Gas Solubility and Vapor Pressure of Electrolytes Based on Alkylcarbonates Containing Litfsi, Lifap, and LiPF6 Lithium Salt: Measurement and Prediction

Most liquid electrolytes used in commercial lithium-ion batteries are composed by alkylcarbonate mixture containing lithium salt. The decomposition of these solvents by oxidation or reduction during cycling of the cell, induce generation of gases (CO2, CH4, C2H4, CO …) increasing of pressure in the sealed cell, which causes a safety problem [1]. The prior understanding of parameters, such as structure and nature of salt, temperature pressure, concentration, salting effects and solvation parameters, which influence gas solubility and vapor pressure of electrolytes is required to formulate safer and suitable electrolytes especially at high temperature.

We present in this work the CO2, CH4, C2H4, CO solubility in different pure alkyl-carbonate solvents (PC, DMC, EMC, DEC) and their binary or ternary mixtures as well as the effect of temperature and lithium salt LiX (X = LiPF6, LiTFSI or LiFAP) structure and concentration on these properties. Furthermore, in order to understand parameters that influence the choice of the structure of the solvents and their ability to dissolve gas through the addition of a salt, we firstly analyzed experimentally the transport properties (Self diffusion coefficient (D), fluidity (h-1), and conductivity (s) and lithium transport number (tLi) using the Stock-Einstein, and extended Jones-Dole equations [2]. Furthermore, measured data for the of CO2, C2H4, CH4 and CO solubility in pure alkylcarbonates and their mixtures containing LiPF6; LiFAP; LiTFSI salt, are reported as a function of temperature and concentration in salt. Based on experimental solubility data, the Henry’s law constant of gases in these solvents and electrolytes was then deduced and compared with values predicted by using COSMO-RS methodology within COSMOthermX software. From these results, the molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvents and electrolytes with the gases in its hypothetical liquid state were calculated and discussed [3]. Finally, the analysis of the CO2 solubility variations with the salt addition was then evaluated by determining specific ion parameters Hi by using the Setchenov coefficients in solution. This study showed that the gas solubility is entropy driven and can been influenced by the shape, charge density, and size of the anions in lithium salt.

References

[1] S.A. Freunberger, Y. Chen, Z. Peng, J.M. Griffin, L.J. Hardwick, F. Bardé, P. Novák, P.G. Bruce, Journal of the American Chemical Society 133 (2011) 8040-8047.

[2] P. Porion, Y.R. Dougassa, C. Tessier, L. El Ouatani, J. Jacquemin, M. Anouti, Electrochimica Acta 114 (2013) 95-104.

[3] Y.R. Dougassa, C. Tessier, L. El Ouatani, M. Anouti, J. Jacquemin, The Journal of Chemical Thermodynamics 61 (2013) 32-44.

A simply effective double-coating cathode with MnO2 nanosheets/graphene as functionalized interlayer for high performance lithium-sulfur batteries

Herein, we report a facile and effective adsorption strategy to improve the performance of Lithium-Sulfur (Li-S) batteries. MnO₂ nanosheets grown on the surface of highly conductive graphene resulted in a coupled composite bilayer electrode when coated onto a sulfur cathode. In this way, a high initial specific capacity of 1395 mA h g^-1 at a rate of 0.5C, a coulombic efficiency approaching 100% and steady cyclic efficiency with a fade rate of 0.3% per cycle from 10 to 100 cycles has been achieved. This hybrid electrode not only shows enhanced electrochemical performance but can also be easily controlled and scaled thereby aiding future commercialization of high-performance Li-S batteries.

Lightweight metal halide and hydride fast Li ion conductors

This work was motivated by the extensive research on lithium solid state materials, which have attracted increasing interest for potential applications in hydrogen storage and/or lithium ion batteries due to their extraordinary properties. In this thesis, LiBH4-derived materials, LiInBr4 and complex phases based on lithium ammonia borane with potential use as solid state electrolytes were successfully synthesised and characterised.

