proton exchange membrane fuel cells (PEMFC) and the metal oxides are used as cathode materials in lithium polymer batters (LPB).</p><p>Crystallinity in cast Nafion films can be introduced by ion beam exposure or aging. Spectroscopic investigations of the crystallinity of the ionomer indicate that the crystalline regions contain less water than amorphous regions and this could in part explain the drying out of the polymer electrolyte membrane in a PEMFC.</p><p>Spectroscopic results on the equilibrated water uptake and the state of water in thin cast ionomer films indicate that there is a full proton transfer from the sulphonic acid group in the ionomer when there is one water molecule per sulphonate group.</p><p>The LPB cathode materials, lithium manganese oxide and lithium cobalt oxide, were incorporated <i>in situ</i> in Nafion membranes. Other manganese oxides and cobalt oxides were incorporated <i>in situ</i> inside the membrane. Ion-exchange experiments from HcoO₂to LiCoO₂within the membrane were also successful.</p><p>Fourier transform infrared spectroscopy, Raman spectroscopy and X-ray diffraction were used for the characterisation of the incorporated species and the Nafion film/membrane.</p>