Dissertations / Theses on the topic 'Magnesium Batteries'

This thesis is a feasibility study of the possible application of magnesium alloys forfuture magnesium-ion batteries. It investigates dierent alloys and characterizesthem with respect to internal resistance, overpotentials and the reversibility of theelectrochemical reaction. SEM and EDS studies of used electrodes have also beencarried out. It has been showed that alloys, easier to handle and at a fraction of thecost, can be used with equal or better performance than pure Mg. The seeminglysuperior alloy, AZ61 exhibits a coloumbic eciency close to 100%, at higher chargerates than pure Mg.

This dissertation focuses on the synthesis and electrochemical testing of new electrolyte salts for rechargeable multivalent ion batteries. In chapters 2 and 3 the synthesis of Mg and Ca hexafluoropnictogenate salts as well as the electrochemical behaviour of Mg(PF6)2 is presented. Pure samples of Mg(EF6)2 (E = P, As, and Sb) can be synthesized using Mg metal and NOPF6/NOSbF6 in CH3CN or via a ammonium salt deprotonation route using Me3NHAsF6 and Bu2Mg. The NOPF6 method was extended to the Ca variant, but isolation of a pure Ca(PF6)2 material required the presence of a crown ether. Electrochemical and microscopy measurements of THF-CH3CN solutions of Mg(PF6)2 show that the electrolyte good electrochemical stability and can facilitate the plating/stripping of Mg. Further, this electrolyte system can be cycled in a full cell using the Chevrel phase Mo6S8 cathode. The electrochemical stability of the AsF6− and SbF6− salts is lower than that of the PF6− salt and electrolyte decomposition is observed when cycling on Mg electrodes. In chapter 4 the development of a series of Mg aluminates [Mg(AlOR4)2] using a general synthetic platform based on Mg(AlH4)2 and various alcohols is presented. Preliminary electrochemical studies performed on these aluminate salts in dimethoxyethane identify the phenoxy and perfluoro-tert-butoxy derivatives as promising electrolyte systems. Electrochemical cycling of these electrolytes using gold and Mg electrodes show that systems containing chloride, brought through to the product from the starting material in the form of NaCl, exhibit lower plating/stripping overpotentials and higher Coulombic efficiencies than systems from which chloride had been removed. Further, these two electrolytes can be used in Mg full cells containing the Chevrel phase cathode. Solid-state 23Na NMR analysis as well as DFT calculations show that chloride-containing electrolytes facilitate the co-insertion of Na into the cathode material. In chapter 5 the hydroboration of pyridines and CO2 in the presence of pinacolborane is presented. An optimized system employing NH4BPh4 and HBpin is developed and a mechanism of pyridine hydroboration is proposed based on multinuclear NMR spectroscopy. The catalytic reaction was found to be catalyzed by a boronium salt, which was structurally characterized in the solid-state by single crystal X-ray diffraction. This new catalytic method is shown to be tolerant to a number of functional groups in the 3-position on pyridine as well as quinoline, and CO2, producing the hydroboration products in good yields.

The importance of energy storage worldwide is increasing with the use of renewable energy sources and electric vehicles. With the intermittent nature of wind and solar power, large-scale grid storage is an extremely important progression needed to reduce the use of fossil fuels. For this to become a reality, rechargeable batteries beyond existing Li-ion technologies need consideration. The development of such batteries requires improvement of understanding their component materials. Modern computer modelling techniques enable valuable insights into the fundamental defect, ion transport and voltage properties of battery materials at the atomic level. Atomistic simulation and ab initio density functional theory (DFT) techniques have been used to study a number of potential cathode materials for Na-ion and Mg batteries. Firstly, the olivine and maricite forms of NaFePO4 are considered in terms of their defect formation energies and Na ion diffusion. The atomistic study indicates that anti-site disorder is the most favourable type of intrinsic defect. The activation energies for Na-ion migration in the olivine and maricite materials are 0.4 eV and 1.6 – 1.8 eV respectively. Moreover, molecular dynamics (MD) studies reveal that there is only substantial Na-ion diffusion in the olivine structure, with diffusion coefficients (DNa) at 300 K of 7 x 10−13 cm2s−1 for maricite and 4 x 10−9 cm2s−1 for olivine NaFePO4. The presence of anti-site defects is shown to decrease Na+ diffusion within the olivine structure, which is of relevance to its rate behaviour. Secondly, the effect of lattice strain on ion transport and defect formation in olivine-type LiFePO4 and NaFePO4 is investigated as a means to enhance their ion conduction properties. It is predicted that lattice strain can have a remarkable effect on the rate performance of olivine cathode materials, with a major increase in ionic conductivity and decrease in blocking defectsat room temperature. Thirdly, DFT techniques have been used to examinesurface and grain boundary formation in P2-NaCoO2. The coordination lossexperienced by ions present at surfaces is found to influence the resultingsurface energy. Layered oxide cathode materials were further investigated byconsidering the effect of Mg2+ doping on P2-Na2 [Ni1 Mn2 ]O2. Na vacancy 333formation energies decreased with 10% Mg2+ doping on the Ni site and an increase in Na diffusion was predicted with MD calculations. This positive effect on Na ion conductivity is caused by displacement of the Mg ions from the transition metal layer and the resulting change in electrostatic potential. Finally, Mg ion conduction, doping and voltage behaviour of MgFeSiO4 were studied. The Mg-ion migration activation energy is relatively low for an olivine-type silicate, and MD simulations predict a diffusion coefficient (DMg) of 10−9 cm2s−1, suggesting favourable electrode kinetics. Partial substitution of Fe by Co or Mn could increase the cell voltage from 2.3 V vs Mg/Mg2+ to 2.8 - 3.0 V.

