N7-(carboxymethyl)guanine-lithium crystalline complex: a bioinspired solid electrolyte

Electrochemical device with components having direct significance to biological life processes is a potent futuristic strategy for the realization of all-round green and sustainable development. We present here synthesis design, structural analysis and ion transport of a novel solid organic electrolyte (G7Li), a compound reminiscent of ion channels, derived from regioisomeric N7-guanine-carboxylate conjugate and Li-ions. G7Li, with it's in-built supply of Li(+)-ions, exhibited remarkably high lithium-ion transference number (= 0.75) and tunable room temperature ionic conductivity spanning three decades (≈10(-7) to 10(-3) Ω(-1) cm(-1)) as a function of moisture content. The ionic conductivity show a distinct reversible transition around 80-100 °C, from a dual Li(+) and H(+) (<100 °C) to a pure Li(+) conductor (>100 °C). Systematic studies reveal a transition from water-assisted Li-ion transport to Li hopping-like mechanism involving guanine-Li coordination. While as-synthesized G7Li has potential in humidity sensors, the anhydrous G7Li is attractive for rechargeable batteries.

Lithium-ion capacitors with 2D Nb2CTx (MXene) - carbon nanotube electrodes

There is a growing interest to hybrid energy storage devices, such as lithium-ion capacitors, in which battery-type electrodes are combined with capacitor-type ones. It is anticipated that the energy density (either gravimetric or volumetric) of lithium-ion capacitors is improved if pseudocapacitive or fast insertion materials are used instead of conventional activated carbon (AC) in the capacitor-type electrode. MXenes, a new family of two-dimensional transition metal carbides, demonstrate metallic conductivity and fast charge-discharge behavior that make them suitable for this application. In this study, we move beyond single electrodes, half-cell studies and demonstrate three types of hybrid cells using Nb2CTx-carbon nanotube (CNT) films. It is shown that lithiated graphite/Nb2CTx-CNT, Nb2CTx-CNT/LiFePO4 and lithiated Nb2CTx-CNT/Nb2CTx-CNT cells are all able to operate within 3 V voltage windows and deliver capacities of 43, 24 and 36 mAh/g (per total weight of two electrodes), respectively. Moreover, the polarity of the electrodes can be reversed in the symmetric Nb2CTx-CNT cells from providing a positive potential between 0 and 3 V to a negative one from -3 to 0 V. It is shown that the volumetric energy density (50-70 Wh/L) of our first-generation devices with MXene electrodes exceeds that of a lithium titanate/AC capacitor.

Synthesis of a porous sheet-like V₂O₅-CNT nanocomposite using an ice-templating 'bricks-and-mortar' assembly approach as a high-capacity, long cyclelife cathode material for lithium-ion batteries

Tailoring the nanostructures of electrode materials is an effective way to enhance their electrochemical performance for energy storage. Herein, an ice-templating "bricks-and-mortar" assembly approach is reported to make ribbon-like V2O5 nanoparticles and CNTs integrated into a two-dimensional (2D) porous sheet-like V2O5-CNT nanocomposite. The obtained sheet-like V2O5-CNT nanocomposite possesses unique structural characteristics, including a hierarchical porous structure, 2D morphology, large specific surface area and internal conducting networks, which lead to superior electrochemical performances in terms of long-term cyclability and significantly enhanced rate capability when used as a cathode material for LIBs. The sheet-like V2O5-CNT nanocomposite can charge/discharge at high rates of 5C, 10C and 20C, with discharge capacities of approximately 240 mA h g-1, 180 mA h g-1, and 160 mA h g-1, respectively. It also retains 71% of the initial discharge capacity after 300 cycles at a high rate of 5C, with only 0.097% capacity loss per cycle. The rate capability and cycling performance of the sheet-like V2O5-CNT nanocomposite are significantly better than those of commercial V2O5 and most of the reported V2O5 nanocomposite.

