Strategies toward the Improvement of Lithium Sulfur Battery Performance

Lithium-sulfur batteries (LSBs) are one of the most alluring next-generation energy storage technologies. This device can produce high specific capacity and energy density by taking advantage of the conversion reaction between lithium and sulfur. Additionally, elemental sulfur is inexpensive, abundant, non-toxic, and safe for the environment. On the other hand, the main barriers impeding a commercial breakthrough are the insulating properties of sulfur, the lithium-polysulfide shuttle effect, and the volumetric variation upon charge and discharge, which contribute to early cell failure. As a result, during the past few decades, significant research efforts have been made to develop the components of LSB. Interlayers, composites, new electrolytes, nanostructured cathode materials, and a new cell design demonstrated to be valid approaches to limit the polysulfide shuttle effect thus improving the battery performance. The current work investigates various strategies to alleviate the LSB's shortcomings. Carbonaceous materials as sulfur hosts were studied. Two unique sulfur-carbon composites containing single-walled carbon nanohorns and double-walled carbon nanotubes, were produced as LSB electrodes using a straightforward and sustainable evaporation process to demonstrate their suitability as cathodic materials. Lithium sulfide was investigated as a starting active material for the production of LSBs cathodes. The lithium-sulfide-based electrode and a biowaste-based anode were tested together in a complete cell configuration. Additionally, the impact of various electrolyte compositions on battery behavior was assessed. Alternative electrolyte salts with various anion donicity were compared to the common LSBs electrolyte. Moreover, a simultaneous investigation of the effects of electrode composition and electrolyte formulation on cell outputs is being conducted using a Design of Experiment. This effective technique takes into account all the parameters having an effect on the system response resulting in a global information on the studied subject. The last section is an overview of the projects completed in association with the ZEISS Company and the Innovations-Institut für Nanotechnologie und korrelative Mikroskopie e.V. in Forchheim, Germany. A complete workflow for battery materials analyses with cutting-edge methodology is suggested in this frame

Inkjet Printing Functionalization of SOFC LSCF Cathodes.

An important segment of the future renewable energy economy is the implementation of novel energy generation systems. Such electrochemical systems are solid oxide fuel cells, which have the advantage of direct conversion of the chemical energy stored in the fuel to electrical energy with high efficiency. Improving the performance and lowering the cost of solid oxide fuel cells (SOFCs) are strongly dependent on finding commercially viable methods for nano-functionalization of their electrodes via infiltration. Inkjet printing technology was proven to be a feasible method providing scalability and high-resolution ink delivery. LaxSr1-xCoyFe1-yO3-δ cathodes were modified using inkjet printing for infiltration with two different materials: Gd-doped ceria (CGO) commonly used as ion-conductor and La0.6Sr0.4CoO3-δ (LCO) commonly used as a mixed ionic electronic conductor. As-modified surface structures promoted the extension of the three-phase boundary (TPB) and enhanced the mechanisms of the oxygen reduction reaction. Electrochemical impedance measurements revealed significantly lowered polarization resistances (between 2.7 and 3.7 times) and maximum power output enhancement of 24% for CGO infiltrated electrodes and 40% for LCO infiltrated electrodes

Inkjet Printing Infiltration of the Doped Ceria Interlayer in Commercial Anode-Supported SOFCs.

Single-step inkjet printing infiltration with doped ceria Ce0.9Ye0.1O1.95 (YDC) and cobalt oxide (CoxOy) precursor inks was performed in order to modify the properties of the doped ceria interlayer in commercial (50 × 50 × 0.5 mm3 size) anode-supported SOFCs. The penetration of the inks throughout the La0.8Sr0.2Co0.5Fe0.5O3-δ porous cathode to the Gd0.1Ce0.9O2 (GDC) interlayer was achieved by optimisation of the inks' rheology jetting parameters. The low-temperature calcination (750 °C) resulted in densification of the Gd-doped ceria porous interlayer as well as decoration of the cathode scaffold with nanoparticles (~20-50 nm in size). The I-V testing in pure hydrogen showed a maximum power density gain of ~20% at 700 °C and ~97% at 800 °C for the infiltrated cells. The latter effect was largely assigned to the improvement in the interfacial Ohmic resistance due to the densification of the interlayer. The EIS study of the polarisation losses of the reference and infiltrated cells revealed a reduction in the activation polarisations losses at 700 °C due to the nano-decoration of the La0.8Sr0.2Co0.5Fe0.5O3-δ scaffold surface. Such was not the case at 800 °C, where the drop in Ohmic losses was dominant. This work demonstrated that single-step inkjet printing infiltration, a non-disruptive, low-cost technique, can produce significant and scalable performance enhancements in commercial anode-supported SOFCs

Synthesis of layered silicon-graphene hetero-structures by wet jet milling for high capacity anodes in Li-ion batteries