Thesis (Ph.D. (Engineering mechanics)) --University of Limpopo, 2004
This thesis explores the important issues associated with the insertion of Mg2+ and Li+ into the solid materials: molybdenum sulphide and titanium disulphide. This process, which is also known as intercalation, is driven by charge transfer and is the basic cell reaction of advanced batteries. We perform a systematic computational investigation of the new Chevrel phase, MgxMo6S8 for 0 ≤ x ≤ 2, a candidate for high energy density cathode in prototype rechargeable magnesium (Mg) battery systems. Mg2+ intercalation property of the Mo6S8 Chevrel phase compound and accompanied structural changes were evaluated. We conduct our study within the framework of both the local-density functional theory and the generalised gradient approximation techniques. Analysis of the calculated energetics for different magnesium positions and composition suggest a triclinic structure of MgxMo6S8 (x = 1 and 2). The results compare favourably with experimental data. Band-structure calculations imply the existence of an energy gap located ~1 eV above the Fermi level, which is a characteristic feature of the electronic structure of the Chevrel compounds. Calculations of electronic charge density suggest a charge transfer from Mg to the Mo6S8 cluster, which has a significant effect on the Mo-Mo bond length. There is relatively no theoretical work, in particular ab initio pseudopotential calculations, reported in literature on structural stability, cations "site energy" calculations, and pressure work. Structures obtained on the basis from experimental studies of other ternary molybdenum sulphides are examined with respect to pressure-induced structural transformation. We report the first bulk and linear moduli of the new Chevrel phase structures. This thesis also studies the reaction between lithium and titanium disulfide, which is the perfect intercalation reaction, with the product having the same structure over the range of reaction 0  x  1 in LixTiS2. Calculated lattice parameters, bulk moduli, linear moduli, elastic constants, density of states, and Mulliken populations are reported. Our calculations confirm that there is a single phase present with an expansion of the crystalline lattice as is typical for a solid solution, about 10% perpendicular to the basal plane layers. A slight expansion of the lattice in the basal plane is also observed due to the electron density increasing on the sulfur ions. Details on the correlation between the electronic structure and the energetic (i.e. the thermodynamics) of intercalation are obtained by establishing the connection between the charge transfer and lithium intercalation into TiS2. The theoretical determination of the densities of states for the pure TiS2 and Li1TiS2 confirms a charge transfer. Lithium charge is donated to the S (3p) and Ti (3d) orbitals. Comparison with experiment shows that the calculated optical properties for energies below 12 eV agrees well with reflectivity spectra. The structural and electronic properties of the intercalation compound LixTiS2, for x = 1/4, 3/4, and 1, are also investigated. This study indicates that the following physical changes in LixTiS2 are induced by intercalation: (1) the crystal expands uniaxially in the c-direction, (2) no staging is observed. We also focus on the intercalation voltage where the variation of the cell potential with the degree of discharge for LiTiS2 is calculated. Our results show that it can be predicted with these well-developed total energy methods. The detailed understanding of the electronic structure of the intercalation compounds provided by this method gives an approach to the interpretation of the voltage composition profiles of electrode materials, and may now clearly be used routinely to determine the contributions of the anode and cathode processes to the cell voltage. Hence becoming an important tool in the selection and design of new systems. Keywords Magnesium rechargeable battery; Chevrel, Lithium batteries; Li and Mg-ion insertion; TiS2; Mo6S8; Charge transfer; reflectivity, intercalation, elastic constants, voltage, EOS, Moduli.
the National Research Foundation, the Royal Society(U.K),the Council for Scientific and Industrial Research,and Eskom

Kyoto University (京都大学)
0048
新制・課程博士
博士(人間・環境学)
甲第19071号
人博第724号
新制||人||174(附属図書館)
26||人博||724(吉田南総合図書館)
32022
京都大学大学院人間・環境学研究科相関環境学専攻
(主査)教授 内本 喜晴, 教授 田部 勢津久, 准教授 藤原 直樹
学位規則第4条第1項該当

Les objectifs de cette thèse sont d’une part, de développer de nouveaux électrolytes par la conception de nouveaux sels de magnésium non dangereux ou par l’utilisation d’additifs aromatiques comme l’anthracène et d’autre part de synthétiser un polymère organique ayant des propriétés redox adaptées à son utilisation comme électrode positive dans des batteries au Magnésium.La première méthodologie a été la synthèse de plusieurs sels de magnésium obtenus par la réaction de phénol substitués ou de thiophénol avec l’anion tetrahydroborate. Les meilleurs résultats ont été obtenus avec le sel obtenu par réaction du thiophénol et du tétrahydroborate. L'impact de ce nouveau sel sur l’amélioration de l'interface Mg/électrolyte a été caractérisé par des électrochimie. En outre, les performances de la cellule complète Mg/Mo6S8 ont été évaluées, et une capacité de 75 mAh/g a été obtenue après 20 cycles, avec une faible polarisation de l'électrode de Mg. La deuxième méthodologie a consisté à étudier l'effet d’additifs aromatiques sur le processus de dépôt/dissolution du Mg, et ainsi permettre d’approfondir notre compréhension du mécanisme assisté sous-jacent. La deuxième partie de cette thèse présente les performances électrochimiques de matériaux organiques utilisés comme électrode positive pour les batteries au lithium et au magnésium. Le polybenzoquinonedisulfure (PBQDS) a été synthétisé avec un rendement très élevé de façon écologique et facile. Les performances obtenues en cellule Li sont intéressantes, alors qu’en cellule Mg, une perte de capacité importante est obtenue associée au piégeage des ions Mg2+ au sein de l’électrode, due à une forte interaction oxygène/Mg2+. L'utilisation d'un additif solvatant, un éther couronne, dans l'électrolyte atténue partiellement ce comportement, proposant ainsi des pistes d'amélioration intéressantes
The objectives of this thesis are, on the one hand, to develop new electrolytes by the design of new non-hazardous magnesium salts or by the use of aromatic additives such as anthracene and, on the other hand, to synthesize an organic polymer with redox properties suitable for its use as a positive electrode in magnesium batteries. The first methodology was the synthesis of several magnesium salts obtained by the reaction of substituted phenol or thiophenol with the tetrahydroborate anion. The best results were obtained with the salt obtained by the reaction of thiophenol and tetrahydroborate. The impact of this new salt on the improvement of the Mg/electrolyte interface was characterized by chronoamperometry and impedance spectroscopy measurements. In addition, the performance of full cell Mg/Mo6S8 was evaluated, a capacity of 75 mAh/g was obtained after 20 cycles, with a weak polarization of the Mg electrode. The second methodology several π-rich compounds were used. The best promising molecule is the 2-(tert-butyl)anthracene with an improvement in the Mg plating/stripping process reversibility. The second part of this thesis will present the electrochemical performance of organic material using as positive electrode for both lithium and magnesium batteries. Polybenzoquinonedisulfide (PBQDS) was synthesized with very high yield in a green and easy way. After the particle size reduction using ball milling technique, the discharge capacity reaches a stable value of 140 mAh/g at C/20 in sulfolane based electrolyte. In Mg cell, even if similar capacity is obtained in the first cycles, a large capacity fading is observed associated with the trapping of Mg2+ in the active material, due to strong oxygen/Mg2+ interaction. The use of solvation additive (crown ether) in the electrolyte mitigates partially this behaviour, given some interesting leads of improvement