MEMS SENSOR PLATFORMS FOR IN SITU CHARACTERIZATION OF LI-ION BATTERY ELECTRODES

Lithium-ion batteries provide high energy density while being compact and light-weight and are the most pervasive energy storage technology powering portable electronic devices such as smartphones, laptops, and tablet PCs. Considerable efforts have been made to develop new electrode materials with ever higher capacity, while being able to maintain long cycle life. A key challenge in those efforts has been characterizing and understanding these materials during battery operation. While it is generally accepted that the repeated strain/stress cycles play a role in long-term battery degradation, the detailed mechanisms creating these mechanical effects and the damage they create still remain unclear. Therefore, development of techniques which are capable of capturing in real time the microstructural changes and the associated stress during operation are crucial for unravelling lithium-ion battery degradation mechanisms and further improving lithium-ion battery performance. This dissertation presents the development of two microelectromechanical systems sensor platforms for in situ characterization of stress and microstructural changes in thin film lithium-ion battery electrodes, which can be leveraged as a characterization platform for advancing battery performance. First, a Fabry-Perot microelectromechanical systems sensor based in situ characterization platform is developed which allows simultaneous measurement of microstructural changes using Raman spectroscopy in parallel with qualitative stress changes via optical interferometry. Evolutions in the microstructure creating a Raman shift from 145 cm−1 to 154 cm−1 and stress in the various crystal phases in the LixV2O5 system are observed, including both reversible and irreversible phase transitions. Also, a unique way of controlling electrochemically-driven stress and stress gradient in lithium-ion battery electrodes is demonstrated using the Fabry-Perot microelectromechanical systems sensor integrated with an optical measurement setup. By stacking alternately stressed layers, the average stress in the stacked electrode is greatly reduced by 75% compared to an unmodified electrode. After 2,000 discharge-charge cycles, the stacked electrodes retain only 83% of their maximum capacity while unmodified electrodes retain 91%, illuminating the importance of the stress gradient within the electrode. Second, a buckled membrane microelectromechanical systems sensor is developed to enable in situ characterization of quantitative stress and microstructure evolutions in a V2O5 lithium-ion battery cathode by integrating atomic force microscopy and Raman spectroscopy. Using dual-mode measurements in the voltage range of the voltage range of 2.8V – 3.5V, both the induced stress (~ 40 MPa) and Raman intensity changes due to lithium cycling are observed. Upon lithium insertion, tensile stress in the V2O5 increases gradually until the α- to ε-phase and ε- to δ-phase transitions occur. The Raman intensity change at 148 cm−1 shows that the level of disorder increases during lithium insertion and progressively recovers the V2O5 lattice during lithium extraction. Results are in good agreement with the expected mechanical behavior and disorder change in V2O5, highlighting the potential of microelectromechanical systems as enabling tools for advanced scientific investigations. The work presented here will be eventually utilized for optimization of thin film battery electrode performance by achieving fundamental understanding of how stress and microstructural changes are correlated, which will also provide valuable insight into a battery performance degradation mechanism.

Synthesis and characterization of low-cost materials for aqueous Na-ion batteries

136 p.

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.

The persistence of phase-separation in LiFePO4 with two-dimensional Li+ transport : the Cahn-Hilliard-reaction equation and the role of defects

We examine the solution of the two-dimensional Cahn-Hilliard-reaction (CHR) equation in the xy plane as a model of Li+ intercalation into LiFePO4 material. We validate our numerical solution against the solution of the depth-averaged equation, which has been used to model intercalation in the limit of highly orthotropic diffusivity and gradient penalty tensors. We then examine the phase-change behaviour in the full CHR system as these parameters become more isotropic, and find that as the Li+ diffusivity is increased in the x direction, phase separation persists at high currents, even in small crystals with averaged coherency strain included. The resulting voltage curves decrease monotonically, which has previously been considered a hallmark of crystals that fill homogeneously.

Nanoindentation study of the mechanical behavior of TiO2 nanotube arrays

Titanium dioxide (TiO2) nanotube arrays are attracting increasing attention for use in solar cells, lithium-ion batteries, and biomedical implants. To take full advantage of their unique physical properties, such arrays need to maintain adequate mechanical integrity in applications. However, the mechanical performance of TiO2 nanotube arrays is not well understood. In this work, we investigate the deformation and failure of TiO2 nanotube arrays using the nanoindentation technique. We found that the load–displacement response of the arrays strongly depends on the indentation depth and indenter shape. Substrate-independent elastic modulus and hardness can be obtained when the indentation depth is less than 2.5% of the array height. The deformation mechanisms of TiO2 nanotube arrays by Berkovich and conical indenters are closely associated with the densification of TiO2 nanotubes under compression. A theoretical model for deformation of the arrays under a largeradius conical indenter is also proposed.

Two-dimensional tin disulfide nanosheets for enhanced sodium storage

Sodium-ion batteries (SIBs) are considered as complementary alternatives to lithium-ion batteries for grid energy storage due to the abundance of sodium. However, low capacity, poor rate capability, and cycling stability of existing anodes significantly hinder the practical applications of SIBs. Herein, ultrathin two-dimensional SnS2 nanosheets (3-4 nm in thickness) are synthesized via a facile refluxing process toward enhanced sodium storage. The SnS2 nanosheets exhibit a high apparent diffusion coefficient of Na+ and fast sodiation/desodiation reaction kinetics. In half-cells, the nanosheets deliver a high reversible capacity of 733 mAh g-1 at 0.1 A g-1, which still remains up to 435 mAh g-1 at 2 A g-1. The cell has a high capacity retention of 647 mA h g-1 during the 50th cycle at 0.1 A g-1, which is by far the best for SnS2, suggesting that nanosheet morphology is beneficial to improve cycling stability in addition to rate capability. The SnS2 nanosheets also show encouraging performance in a full cell with a Na3V2(PO4)3 cathode. In addition, the sodium storage mechanism is investigated by ex situ XRD coupled with high-resolution TEM. The high specific capacity, good rate capability, and cycling durability suggest that SnS2 nanosheets have great potential working as anodes for high-performance SIBs. © 2015 American Chemical Society.