In situ prepared V2O5/graphene hybrid as a superior cathode material for lithium-ion batteries

Developing synthetic methods for graphene based cathode materials, with low cost and in an environmentally friendly way, is necessary for industrial production. Although the precursor of graphene is abundant on the earth, the most common precursor of graphene is graphene oxide (GO), and it needs many steps and reagents for transformation to graphite. The traditional approach for the synthesis of GO needs many chemicals, thus leading to a high cost for production and potentially great amounts of damage to the environment. In this study, we develop a simple wet ball-milling method to construct a V2O5/graphene hybrid structure in which nanometre-sized V2O5 particles/aggregates are well embedded and uniformly dispersed into the crumpled and flexible graphene sheets generated by in situ conversion of bulk graphite. The combination of V2O5 nanoparticles/aggregates and in situ graphene leads the hybrid to exhibit a markedly enhanced discharge capacity, excellent rate capability, and good cycling stability. This study suggests that nanostructured metal oxide electrodes integrated with graphene can address the poor cycling issues of electrode materials that suffer from low electronic and ionic conductivities. This simple wet ball-milling method can potentially be used to prepare various graphene based hybrid electrodes for large scale energy storage applications.

Disordered spinel LiNi0.5Mn1.5O4 cathode with improved rate performance for lithium-ion batteries

The high voltage LiNi0.5Mn1.5O4 cathode with a disordered spinel structure is synthesized by a glycine-assisted low-temperature reaction follows by a thermal treatment at 750 °C, 850 °C, and 950 °C for 12 h. Glycine is used as a chelating agent for the first time to build required environment for shaping the precursor of LiNi0.5Mn1.5O4 materials. The microstructure and morphology of the LiNi0.5Mn1.5O4 product are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Brunauer-Emmett-Teller, and transmission electron microscopy. The sample prepares at 750 °C reveals small particles with well-defined crystals as confirmed by electron microscopy. Electrochemical results demonstrate that LiNi0.5Mn1.5O4 electrode anneal at 750 °C (compare to other two samples) delivers the highest reversible capacity of 110 mAh g-1 at 0.2C after 100 cycles with good rate capability. The enhanced electrochemical performance could be attributed to the smaller particle sizes as well as well-defined crystals which provide a directional and shorter diffusion path length for Li+ transportation within the crystals.

Unexpected effect of tetraglyme plasticizer on lithium ion dynamics in PAMPS based ionomers

Li(+) cation conducting ionomers based on poly(2-acrylamido-2-methyl-1-propane sulphonic acid) (PAMPS) incorporating a low molecular weight plasticizer have been characterized. Previously we have observed an apparent decoupling of ionic conductivity and lithium ion dynamics from the Tg of this ionomer along with an increase in ionic conductivity obtained by incorporating a quaternary ammonium co-cation. The incorporation of tetraglyme as a coordinating plasticizer was investigated in order to further improve the ion dissociation and dynamics. Solid-state NMR, thermal analysis, impedance spectroscopy and infrared spectroscopy were used to characterize these systems. As expected, the glass transition temperature Tg decreased upon the addition of the plasticizer. However, in contrast to the previously reported Na-conducting systems, the ionic conductivity was also decreased by several orders of magnitude, indicating that the tetraglyme recouples the conductivity back to the polymer dynamics. Temperature dependent (7)Li NMR line width and T1 measurements were used to probe the Li(+) dynamics, which were found to be dependent on the Li(+) concentration, the nature of the co-cation and the presence or absence of tetraglyme.

In situ MRI of operating solid-state Lithium metal cells based on ionic plastic crystal electrolytes

Solid-state ion conductors based on organic ionic plastic crystals (OIPCs) are a promising alternative to conventional liquid electrolytes in lithium battery applications. The OIPC-based electrolytes are safe (nonflammable) and flexible in terms of design and operating conditions. Magnetic resonance imaging (MRI) is a powerful noninvasive method enabling visualization of various chemical phenomena. Here, we report a first quantitative in situ MRI study of operating solid-state lithium cells. Lithium ion transfer into the OIPC matrix during the ongoing discharge of the anode results in partial liquefaction of the electrolyte at the metal interface. The developed liquid component enhances the ion transport across the interface and overall battery performance. Displacement of the liquefaction front is accompanied by a faster Li transfer through the grain boundaries and depletion at the cathode. The demonstrated solid-liquid hybrid properties, inherent in many OIPCs, combine benefits of highly conductive ionic liquids with safety and flexibility of solids.