The research activity described in this thesis has been focused on the development and study of novel electrolyte and electrode materials for application in Lithium and Magnesium secondary batteries. The proposed materials belong to the “beyond Li-ion” class of compounds, where systems exceeding the energy density values of classic Li-ion batteries or completely innovative chemistries are presented. Three different classes of electrolytes have been prepared and studied. A solid polymer electrolyte has been obtained by a lithium functionalization of a poly(vinyl alcohol-co-vinyl acetate), forming lithium alkoxide functional groups. In this way, the counter anion of Li+ was the overall polymer chain, giving rise to a single lithium ion conductivity. However, the room-temperature conductivity value observed for this material was quite low (4.6·10-10 S·cm-1). By ionic liquid (IL) doping of the solid polymer electrolyte, we have obtained a double effect: i) lithium cations have been exchanged by the cations of IL, enhancing the mobility of the active species; and ii) the flexibility of polymer chains has been increased by the plasticizing effect of the IL. Thus, a room temperature conductivity of 1.3·10-5 S·cm-1 has been reached, maintaining a high value of Li transference number (0.59). By reacting glycerol with different quantities of lithium hydride, a new family of lithium-ion conducting electrolytes has been synthetized. In these electrolytes the lithium glycerolate component acts as a large and flexible macro-anion which is able to provide a singleion conductivity to the material (2.0∙10-4 at 30 °C and 1.6∙10-2 S∙cm-1 at 150 °C). In the last class of electrolytes, ionic liquid-based materials for magnesium batteries, the cation and anion replacement effect on the structure, conductivity mechanism, and electrochemical performances has been studied. The proposed materials have exhibited a conductivity value between 10-3 and 10-4 S∙cm-1, an overpotential in the magnesium deposition lower than 50 mV vs. Mg/Mg2+, an anodic stability up to +2.35 V vs. Mg/Mg2+, and a coulombic efficiency up to 99.94 %. In the second part of this Ph.D. project, the improvement of the electrochemical features of various cathode materials has been studied. In the first case, it has been found that, by adding CuCO3 to the precursors, segregated CuO particles have been formed. The presence of these particles has improved the charge-transfer kinetics during the charge/discharge processes of the cathode material. On the other hand, graphite addition to the precursors has been found to improve the elasticity of the 3D structure of the cathode backbone. Thus, an increased structural flexibility that facilitates the percolation of lithium ions along the 1D channels of the cathode material has been observed. In the second approach, the improvement of the electron conductivity of a high-voltage cathode has been gauged by V, Nb, or Ta insertion within its olivine structure. This approach has allowed for an improved kinetic and reversibility of Li+ insertion reaction. The specific capacity reached by these cathodes was equal to 149 mAh∙g-1. The last cathode material has been implemented in a magnesium secondary battery device. A graphene oxide surface functionalization of vanadium-based nanoparticles has been obtained thanks to electrostatic interactions through ammonium bridges. This functionalization has allowed for the obtaining of a material able to: a) sustain extremely high current rates (1000 mA∙g-1, 1700 mW∙g-1 of specific power); and b) give reasonable specific capacity values (72 mAh∙g-1).

With the growing global population comes the ever-increasing consumption of energy in powering cities, electric vehicles, and portable devices such as cell-phones. While the power grid is used to distribute energy to consumers, the energy sources needed to power the grid itself are unsustainable and inefficient. The primary energy sources powering the grid, being fossil fuels, natural gas, and nuclear, are unsustainable as the economically-accessible reserves are continually depleted in exchange for detrimental emissions and air-pollutants. Cleaner, renewable sources, such as solar, wind, and hydroelectric, are intermittent and unreliable during the peak hours of energy usage, that is dawn and dusk. However, during waking hours and nighttime sleeping hours, energy consumption plummets resulting in substantial losses of potential energy as these intermittent energy providers do not have the infrastructure to store unused energy. Therefore, the research and development of efficient energy storage materials and renewable energy sources is critical to meet the needs of society in their fundamental operation while reducing harmful emissions. The research presented in this thesis focuses on selected energy storage materials and electrocatalysts as attractive technology for sustainable and benign renewable energy chemistry. Specifically, (1) theoretical studies on magnesium chloride / aluminum chloride electrolytes provide insight for further development of Mg batteries; (2) theoretical and experimental studies on viologen derivatives for organic redox flow batteries advance the development of these two-electron storage systems; and (3) a new iron(II) polypyridine catalyst that was found to electrochemically reduce CO2 to produce renewable fuels such as carbon monoxide (CO), hydrogen (H2), and methane (CH4), as well as promote the photochemical CO2-to-methane conversion with visible light.

>Magister Scientiae - MSc
Architecturally enhanced electrode materials for lithium ion batteries (LIB) with permeable morphologies have received broad research interests over the past years for their promising properties. However, literature based on modified porous nanoparticles of lithium manganese phosphate (LiMnPO₄) is meagre. The goal of this project is to explore lithium manganese phosphate (LiMnPO₄) nanoparticles and enhance its energy and power density through surface treatment with transition metal nanoparticles. Nanostructured materials offer advantages of a large surface to volume ratio, efficient electron conducting pathways and facile strain relaxation. The material can store lithium ions but have large structure change and volume expansion during charge/discharge processes, which can cause mechanical failure. LiMnPO₄ 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. Ag/AgCl which falls within the electrochemical stability window of conventional electrolyte solutions. LiMnPO₄ has safety features due to the presence of a strong P–O covalent bond. The LiMnPO₄ nanoparticles were synthesized via a sol-gel method followed by coating with gold nanoparticles to enhance conductivity. A magnesium oxide (MgO) nanowire was then coated onto the LiMnPO₄/Au, in order to form a support for gold nanoparticles which will then form a thin film on top of LiMnPO₄ nanoparticles crystals. The formed products will be LiMnPO₄/Mg-Au composite. MgO has good electrical and thermal conductivity with improved corrosion resistance. Thus the electronic and optical properties of MgO nanowires were sufficient for the increase in the lithium ion diffusion. The pristine LiMnPO₄ and LiMnPO₄/Mg-Au composite were examined using a combination of spectroscopic and microscopic techniques along with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Microscopic results revealed that the LiMnPO₄/Mg-Au composite contains well crystallized particles and regular morphological structures with narrow size distributions. The composite cathode exhibits better reversibility and kinetics than the pristine LiMnPO₄ due to the presence of the conductive additives in the LiMnPO₄/Mg-Au composite. This is demonstrated in the values of the diffusion coefficient (D) and the values of charge and discharge capacities determined through cyclic voltammetry. For the composite cathode, D= 2.0 x 10⁻⁹ cm²/s while for pristine LiMnPO₄ D = 4.81 x 10⁻¹⁰ cm2/s. The charge capacity and the discharge capacity for LiMnPO₄/Mg-Au composite were 259.9 mAh/g and 157.6 mAh/g, respectively, at 10 mV/s. The corresponding values for pristine LiMnPO₄ were 115 mAh/g and 44.75 mAh/g, respectively. A similar trend was observed in the results obtained from EIS measurements. These results indicate that LiMnPO₄/Mg-Au composite has better conductivity and will facilitate faster electron transfer and therefore better electrochemical performance than pristine LiMnPO₄. The composite cathode material (LiMnPO₄/Mg-Au) with improved electronic conductivity holds great promise for enhancing electrochemical performances, discharge capacity, cycle performance and the suppression of the reductive decomposition of the electrolyte solution on the LiMnPO₄ surface. This study proposes an easy to scale-up and cost-effective technique for producing novel high-performance nanostructured LiMnPO₄ nanopowder cathode material.