Synthesis and characterization of self-assembled nanofiber-bundles of V(2)O(5): their electrochemical and field emission properties

High-quality self-assembled V(2)O(5) nanofiber-bundles (NBs) are synthesized by a simple and direct hydrothermal method using a vanadium(V) hydroxylamido complex as a vanadium source in the presence of HNO(3). The possible reaction pathway for the formation of V(2)O(5) NBs is discussed and demonstrated that HNO(3) functions both as an oxidizing and as an acidification agent. V(2)O(5) NBs are single-crystals of an orthorhombic phase that have grown along the [010] direction. A bundle is made of indefinite numbers of homogeneous V(2)O(5) nanofibers where nanofibers have lengths up to several micrometres and widths ranging between 20 and 50 nm. As-prepared V(2)O(5) NBs display a high electrochemical performance in a non-aqueous electrolyte as a cathode material for lithium ion batteries. Field emission properties are also investigated which shows that a low turn-on field of similar to 1.84 V mu m(-1) is required to draw the emission current density of 10 mu Lambda cm(-2).

Time-Temperature Scaling of Conductivity Spectra of Organic Plastic Crystalline Conductors

Organic plastic crystalline soft matter ion conductors are interesting alternatives to liquid electrolytes in electrochemical storage devices such as Lithium-ion batteries. The solvent dynamics plays a major role in determining the ion transport in plastic crystalline ion conductors. We present here an analysis of the frequency-dependent ionic conductivity of succinonitrile-based plastic crystalline ion conductors at varying salt composition (0.005 to 1 M) and temperature (-20 to 60 degrees C) using time-temperature superposition principle (TTSP). The main motivation of the work has been to establish comprehensive insight into the ion transport mechanism from a single method viz, impedance spectroscopy rather than employing cluster of different characterization methods probing various length and time scales. The TTSP remarkably aids in explicit identification of the extent of the roles of solvent dynamics and ion-ion interactions on the effective conductivity of the orientationally disordered plastic crystalline ion conductors.

Nanostructured electrode materials for electrochemical energy storage and conversion

Manipulation of matter at the nanoscale is a way forward to move beyond our current choices in electrochemical energy storage and conversion technologies with promise of higher efficiency, environmental benignity, and cost-effectiveness. Electrochemical processes being basically surface phenomena, tailored multifunctional nanoarchitecturing can lead to improvements in terms of electronic and ionic conductivities, diffusion and mass transport, and electron transfer and electrocatalysis. The nanoscale is also a domain in which queer properties surface: those associated with conversion electrodes, ceramic particles enhancing the conductivity of polymer electrolytes, and transition metal oxide powders catalyzing fuel cell reactions, to cite a few. Although this review attempts to present a bird's eye view of the vast literature that has accumulated in this rather infant field, it also lists a few representative studies that establish the beneficial effects of going `nano'. Investigations on nanostructuring and use of nanoparticles and nanoarchitectures related to lithium-ion batteries (active materials and electrolytes), supercapacitors (electrical double-layer capacitors, supercapacitors based on pseudo-capacitance, and hybrid supercapacitors), and fuel cells (electrocatalysts, membranes and hydrogen storage materials) are highlighted. (C) 2012 John Wiley & Sons, Ltd.

Development and Application of Embedding Methods for the Simulation of Large Chemical Systems

The high computational cost of correlated wavefunction theory (WFT) calculations has motivated the development of numerous methods to partition the description of large chemical systems into smaller subsystem calculations. For example, WFT-in-DFT embedding methods facilitate the partitioning of a system into two subsystems: a subsystem A that is treated using an accurate WFT method, and a subsystem B that is treated using a more efficient Kohn-Sham density functional theory (KS-DFT) method. Representation of the interactions between subsystems is non-trivial, and often requires the use of approximate kinetic energy functionals or computationally challenging optimized effective potential calculations; however, it has recently been shown that these challenges can be eliminated through the use of a projection operator. This dissertation describes the development and application of embedding methods that enable accurate and efficient calculation of the properties of large chemical systems.

Chapter 1 introduces a method for efficiently performing projection-based WFT-in-DFT embedding calculations on large systems. This is accomplished by using a truncated basis set representation of the subsystem A wavefunction. We show that naive truncation of the basis set associated with subsystem A can lead to large numerical artifacts, and present an approach for systematically controlling these artifacts.