Study of lithium conducting single ion conductor based on polystyrene sulfonate for lithium battery application

The effect of processing history and morphology is of particular importance for lithium-ion electrolytes for achieving higher ionic conductivities. In this study, single ion conducting poly (4-lithium styrene sulfonic acid) was synthesized by neutralization reaction from polystyrene sulfonic acid, and the effect of morphology and processing method was studied by comparing pelletized, electrospun and gel samples. The PSSLi gels displayed best ionic conductivity, while the pelletized samples showed the worst ionic conductivity. Although electrospinning led to a free standing electrolyte, the lower amount of solvent phase led to lower ionic conductivity when compared to the PSSLi gel. The ionic conductivity at room temperature improved from 6.6 × 10−5 S/cm to 1.4 × 10−3 S/cm by optimizing the processing methodology and the lithium ion concentration. The results show that PSSLi based single ion conducting lithium (SICL) gels are a promising candidate for lithium ion battery application.

CO-ELECTROPHORETIC DEPOSITION OF LIQUID METAL AND SILICON FOR LITHIUM-ION BATTERY APPLICATION

A low cost electrophoretic deposition (EPD) process was successfully used for liquid metal thin film deposition with a high depositing rate of 0.6 µ/min. Furthermore, silicon nano-powder and liquid metal were then simultaneously deposited as the negative electrode of lithium-ion battery by a technology called co-EPD. The liquid metal was hoping to act as the matrix for silicon particles during lithium ion insertion and distraction. Half-cell testing was performed using as prepared co-EPD sample. An initial discharge capacity of 1500 mAh/g was reported for nano-silicon and galinstan electrode, although the capacity fading issue of these samples was also observed.

High Pressure and Low Temperature Study of Ammonia Borane and Lithium Amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.

A NOVEL MODELING AND STATE OF CHARGE ESTIMATION SCHEME FOR LITHIUM-ION BATTERIES

Lithium Ion (Li-Ion) batteries have got attention in recent decades because of their undisputable advantages over other types of batteries. They are used in so many our devices which we need in our daily life such as cell phones, lap top computers, cameras, and so many electronic devices. They also are being used in smart grids technology, stand-alone wind and solar systems, Hybrid Electric Vehicles (HEV), and Plug in Hybrid Electric Vehicles (PHEV). Despite the rapid increase in the use of Lit-ion batteries, the existence of limited battery models also inadequate and very complex models developed by chemists is the lack of useful models a significant matter. A battery management system (BMS) aims to optimize the use of the battery, making the whole system more reliable, durable and cost effective. Perhaps the most important function of the BMS is to provide an estimate of the State of Charge (SOC). SOC is the ratio of available ampere-hour (Ah) in the battery to the total Ah of a fully charged battery. The Open Circuit Voltage (OCV) of a fully relaxed battery has an approximate one-to-one relationship with the SOC. Therefore, if this voltage is known, the SOC can be found. However, the relaxed OCV can only be measured when the battery is relaxed and the internal battery chemistry has reached equilibrium. This thesis focuses on Li-ion battery cell modelling and SOC estimation. In particular, the thesis, introduces a simple but comprehensive model for the battery and a novel on-line, accurate and fast SOC estimation algorithm for the primary purpose of use in electric and hybrid-electric vehicles, and microgrid systems. The thesis aims to (i) form a baseline characterization for dynamic modeling; (ii) provide a tool for use in state-of-charge estimation. The proposed modelling and SOC estimation schemes are validated through comprehensive simulation and experimental results.

One-step preparation of graphene nanosheets via ball milling of graphite and the application in lithium-ion batteries

An improved method for mass production of good-quality graphene nanosheets (GNs) via ball milling pristine graphite with dry ice is presented. We also report the enhanced performance of these GNs as working electrode in lithium-ion batteries (LIBs). In this improved method, the decrease of necessary ball milling time from 48 to 24 h and the increase of Brunauer–Emmett–Teller surface area from 389.4 to 490 m2/g might be resulted from the proper mixing of stainless steel balls with different diameters and the optimization of agitation speed. The as-prepared GNs are investigated in detail using a number of techniques, such as scanning electron microscope, atomic force microscope, high-resolution transmission electron microscopy, selected area electron diffraction, X-ray diffractometer, and Fourier transform infrared spectroscopic. To demonstrate the potential applications of these GNs, the performances of the LIBs with pure Fe3O4 electrode and Fe3O4/graphene (Fe3O4/G) composite electrode were carefully evaluated. Compared to Fe3O4-LIBs, Fe3O4/G-LIBs exhibited prominently enhanced performance and a reversible specific capacity of 900 mAh g−1 after 5 cycles at 100 and 490 mAh g−1 after 5 cycles at 800 mA g−1. The improved cyclic stability and enhanced rate capability were also obtained.