The aim of this thesis is to investigate pyroborates, M2B2O5, and orthoborates, M3(BO3)2, where M = Mg, Mn, Co, Ni, as high capacity and high voltage Li- and Mg-ion cathode materials. We explore the layered orthoborates (M3(BO3)2 which, to our knowledge, have not been previously considered as Li- or Mg-ion cathodes, perhaps due to the lack of Li analogues. Structural analysis shows that mixed metal orthoborates form a solid solution, with cation order driven by the presence of directional d orbitals. Electrochemical studies show that Mg can be removed from the structure and replaced with Li in a 1:1 ion ratio. In the compound Mg2Mn(BO3)2 removal of 1 Mg is achieved giving a capacity of 209.9 mAh g 1. The pyroborates (M2B2O5) are an unexplored family of borate polyanions, which offer higher theoretical capacities and voltages than LiMBO3 due to their more condensed frameworks. There are no known Li containing pyroborates, we use electrochemical ion exchange, with the aim of replacing each Mg with 2 Li to form LixMB2O¬5. The stoichiometry can be varied to alter the redox couple utilised and the Mg available for removal. MgxM2-xB2O5 has been synthesised for M = Mn, Co, Fe and Ni and all forms have been shown to form a solid solution with cation ordering over the two M sites. In MgMnB2O5 we have shown that Mg can be fully removed while retaining the pyroborate structure. Subsequently up to 1.1 Li can be inserted giving discharge capacities of 240 mAhg-1 above 1.5 V. After 100’s of cycles 2 Li can be reversibly cycled. The insertion of Li has been confirmed by 7Li NMR and the oxidation state changes in Mn have been investigated by SQUID magnetometry and XANES spectroscopy. Electrochemical studies in materials where M = Fe, Co, and Ni show high voltage plateaus ( > 3.5 V) but limited capacity at room temperature. Increased temperatures improves cycling, with Co and Fe based compounds reaching full theoretical capacities ( > 200 mAhg-1). As Mg can be removed from the structure, the pyroborates could be of interest in Mg-ion batteries, which offer benefits in energy density, cost, and safety. Mg-ion battery research is still in its infancy, therefore here we develop methods to reliably test Mg-ion cathodes and electrolytes. We demonstrate that despite significant side reactions, Mg can be reversibly cycled in the MgMnB2O5 system in a full Mg-ion cell, showing that pyroborates are a promising family of materials for high capacity, high voltage Mg-ion cathodes. This study shows that the pyroborates and orthoborates are a promising family of materials for Li- and Mg-ion cathodes, with the light weight structure leading to high specific capacities. The ability to replace Mg for Li in polyanion materials without disrupting the crystal structure opens a new way to search for novel, high energy density, Li-ion cathodes.

L’accélération continuelle de la demande en lithium, combinée à son abondance limitée et sa concentration inhomogène dans la croûte terrestre risque d’augmenter considérablement son prix dans un futur proche. Les batteries au Mg sont une alternative prometteuse aux batteries Li-ion du fait de la grande abondance, du coût et des capacités du Mg. Néanmoins le Mg métal réagit avec les électrolytes conventionnels pour former une couche de passivation à sa surface rendant l’échange de cations impossible. Une alternative intéressante réside dans le remplacement du Mg métal par une électrode négative hôte, surmontant le problème de compatibilité avec les électrolytes. L’objectif de ce travail est d’étudier le comportement électrochimique et les mécanismes de réactions de deux alliages d’éléments du bloc p en tant qu’électrode négative de batteries Mg : In-Pb:C et InSb, synthétisés par broyage.Une forte synergie entre In et Sb est mise en évidence dans InSb avec la promotion de l'activité électrochimique du Sb avec Mg, impossible dans le cas de Sb seul. Cet effet synergique n’est présent qu’au premier cycle électrochimique pour In-Pb:C. En couplant des caractérisations DRX ex situ et operando et XAS, nous avons suivi les transformations de phases durant les processus de (dé)magnésiation. En particulier, une amorphisation de la phase MgIn est induite par la première magnésiation de InSb et In-Pb:C. Afin d’améliorer les performances de InSb, la morphologie des poudres a été modifiée via une synthèse par réduction. Bien que les performances soient peu améliorées, la cristallisation de la phase MgIn est favorisée quand les particules sont nanostructurées. Ce comportement suggère une compétition entre cristallisation et amorphisation dépendante de la morphologie
The perpetual acceleration of the lithium demand combined with its relatively low abundance and uneven concentration on the Earth’s crust might dramatically increase its price in a near future. Mg batteries are a promising alternative to Li-ion batteries thanks to Mg high abundance, low cost and capacity. Yet, metallic Mg reacts with conventional electrolytes to form a barrier on its surface, preventing cation exchange. An interesting alternative is to replace Mg metal with a host negative electrode, overcoming the electrolyte compatibility problem. The objective of this work is to study the electrochemical behaviour and reaction mechanisms of two p-block elements alloys used as a negative electrode in Mg-ion systems: In-Pb:C and InSb made by ball-milling.A strong synergy between In and Sb is evidenced in InSb with the electrochemical activation of Sb with Mg, inactive as a pure element. This synergetic effect is only present on the first magnesiation for In-Pb:C. By coupling operando and ex situ XRD with XAS, we followed the phase transformations during (de)magnesiation. Especially, an amorphization of MgIn is induced by the first magnesiation of InSb and In-Pb:C. To improve the performance of InSb, the morphology of the powder was modified via a reduction synthesis. Although performances are slightly improved, the crystallization of the MgIn phase is favored for nanostructured particles. This behavior suggests a competition between crystallization and amorphization depending of the material’s morphology