Chapter 2 describes the application of the projection-based embedding method to investigate the oxidative stability of lithium-ion batteries. We study the oxidation potentials of mixtures of ethylene carbonate (EC) and dimethyl carbonate (DMC) by using the projection-based embedding method to calculate the vertical ionization energy (IE) of individual molecules at the CCSD(T) level of theory, while explicitly accounting for the solvent using DFT. Interestingly, we reveal that large contributions to the solvation properties of DMC originate from quadrupolar interactions, resulting in a much larger solvent reorganization energy than that predicted using simple dielectric continuum models. Demonstration that the solvation properties of EC and DMC are governed by fundamentally different intermolecular interactions provides insight into key aspects of lithium-ion batteries, with relevance to electrolyte decomposition processes, solid-electrolyte interphase formation, and the local solvation environment of lithium cations.

The use of non-dimensional parameters to study stress in lithiumion battery electrode storage particles

Mechanical degradation is thought to be one of the causes of capacity fade within Lithium-Ion batteries. In this work we develop a coupled stress-diffusion model for idealized spherical storage particles, which is analogous to the development of thermal strains. We then non-dimensionalize the model and identify three important parameters that control the development of stress within these particles. We can therefore use a wide number of values for these parameters to make predictions about the stress responses of different materials. The maximum stress developed within the particle for different values of these parameters are plotted as stress maps. A two dimensional model of a battery was then developed, in order to study the effect of particle morphology. Copyright © 2012 by ASME.

聚合物锂离子电池和生物燃料电池的相关研究

本论文分为两个部分研究了铿离子电池和生物燃料电池中的关键材料，主要的创新点和结论如下。采用聚合物电解质是提高铿二次电池性能的有效方法之一。聚合物电解质良好电导率、高铿离子迁移数、宽电化学窗口以及好的机械性能是其应用于铿二次电池中的关键。论文的第一部分主要讨论了聚合物、增塑剂和无机纳米粒子等对复合电解质体系的化学和物理性质的影响。我们采用溶液浇注一浸渍法制备了各种纳米复合聚合物电解质，例如开发出基于PVDFHFP或梳状聚合物基体的全固态以及聚合物和碳酸醋形成的胶体聚合物电解质体系。首次制备了具有较高离子电导率的单离子聚合物电解质。考察了两类纳米粒子填充物对体系的影响：一种是“惰性”发烟硅；另一种是“活性”蒙脱土。比较了全固态和胶体聚合物电解质体系电化学性质的不同之处。采用电化学交流阻抗，示差扫描量热法，X衍射，拉曼光谱，红外光谱，扫描电镜，循环伏安等方法详细研究了聚合物电解质中各组分对体系离子电导率和机械性能的影响。研究结果表明，纳米复合物为开发具有特定电化学和机械性能的电解质提供了一种有效的途径，它对聚合物电解质的物理性质影响明显。纳米粒子的加入增强了体系的机械性能，同时也使体系对溶剂的吸附能力增加。在全固态聚合物电解质中加入增塑剂，形成胶体态聚合物电解质，体系的电导率大大增加。所制备的胶体复合物电解质的室温电导率可以达到10-3s cm-1的数量级，机械强度好，阳离子迁移数高。指出选择合适的添加剂及复合方法，控制界面的结构和形态，形成尽可能多的高导电的界面，是获得电导率高和机械性能良好的聚合物电解质的有效途径。并讨论了聚合物电解质在铿离子电池中的应用。 近年来，针对生物燃料电池的研究得到了广泛关注，其中实现蛋白质酶分子和电极之间的直接电子传递是研究中的热点。论文的第二部分主要研究了生物燃料电池中的酶电极。通过对碳纳米管（MWNTs）进行预处理，使其表面带有功能性官能团，从而可以实现酶分子在碳纳米管表面的固定，同时还保持了其生物活性。采用吸附法将微过氧化物酶-11（MP-11）或葡萄糖氧化酶（GOx）等生物分子固定到MWNTs上制成酶修饰电极，研究MWNTs对酶和电极之间电子传递的促进作用。当酶分子（MP-11，GOX）固定到MWNTs表面后，循环伏安结果显示出一对可逆的氧化还原峰，对应酶分子的直接电子转移。研究结果表明这种方法可以扩展到固定其他生物酶分子以及实现蛋白质酶分子和电极之间的直接电化学，可以获得一系列氧化还原酶分子的电化学参数，如反应速率常数等。同时，我们还研究了酶修饰电极对其底物的电催化反应。研究结果表明，该修饰电极对底物的电化学反应表现出较好的催化活性。我们还研究了酶分子在MWNTs修饰铂微电极上的电化学行为。这些研究为研制生物燃料电池提供了一种固定酶以及制备电极材料较好的方法。