Investigation of Phosphonium Bis(fluorosulfonyl)imide-based ionic liquid electrolytes for lithium batteries

The project was about improving the performance of lithium batteries by using alternative electrolytes, combining aspects of applied technology and high-end scientific research. It showed the possibility of using novel ionic electrolytes as a superior alternative to conventional electrolytes, improving performance and safety, resulting in three high quality journal publications.

Advances in integration of photovoltaic power and energy production in practical systems

This thesis presents advances in integration of photovoltaic (PV) power and energy in practical systems, such as existing power plants in buildings or directly integrated in the public electrical grid. It starts by providing an analyze of the current state of PV power and some of its limitations. The work done in this thesis begins by providing a model to compute mutual shading in large PV plants, and after provides a study of the integration of a PV plant in a biogas power plant. The remainder sections focus on the work done for project PVCROPS, which consisted on the construction and operation of two prototypes composed of a PV system and a novel battery connected to a building and to the public electrical grid. These prototypes were then used to test energy management strategies and validate the suitability of the two advanced batteries (a lithium-ion battery and a vanadium redox ow battery) for households (BIPV) and PV plants. This thesis is divided in 7 chapters: Chapter 1 provides an introduction to explain and develop the main research questions studied for this thesis; Chapter 2 presents the development of a ray-tracing model to compute shading in large PV elds (with or without trackers); Chapter 3 shows the simulation of hybridizing a biogas plant with a PV plant, using biogas as energy storage; Chapters 4 and 5 present the construction, programming, and initial operation of both prototypes (Chapter 4), EMS testing oriented to BIPV systems (Chapter 5). Finally, Chapters 6 provides some future lines of investigation that can follow this thesis, and Chapter 7 shows a synopsis of the main conclusions of this work; Resumo: Avanços na integracão de potência fotovoltaica e producão de energia em sistemas práticos Esta tese apresenta avanços na integração de potência e energia fotovoltaica (PV) em sistemas práticos, tais como centrais existentes ou a rede eléctrica pública. Come ça por analisar o estado corrente do fotovoltaico no mundo e aborda algumas das suas limitações. O trabalho feito para esta tese de doutoramento começou pelo desenvolvimento de um modelo para calcular os sombreamentos que ocorrem em grandes campos fotovoltaicos, e depois apresenta um estudo sobre a integração um sistema fotovoltaico em uma central eléctrica a bióg as. As ultimas secções da tese focam-se no trabalho feito para o projecto PVCROPS, que consistiu na construção e operação de dois demonstratores, cada um formado por um sistema fotovoltaico e bateria conectados a um edíficio e a rede eléctrica pública. Estes protótipos foram posteriormente utilizados para testar estratégias de gestão de energia (EMS) e para validar a operação de duas baterias avançadas (bateria de Iões de Li tio e bateria de Fluxo Redox de Van adio) e a sua utiliza ção para habitações e centrais PV. A tese está dividida em 7 capitulos: O capitulo 1 apresenta uma introdução para explicar e desenvolver as principais questões que foram investigadas nesta tese; O capitulo 2 mostra o desenvolvimento de um modelo baseado em traçados de raios para calcular sombreamentos mútuos em grandes centrais PV (com e sem seguidores); O capitulo 3 mostra a simulação da hibridização de uma central electrica a biogas com uma central PV, e utilizando o biógas como armazenamento de energia. Os capitulos 4 e 5 apresentam a construção, programação e operação inicial dos dois demonstradores (Capitúlo 4), o teste de EMS orientadas para sistemas PV em habitações (Capítulo 5). Finalmente, o capítulo 6 sugere algumas futuras linhas de investigação que poderão seguir esta tese, e o Capítulo 7 faz uma sinopse das principais conclusões deste trabalho.