Orientador: Prof. Dr. Jorge Tomioka
Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Engenharia Elétrica, 2014.
No contexto energético, as mudanças climáticas e as crescentes crises energéticas aumentaram as preocupações e as pesquisas na área de acumuladores de energia, visando alcançar melhorias no cenário energético e ambiental global. Ao mesmo tempo, a sociedade tornou-se dependente do consumo de energia elétrica, sendo que falhas no fornecimento não são permitidas. Portanto, observa-se a necessidade da energia ofertada ser de boa qualidade e, principalmente, não sofrer interrupções. Atrelado a esses fatores, a bateria de Magnésio ¿ Ar passou a ser considerada uma fonte promissora de energia elétrica, principalmente pela abundância de Magnésio (sétimo elemento mais presente no planeta), por não poluir o meio ambiente, ser barata e possuir energia especifica elevada. Essas características transformam esse acumulador em um potencial substituto para outras tecnologias. No entanto, a bateria demagnésio possui desvantagens que precisam ser vencidas por meio de pesquisas para alavancar o seu uso comercial massivo. Sob essa perspectiva, neste trabalho propõe-se o estudo da liga de magnésio AZ91 para aplicação em baterias de Magnésio ¿ Ar, por meio de ensaios de porosidade e de dureza, como também análise microestrutural e mensuração do potencial de circuito aberto e das curvas de polarização potenciodinâmica, utilizando-se uma célula eletroquímica de três eletrodos e um potenciostato em diferentes tempos de imersão da liga AZ91 na solução eletrolítica de NaCl 0,1 M. A porosidade da peça, observada no microscópio óptico com ampliação de 50 vezes, revelou que em cada fase de solidificação existem poros de tamanhos diferentes, com distribuição específica. Conforme o processo de resfriamento ocorre, nota-se a presença de poros maiores. Relacionado à porosidade, a dureza apresentou valores maiores na fase inicial de solidificação, onde a porosidade é menor. Por meio da análise microestrutural, foi possível verificar a presença de dendritas, com uma complexa dispersão de segunda fase na liga (alumínio), porosidades e inclusões. As medidas de potencial de circuito aberto indicam uma tendência de resistência à corrosão em temposmaiores de contato da amostra com a solução de NaCl. Não foi possível observar passivação aparente na amostra, nem pontos de corrosão localizada (pite) nas curvas de polarização potenciodinâmica. As variações no potencial de corrosão apontaram uma maior resistência à corrosão em tempos de imersão maiores; contudo, os valores estáveis de densidade de corrente de corrosão demonstram que a velocidade de corrosão permaneceu constante, sendo que a camada de óxido formada não contribuiu na proteção do material. Para a aplicação em baterias de magnésio, esses resultados conferem uma limitação da liga AZ91, pois a camada de óxido formada pode prejudicar o funcionamento do dispositivo em processos de descarga intermitente. As principais formas de controlar a eficiência da bateria de Magnésio ¿ Ar são por meio da composição da liga, da oxigenação, do pH, da temperatura e da concentração de sais NaCl no eletrólito.
In the energy sector, weather changes and rising energy crisis raised concerns and research in energy accumulators to achieve improvements in overall environmental and energy scenario. At the same time, society has become dependent on electricity consumption, so failures in supply are not tolerated. Therefore, the energy needs to have a good quality, and not suffer interruptions. Coupled to these factors, the battery Magnesium ¿ Air has been considered a promising source of electricity, mainly by the abundance of magnesium (seventh-most element present on the planet), not to pollute the environment, be cheap and have high specific energy. These characteristics transform this accumulator in a potential substitute for other technologies. However, the magnesium battery has disadvantages that need to be overcome through research to leverage their massive commercial use. From this point of view, this study proposes the characterization of magnesium alloy AZ91 for application in batteries Magnesium ¿ Air, testing the porosity and hardness, as well as microstructural analysis, and the measurement of the open potential circuit and the potentiodynamic polarization, in various immersion times using an electrochemical cell with three electrodes. The porosity of the part, observed in the optical microscope, revealed that at each stage of solidification, the pores have different sizes and distribution. As the cooling process occurs, could observe the presence of larger pores. Associated to the porosity, hardness values were higher in the initial phase of solidification, where the porosity was less. Through microstructural analysis was verified the presence of dendrites, with a complex dispersion of second phase in the alloy (aluminum), porosity and inclusions. The open potential circuit indicated a tendency for corrosion resistance in greater immersion time in the solution of NaCl. In all cases, the potentiodynamic polarization curves did not exhibit apparent passivity, or points of localized corrosion (pitting). The changes in corrosion potential showed greater resistance to corrosion in immersion times larger, however, the steady state values of corrosion current density demonstrated that the corrosion rate remained constant and the oxide layer formed did not protect the material. For use in magnesium batteries, these results provided a limitation of the AZ91 alloy, because the oxide layer can disturb the functioning of the device in cases of intermittent discharge. The main ways to control the battery efficiency Magnesium ¿ Air are through the alloy composition, oxygenation, pH, temperature and salt concentration of NaCl in the electrolyte.

This thesis deals with novel electrolytes for magnesium batteries. Prepared electrolytes were composed of affordable solvents and chemicals, which can be handled at normal laboratory conditions. Specifically, solutions of tetrahydrofurane and dimethylsulfoxide with magnesium chloride, aluminium chloride, nitrilotriacetic acid and disodium ethylenediaminetetraacetic acid, were prepared. To determine electrolyte ability of magnesium stripping and deposition, the cyclic voltammetry was used. The kinetics of electrochemical reactions in terms of polarization resistance was studied by electrochemical impedance spectroscopy. Based on scanning electron microscopy and EDS analysis, the effect of atmospheric oxygen and humidity on magnesium electrode corrosion during cycling was discussed.

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Neste trabalho avaliou-se a ação positiva da substituição de lantânio por praseodímio e de lantânio por magnésio na performance eletroquímica de eletrodos de ligas de armazenamento de hidrogênio em estado bruto de fusão e com tratamento térmico. O La foi substituído por Mg nas ligas La0,7-xMgxPr0,3Al0,3Mn0,4Co0,5Ni3,8 (x=0,0-0,7) e por Pr nas ligas La0,7-yPryMg0,3Al0,3Mn0,4Co0,5Ni3,8 (y=0,0-0,7). Os parâmetros eletroquímicos analisados foram ativação, capacidade de descarga, retenção da capacidade de descarga, autodescarga e alta taxa de descarga. As ligas apresentaram comportamento passivo em relação à corrosão. As análises por MEV/EDS e por DRX com refinamento por Rietveld revelaram a presença majoritária de fases similares às fases LaNi5, PrNi5, LaMg2Ni9 e PrMg2Ni9 em função das composições das ligas estudadas. Os parâmetros de rede e os volumes da célula unitária das fases diminuíram com a substituição crescente de La por Mg e de La por Pr. As capacidades de descarga máxima decresceram com a substituição crescente de La por Mg e de La por Pr, acompanhando o decréscimo da abundância da fase similar à fase LaNi5 e o aumento da abundância da fase similar à fase LaMg2Ni9. Comparativamente, menores taxas de autodescarga e maior estabilidade cíclica foram observadas para o eletrodo da liga na condição x=0,1, ao passo que o eletrodo da liga na condição y=0,0 apresentou maiores valores de alta taxa de descarga, indicando melhor performance cinética.
Tese (Doutorado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

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Dissertação (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