While silicon-based negative electrode materials have been extensively studied, to develop high capacity lithium-ion batteries, implementing a large-scale production method that can be easily transferred to industy, has been a crucial challenge. Here, a scalable wet-jet milling method was developed to prepare a silicon-graphene hybrid material to be used as negative electrode in lithium-ion batteries. This synthesized composite, when used as an anode in lithium cells, demonstrated high Li ion storage capacity, long cycling stability and high-rate capability. In particular, the electrode exhibited a reversible discharge capacity exceeding 1763 mAh g-1 after 450 cycles with a capacity retention of 98% and a coulombic efficiency of 99.85% (with a current density of 358 mA g-1). This significantly supersedes the performance of a Si-dominant electrode structures. The capacity fade rate after 450 cycles was only 0.005% per cycle in the 0.05-1 V range. This superior electrochemical performance is ascribed to the highly layered, silicon-graphene porous structure, as investigated via focused ion beam in conjunction with scanning electron microscopy (FIB-SEM) tomography. The hybrid electrode could retain 89% of its porosity (under a current density of 358 mA g-1) after 200 cycles compared with only 35% in a Si-dominant electrode. Moreover, this morphology can not only accommodate the large volume strains from active silicon particles, but also maintains robust electrical connectivity. This confers faster transportation of electrons and ions with significant permeation of electrolyte within the electrode. Physicochemical characterisations were performed to further correlate the electrochemical performance with the microstructural dynamics. The excellent performance of the hybrid material along with the scalability of the synthesizing process is a step forward to realize high capacity/energy density lithium-ion batteries for multiple device applications

Inkjet Printing Functionalization of SOFC LSCF Cathodes.

An important segment of the future renewable energy economy is the implementation of novel energy generation systems. Such electrochemical systems are solid oxide fuel cells, which have the advantage of direct conversion of the chemical energy stored in the fuel to electrical energy with high efficiency. Improving the performance and lowering the cost of solid oxide fuel cells (SOFCs) are strongly dependent on finding commercially viable methods for nano-functionalization of their electrodes via infiltration. Inkjet printing technology was proven to be a feasible method providing scalability and high-resolution ink delivery. LaxSr1-xCoyFe1-yO3-δ cathodes were modified using inkjet printing for infiltration with two different materials: Gd-doped ceria (CGO) commonly used as ion-conductor and La0.6Sr0.4CoO3-δ (LCO) commonly used as a mixed ionic electronic conductor. As-modified surface structures promoted the extension of the three-phase boundary (TPB) and enhanced the mechanisms of the oxygen reduction reaction. Electrochemical impedance measurements revealed significantly lowered polarization resistances (between 2.7 and 3.7 times) and maximum power output enhancement of 24% for CGO infiltrated electrodes and 40% for LCO infiltrated electrodes

Tuning the morphology of sulfur-few layer graphene composites via liquid phase evaporation for battery application

A comparative study on sulfur-based composite electrodes comprising different few-layer graphene contents prepared via a facile evaporation method is presented here. The active material production process employed here, exploring different sulfur-few layer graphene ratios, enabled tuning and optimization of the sample morphology, as confirmed via a scanning electron microscopy study. The results reveal that the graphene content is a crucial parameter yielding an optimized morphology of spherical particles composed of an elemental sulfur inner core covered by the carbonaceous compound. The electrodes are characterized in lithium metal half-cells in terms of cyclic voltammetry, galvanostatic cycling tests, rate capability and electrochemical impedance spectroscopy. Moreover, the lithium-ion diffusion coefficients of each sample are obtained by the Randles-Sevcik equation in order to evaluate the reliability of the electrochemical processes. The lithium metal half-cell with the sulfur carbon composite active material exploiting a spherical particle morphology delivers a high specific capacity of 950 mA h g(-1) after 100 cycles at C/4 with a coulombic efficiency of 98%. An optimized sample, tuned in terms of sulfur content and morphology, shows superior performance, exhibiting capacities of 1128 mA h g(-1) and 842 mA h g(-1) over 80 cycles at C/4 and 2C, respectively

Sustainable Synthesis of Sulfur-Single Walled Carbon Nanohorns Composite for Long Cycle Life Lithium-Sulfur Battery

Lithium–sulfur batteries are considered one of the most appealing technologies for next-generation energy-storage devices. However, the main issues impeding market breakthrough are the insulating property of sulfur and the lithium-polysulfide shuttle effect, which cause premature cell failure. To face this challenge, we employed an easy and sustainable evaporation method enabling the encapsulation of elemental sulfur within carbon nanohorns as hosting material. This synthesis process resulted in a morphology capable of ameliorating the shuttle effect and improving the electrode conductivity. The electrochemical characterization of the sulfur–carbon nanohorns active material revealed a remarkable cycle life of 800 cycles with a stable capacity of 520 mA h/g for the first 400 cycles at C/4, while reaching a value around 300 mAh/g at the 750th cycle. These results suggest sulfur–carbon nanohorn active material as a potential candidate for next-generation battery technology

Comparative Study of Lithium Halide-Based Electrolytes for Application in Lithium-Sulfur Batteries

Among the next-generation energy storage technologies, lithium-sulfur batteries are considered one of the most appealing solutions owing to their remarkable theoretical capacity. However, to become commercially competitive, there is a strong need to address some issues still characterizing this technology. One of the explored strategies is the optimization of the electrolyte formulation. To this aim, we compared 1,3-dioxolane/1,2-dimethoxyethane-based electrolytes containing two lithium halides, i.e., lithium bromide (LiBr) and lithium iodide (LiI), with lithium bis (trifluoromethane)sulfonylimide (LiTFSI) as a reference electrolyte. The obtained results show how the donicity of the lithium-salt anions might affect the solid electrolyte interphase stability and the lithium sulfide deposition morphology, therefore influencing the electrochemical performance of the cells. Among the tested electrolytes, the sulfur cell containing LiBr salt exhibited the best electrochemical performance maintaining a specific capacity of 900 mAh g−1 at C/4 and a stable trend along cycling at 1C with a specific capacity of about 770 mAh g−1 for 200 cycles