In order to obtain advanced energy storage systems with high energy density, the research activity here described, is focused on the study of electrolyte and cathodic materials for application in Lithium and Magnesium batteries. The materials are synthesized through inert atmosphere procedures and characterized with several techniques such as: Thermogravimetric Analyses (TGA), Differential Scanning Calorimetry (DSC), Vibrational spectroscopies (MIR, FIR, Raman), Solid state MAS-NMR, several electrochemical techniques (CV, CA, EIS) and Broadband Electrical Spectroscopy (BES). The results are used to study the interplay between the structure and the conduction mechanism of these materials. The most promising materials are then tested in prototype cells in order to evaluate their performance in operating devices. As a general procedure, the electrolytes are synthesized with different concentrations of Li+ or Mg2+ charge carriers in order to evaluate the effect of the cation concentration on the thermal properties and conductivity of the materials. In addition, the complexation of the cations and its effect on the long-range charge transfer migration is carefully studied by Infrared and Raman spectroscopy. In the case of the cathodic materials the and their composition are modulated in order to study their effect on the lithium intercalation/deintercalation processes, efficiencies and on battery prototype performance. The investigated materials comprise: a) an inorganic Solid-state Li-ion conductors, based on lithium-functionalized fluorinated titanium oxide NPs; b) a new class of single-ion conducting nanocomposite polymer electrolytes for Li batteries; and c) two electrolytes for Mg secondary batteries based on ILs and an innovative Mg salt. Moreover two studies about dielectric relaxation phenomena in 4a) Magnesium-polymer electrolytes and 4b) clay-based solid polymer electrolytes (SPEs) are presented which elucidate the interplay existent between molecular relazations in host polymer matrices and long range charge transfer processes. Concerning cathodic materials a family of high voltage multi-metal phosphate cathodic materials for secondary lithium batteries is proposed, studied and tested in button battery prototypes. Firstly, a general introduction about the state of art of electrolytes and cathodes, with a particular attention on drawbacks and possible solution, which characterize these materials, is presented. Secondly, details about the synthesis and the characterizations of each class of materials is described in great details. Thirdly a concluding remark is provided.
Al fine di ottenere sistemi di accumulo di energia elettrica sempre più performanti, l'attività di ricerca qui descritta, è focalizzata sullo studio di elettroliti e materiali catodici per applicazioni in batterie al litio e magnesio. I materiali vengono sintetizzati attraverso sintesi in atmosfera inerte e caratterizzati con diverse tecniche quali: analisi termogravimetrica (TGA), calorimetria a scansione differenziale (DSC), spettroscopie vibrazionali (FT-MIR, FT-FIR, Raman), NMR di stato solido, diverse tecniche elettrochimiche (voltammetria ciclica, cronoamperometria, impedenza elettrochimica) e spettroscopia elettrica a banda larga. I risultati sono utilizzati per studiare l'interazione tra la struttura e il meccanismo di conduzione di questi materiali. I materiali più promettenti sono testati in batterie a bottone prototipo tipo CR2032 per valutare la loro ciclabilità e stabilità su lungo periodo. Come procedura generale, gli elettroliti vengono sintetizzati con differenti concentrazioni di portatori di carica tipo Mg2+ o Li+ per valutare l'effetto della concentrazione di cationi sulle proprietà termiche e sulla conducibilità dei materiali. Inoltre, la complessazione dei cationi e il suo effetto sul trasferimento di carica a lungo raggio sono studiati accuratamente tramite spettroscopia infrarossa e Raman. Nel caso dei materiali catodici la struttura e la composizione chimica di questi sistemi è modulata al fine di studiare il loro effetto sul processo di intercalazione/deinteracalazione dello ione litio, sull’efficienza e le prestastazioni dei prototipi di batteria a bottone tipo CR2032. I materiali studiati comprendono: a) un conduttore inorganico di stato solido a singolo catione di litio basato su di un ossido di titanio fluorurato; b) una nuova classe di elettroliti nanocompositi polimerici per batterie al litio; e c) due elettroliti per batterie al magnesio basati su liquidi ionici e un sale innovativo di Mg. Inoltre, al fine di evidenziare le correlazioni esistenti tra le dinamiche dei rilassamenti molecolari degli elettroliti e i processi di trasferimento di carica a lungo raggio, sono stati effettuati due studi sui meccanismi di rilassamento dielettrico di: a) elettroliti polimerici al Mg; e b) elettroliti polimerici solidi a base di alluminio silicati (SPE). Infine viene proposta una nuova promettente famiglia di materiali catodici di cui si studiano le correlazioni tra struttura, morfologia e prestazioni in batterie secondare prototipo a bottone. La tesi inizia con un’ introduzione generale sullo stato dell'arte degli elettroliti e dei catodi. Particolare attenzione è rivolta sugli svantaggi e sulle possibili future soluzioni. In secondo luogo, vengono descritti I n dettaglio la sintesi e caratterizzazione di ciascuna classe di materiali qui proposti. Quindi, si conclude evidenziando I risultati più salient ottenuti sui vari sistemi proposti.

碩士
國立中央大學
化學工程與材料工程學系
103
Thermodynamic properties of magnesium make it an attractive anode material in secondary battery. As compared to lithium and lead, magnesium has advantages of low cost, environmental friendliness, high safety and easy handling. But there are still two major challenges in developing magnesium batteries. The first one is the high chemical activity of magnesium, leading to the formation of passive layer on Mg surface (obstructing Mg ions transportation) and limiting the selection of a suitable electrolyte. The other one is the selection of the cathode materials because magnesium ions are difficult to intercalate/deintercalate into the structure in most of cathode materials. Up to now, Mo6S8, reported in 2000, is one of a few cathode materials that can accommodate magnesium ions, but still faces the drawback of the magnesium ions. In this study, Mo6S8 is chosen as the first active material for establishing the Mg battery system. Mo6S8 is fabricated by solid state reaction synthesis of Chevrel-phase Cu2Mo6S8, followed by removing copper ions in 6 M HCl. At room temperature, the capacity of Mg//Mo6S8 cell in APC electrolyte is about 60 mAh/g. In contrast, the cell capacity significantly increases to 117 mAh/g at elevated temperature of 60 C. Besides, adding lithium salt into APC electrolyte improves the cell capacity to 127 mAh/g even at room temperature. The changes of working ion and ion mobility are believed to play important roles in electrochemical and energy storage performance. After showing the remarkable benefits of lithium salt addition in Mg//Mo6S8 cell, it is worth expanding this concept to other cathode materials, which are not capable of being intercalated/deintercalated by magnesium ions before. Among them, we introduce another active material MoS2, which magnesium ions cannot intercalate/deintercalate into the structure in APC electrolyte. After adding the lithium ion in the APC electrolyte, the Mg//MoS2 cell starts storing energy and its electrochemical behavior is very similar to MoS2 in lithium-ion system. The cell delivers impressive capacities of 159 mAh/g (at 25 mA/g) and 110 mAh/g at higher current rate of 500 mA/g, respectively. To further improve the conductivity of MoS2, 10 wt% carbon nanotubes or graphene is incorporated into MoS2 via a ball milling process. The capacity of Mg//MoS2 cell is thus significantly advanced. Specifically, 190, and 210 mAh/g discharge capacities are obtained at 25 mA/g for the cells consisting of MoS2 cathode with carbon nanotubes and with graphene, respectively. At a higher current rate of 500 mA/g, the cells with carbon nanotubes and with graphene still deliver 134 and 151 mAh/g, respectively, outperforming 110 mAh/g obtained for the cell without carbon addition.

碩士
元智大學
化學工程與材料科學學系
105
This study investigates the electrochemical behavior of Mg-ion batteries using magnesium perchlorate as electrolyte. The operating temperature ranges from 298 to 318 K, and the applied voltage falls into the region of -0.2-0.2 V. The electrical conductivity, diffusion coefficient, and surface topography of polymeric separators have been systematically examined. To inspect the electrochemical behavior, three sets of experiments in the two-electrode configuration system including (a) magnesium perchlorate dissolved in propylene carbonate without separator, (b) magnesium perchlorate dissolved in propylene carbonate with separator, and (c) magnesium perchlorate dissolved in propylene carbonate and ethylene carbonate mixture with separator, have been carried out in the present work. Experimental results reveal that the electrical conductivity is an increasing function of the operating temperature. The influence of applied voltage on the electrical conductivity seems to be minor, whereas both the ionic conductivity and the diffusion coefficient show an increasing trend when operating at high temperatures. This study shed some lights on how to operate Mg-ion batteries with high electrochemical performance based on the selection of electrolyte type and appropriate temperature range.

碩士
國立中央大學
化學工程與材料工程學系
104
Magnesium is an attractive anode material for secondary batteries because of low cost, low pollution, abundance, high energy density and high safety. However, there are two major obstacle in developing ideal magnesium ion batteries (MIBs). The first one is the formation of passivation layer on the surface due to the high chemical activity of magnesium. This result in restrictions on selecting suitable electrolytes. The other one is the strong coulombic interaction between Mg2+ and the intercalation host, which makes the ion diffusion sluggish, creating a barrier for the development of the cathode materials for MIBs. In this study, MoS2 is chosen as the active material which Mg2+ ion cannot intercalate/deintercalate into the host structure in the presence of APC electrolyte. After adding the lithium salt (LiCl) in the APC electrolyte, the Mg//MoS2 cell starts storing energy and its electrochemical behavior is very similar to MoS2 in lithium-ion battery system. The electrochemical performances significantly increase with the increase of lithium-ion concentration. At low concentration (0.1 M), the cell delivers reversible capacity of 45 mAh/g (at 25 mA/g), whereas at high concentration (0.7 M) the cell delivers superior capacity of 166 mAh/g. Similarly, the cell with high concentration of Li salt showed excellent high rate retention of 64% at 1000 mA/g, whereas the cell with low concentration of Li salt showed poor retention of 31%. The ion mobility is believed to play important role in electrochemical performance. After showing the remarkable benefits of dual-salts electrolyte, it is worth expanding this concept to other electrolytes, which have the nature of high safety and environmental friendliness. Therefore, we introduce Mg(BH4)2 salt and Glyme-based solvents as electrolyte. The present study indicate that substrates, temperature, concentration, solvent and the additive effects the reversibility of Magnesium deposition and dissolution. The study showed addition of LiBH4 and NaBH4 can improve the electrochemical performance of MIBs to a greater extent. To investigate the properties of different dual-salts Mg(BH4)2 (MBH) electrolyte, MoS2/Graphene composite is chosen as the active material. Among them, MBH-diglyme electrolyte delivered highest capacity, whereas MBH-triglyme and MBH-tetraglyme electrolytes showed slightly decreased capacity owing to their high viscosity. Despite the electrochemical performance between MBH and APC electrolyte are similar, MBH electrolyte is expected to replace APC electrolyte for practical application. This study reports the possibility of Na/Mg hybrid battery based on intercalated cathode material for the first time. Compared to lithium-ion and Li/Mg hybrid battery, the high rate retention of Na/Mg hybrid battery is much higher (up to 76%) but the capacity at low current density needs to be further improved. These results provide insight for further development of Na/Mg hybrid battery.

碩士
國立臺北科技大學
材料科學與工程研究所
105
In recent years, many scientists have been searching for other metal-ion batteries to replace lithium-ion batteries. Among them, magnesium ion batteries have the opportunity to become the new generation of secondary batteries. Magnesium ion battery has higher theoretical volumetric capacity and are safer than lithium-ion battery. In this study, we synthesized layered VOx nanotubes with micron-size length and an average diameter of 154 nm as the cathode. The 0.25 M APC was employed as the electrolyte and was added with 0.5 M LiCl/NaCl/MgCl2. The cells were then charged and discharged galvanostatically at 50 mA g-1 between 2.6 and 0 V (vs.Mg2+/Mg). The first discharge capacities of APC and LiCl/NaCl added APC were 285/309/354 mA h g-1, respectively. The fifth discharge capacities reached 81/163/168 mA h g-1, respectively. We further tested of VOx prepared cathodes using low (LT-VOx) and high (HT-VOx) octadecylamine concentration in 0.5 M NaCl added 0.25 M APC electrolyte. The cells were charged and discharged galvanostatically at 100 mA g-1. After 30 cycles, the discharge capacities of LT-VOx and HT-VOx achieve 68.47/88.61 mA h g-1, respectively. The EDS analyses show that the magnesium strips and deposits at the cathode with charging and discharging, and the surface morphology of VOx does not change significantly during the cycles. The LiCl/NaCl/MgCl2 added APC electrolytes all improve the stability of magnesium and increase current density of the cells. The NaCl added APC electrolyte gives rise to the optimal electrical characteristics among the magnesium ion batteries tested.

Room temperature molten liquids are proposed to be good alternates for volatile and harmful organic compounds. They are useful in varied areas of applications ranging from synthesis, catalysis to energy storage molten electrolytes have certain unique characteristics such as low vapour pressure, reasonably high ionic conductivity, high thermal stability and wide electrochemical window. These molten liquids can be classified in to two types depending on the nature of the species present in the liquids. One, those liquids consists only of ions (e.g) conventional imidazolium based ionic liquids and other that consists of ions and solvents (e g) acetamide eutectics. Acetamide and its eutectics from room temperature molten solvents that is unique with interesting physicochemical properties. The solvent properties of molten acetamide are similar to water, with high dielectric consist of 60 at 353 k. its acid – base properties are also similar to water, and it can solublise variety of organic and inorganic compounds as well. in the present studies room temperature molten liquids consisting of acetamide as one of the components have been prepared and used for various applications. Room temperature molten electrolytes consisting of magnesium perchlorate/magnesium triflate as one of the constituents have been used for rechargeable magnesium batteries where as those consisting of zinc perchlorate /zinc triflate have been used for zinc based rechargeable batteries. Full utilization of cathode material (y-mno2) is achieved using amide-based molten liquid as electrolyte in rechargeable zinc based batteries. Ammonium nitrate/ lithium nitrate containing electrolytes have been used for electrochemical super capacitors. They have been used as solvent cum stabilizers for metallic nanochains that can be used as substrate in surface enchanced Raman scattering studies.

碩士
元智大學
化學工程與材料科學學系
105
The dissertation investigates the electrochemical performance of electrode materials synthesize with co-precipitation method for lithium-ion and magnesium-ion batteries. This study can be qualitatively divided into two parts: (i) MgCo2O4/Li4Ti5O12 (ML) for lithium-ion batteries, (ii) MgCo2O4/Graphite (MG) for magnesium-ion batteries. (i) MgCo2O4/Li4Ti5O12 for lithium-ion batteries In the present work, MgCo2O4 (MCO)/Li4Ti5O12 (LTO) composites with different MCO contents are synthesized by a co-precipitation method in order to partially replace expensive Co with Mg as well as to exploit advantages of MCO and LTO as anode materials for Li-ion batteries. X-ray diffraction patterns of as-prepared materials confirm successful fabrication of the MCO/LTO composites. The average particle size of MCO nanoparticles of the three samples are 38.1, 56.9 and 58.5 nm. Electrochemical results show that MCO/LTO anode offers a discharge capacity of 300 mAh g-1, which is two times higher than that achieved by pristine LTO. In addition, cyclic stability test reveals that the composite anode retains 86.1% of its initial capacity after 50 cycles. Electrochemical Impedance spectrum indicates that the electronic conductivity of MCO/LTO electrodes is significantly higher than that of LTO. The superior performance of the composite electrodes can be attributed to its improved conductivity as well as to the formation of active sites of MCO on LTO. (ii) MgCo2O4/Graphite for magnesium batteries This study uses co-precipitation method to synthesize MCO nanocrystals, followed by the formation of MG cathode by using mechanical mixing method. The weight ratios of MCO to graphite are set at 7:3(M7G3), 5:5(M5G5), 3:7(M3G7), according to different proportion can be divided into M7G3, M5G5 and M3G7. Through the method, MCO nanoparticles are uniformly coated over the graphite. The coin cells fabricated with the hybrid anodes were systematically investigated by CV and charge-discharge cycling test at different C rates. The current density of MG is found to have an increasing function of the loading of graphite. The maximal specific capacity of M3G7 cathode is up to 180 mAh g-1, which is two times higher than M7G3. The electrochemical impedance spectroscopy shows that the resistance of M7G3, M5G5 and M3G7 are 250.1 , 158.2  and 82.3 , respectively. On the basis of the results, the improved performance is attributed to the high conductivity of MCO and graphite which enhance the number of active sites and reduce the resistance during the electrochemical reaction. The MG cathode displays high specific capacity and low inner resistance, showing a promising feasibility for Mg-ion battery applications.

Global warming and depletion in fossil fuels have forced the society to search for alternate, clean sustainable energy sources. An obvious solution to the aforesaid problem lies in electrochemical energy storage systems like fuel cells and batteries. The desirable properties attributed to these devices like quick response, long life cycle, high round trip efficiency, clean source, low maintenance etc. have made them very attractive as energy storage devices. Compared to many advanced battery chemistries like nickel-metal hydride and lithium - ion batteries, metal-air batteries show several advantages like high energy density, ease of operation etc. The notable characteristics of metal - air batteries are the open structure with oxygen gas accessed from ambient air in the cathode compartment. These batteries rely on oxygen reduction and oxygen evolution reactions during discharging and charging processes. The efficiency of these systems is determined by the kinetics of oxygen reduction reaction. Platinum is the most preferred catalyst for many electrochemical reactions. However, high cost and stability issues restrict the use of Pt and hence there is quest for the development of stable, durable and active electrocatalysts for various redox reactions. The present thesis is directed towards exploring the electrocatalytic aspects of titanium carbonitride. TiCN, a fascinating material, possesses many favorable properties such as extreme hardness, high melting point, good thermal and electrical conductivity. Its metal-like conductivity and extreme corrosion resistance prompted us to use this material for various electrochemical studies. The work function as well as the bonding in the material can be tuned by varying the composition of carbon and nitrogen in the crystal lattice. The current study explores the versatility of TiCN as electrocatalyst in aqueous and non-aqueous media. One dimensional TiC0.7N0.3 nanowires are prepared by simple one step solvothermal method without use of any template and are characterized using various physicochemical techniques. The 1D nanostructures are of several µm size length and 40 ± 15 nm diameter (figure 1). Orientation followed by attachment of the primary particles results in the growth along a particular plane (figure 2). (a) (b) (c) Figure 1. (a) SEM images of TiC0.7N0.3 nanowires (b) TEM image and (c) High resolution TEM image showing the lattice fringes. (a) (b) (d) Figure 2. Bright field TEM images obtained at different time scales of reaction. (a) 0 h; (b) 12 h; (c) 72 h and (d) 144 h. The next aspect of the thesis discusses the electrochemical performance of TiC0.7N0.3 especially for oxygen reduction. Electrochemical oxygen reduction reaction (ORR) reveals that the nanowires possess high activity for ORR and involves four electron process leading to water as the product. The catalyst effectively converts oxygen to water with an efficiency of 85%. A comparison of the activity of different (C/N) compositions of TiCN is shown in figure 3. The composition TiC0.7N0.3 shows the maximum activity for the reaction. The catalyst is also very selective for ORR in presence of methanol and thus cross-over issue in fuel cells can be effectively addressed. Density functional theory (DFT) calculations also lead to the same composition as the best for electrocatalysis, supporting the experimental observations. Figure 3. Linear sweep voltammetric curves observed for different compositions of titanium carbonitride towards ORR. The next chapter deals with the use of TiC0.7N0.3 as air cathode for aqueous metal - air batteries. The batteries show remarkable performance in the gel- and in liquid- based electrolytes for zinc - air and magnesium - air batteries. A partial potassium salt of polyacrylic acid (PAAK) is used as the polymer to form a gel electrolyte. The cell is found to perform very well even at very high current densities in the gel electrolyte (figures 4 and 5). Figure 4 Photographs of different components of the gel - based zinc - air battery. (a) (b) Figure 5. a) Discharge curves at different current densities of 5, 20, 50 and 100 mA/cm2 for zinc-air system with TiC0.7N0.3 cathode b) Charge – discharge cycles at 50 mA/cm2 for the three electrode configuration with TiC0.7N0.3 nanowire for ORR and IrO2 for OER and Zn electrode (2h. cycle period). Similarly, the catalytic activity of TiC0.7N0.3 has also been explored in non-aqueous electrolyte. The material acts as a bifunctional catalyst for oxygen in non- aqueous medium as well. It shows a stable performance for more than 100 cycles with high reversibility for ORR and OER (figure 6). Li-O2 battery fabricated with a non-aqueous gel- based electrolyte yields very good output. (a) (b) (c) Figure 6. Galvanostatic charge –discharge cycles. (a) at 1 mA/cm2 (b) specific capacity as a function of no. of cycles (c) photographs of PAN-based gel polymer electrolyte. Another reaction of interest in non –aqueous medium is I-/I3-. redox couple. TiC0.7N0.3 nanowires show small peak to peak separation, low charge transfer resistance and hence high activity. The catalyst is used as a counter electrode in dye sensitized a solar cell that shows efficiencies similar to that of Pt, state of the art catalyst (figure 7). (a) (b) (c) Figure 7 (a) Cyclic voltammograms for I-/I3 - redox species on TiC0.7N0.3 nanowires (red), TiC0.7N0.3 particle (black) and Pt (blue). (b) Photocurrent density - voltage characteristics for DSSCs with different counter electrodes. TiC0.7N0.3 nanowire (black), TiC0.7N0.3 particle (blue), Pt (red). (c) Photograph of a sample cell. (a) (b) (c) (d) Figure 8 a) Comparison ORR activity for (i) NiTiO3(black), (ii) N-rGO (red), (iii) NiTiO3 – N-rGO (green) and (iv) Pt/C (blue) (b) Linear sweep voltammograms for OER observed on NiTiO3 – N-rGO composite (black), NiTiO3 (brown), N-rGO (blue), glassy carbon (red) in 0.5 M KOH. (c) Galvanostatic discharge curves of NiTiO3 – N-rGO as air electrode (d) Charge – discharge cycle at 5 mA/cm2 for the rechargeable battery with 10 min. cycle period. The last part of the thesis discusses about a ceramic oxide, nickel titanate. The electrocatalytic studies of the material towards ORR and OER reveal that the catalyst shows remarkable performance as a bifunctional electrode. A gel - based zinc - air battery fabricated with nickel titanate – reduced graphene oxide composite shows exceptional performance of 1000 charge-discharge cycles in the rechargeable mode (figure 8). Of course, the primary battery configuration works very well too The thesis contains seven chapters on the aspects mentioned above with summary and future perspectives given as the last chapter. An appendix based on TiN nanotubes and supercapacitor studies is given at the end.