Du-Hyun Lim

Role of organic solvent addition to ionic liquid electrolytes for lithium–sulphur batteries

We investigate the role of the addition of an organic solvent to an ionic liquid electrolyte for the performance of lithium–sulphur (Li–S) batteries. We find that with a mixed electrolyte, formed by adding 10 wt% 1,3-dioxolane (DIOX) to an ionic liquid, the capacity of a Li–S cell is more than doubled, the rate capability and the cycling performance considerably improved, compared to a cell utilizing a neat ionic liquid electrolyte. The improved performance can be correlated with an enhanced ion transport, evidenced by an increased ionic conductivity and higher limiting current density, directly related to a decrease in viscosity and glass transition temperature of the mixed electrolytes. We show that this in turn is linked to a change in the local environment of the Li-ions where the organic solvent is incorporated in the coordination shell. In addition we show that the mixed electrolytes have a considerably higher thermal stability, in particular a dramatically increased flash point, and improved low temperature properties with respect to a conventional organic solvent based electrolyte currently used for Li–S batteries.

Stabilizing the Performance of High-Capacity Sulfur Composite Electrodes by a New Gel Polymer Electrolyte Configuration

Increased pollution and the resulting increase in global warming are drawing attention to boosting the use of renewable energy sources such as solar or wind. However, the production of energy from most renewable sources is intermittent and thus relies on the availability of electrical energy-storage systems with high capacity and at competitive cost. Lithium-sulfur batteries are among the most promising technologies in this respect due to a very high theoretical energy density (1675 mAh g-1 ) and that the active material, sulfur, is abundant and inexpensive. However, a so far limited practical energy density, life time, and the scaleup of materials and production processes prevent their introduction into commercial applications. In this work, we report on a simple strategy to address these issues by using a new gel polymer electrolyte (GPE) that enables stable performance close to the theoretical capacity of a low cost sulfur-carbon composite with high loading of active material, that is, 70 % sulfur. We show that the GPE prevents sulfur dissolution and reduces migration of polysulfide species to the anode. This functional mechanism of the GPE membranes is revealed by investigating both its morphology and the Li-anode/GPE interface at various states of discharge/charge using Raman spectroscopy.

Route to sustainable lithium-sulfur batteries with high practical capacity through a fluorine free polysulfide catholyte and self-standing Carbon Nanofiber membranes

We report on a new strategy to improve the capacity, reduce the manufacturing costs and increase the sustainability of Lithium-Sulfur (LiS) batteries. It is based on a semi-liquid cathode composed of a Li2S8 polysulphide catholyte and a binder-free carbon nanofiber membrane with tailored morphology. The polysulphides in the catholyte have the dual role of active material and providing Li+-conduction, i.e. no traditional Li-salt is used in this cell. The cell is able to deliver an areal capacity as high as 7 mAh cm−2, twice than that of commercial Lithium-ion batteries (LiBs) and 2–4 times higher than that of state-of-the-art LiS cells. In addition, the battery concept has an improved sustainability from a material point of view by being mainly based on sulfur and carbon and being completely fluorine-free, no fluorinated salt or binders are used, and has potential for upscaling and competitive price. The combination of these properties makes the semi-liquid LiS cell here reported a very promising new concept for practical large-scale energy storage applications.

Tailor-Made Electrospun Multilayer Composite Polymer Electrolytes for High-Performance Lithium Polymer Batteries

A novel tailor-made multilayer composite polymer electrolyte, consisting of two outer layers of electrospun polyacrylonitrile (PAN) and one inner layer of poly(vinyl acetate) (PVAc)/poly(methyl methacrylate) (PMMA)/poly(ethylene oxide) (PEO) fibrous membrane, was prepared using continuous electrospinning. These membranes, which are made up of fibers with diameters in the nanometer range, were stacked in layers to produce interconnected pores that result in a high porosity. Gel polymer electrolytes (GPEs) were prepared by entrapping a liquid electrolyte (1 M LiPF6 in ethylene carbonate/dimethyl carbonate) in the membranes. The composite membranes exhibited a high electrolyte uptake of 450-510%, coupled with an improved room temperature ionic conductivity of up to 4.72 mS cm-1 and a high electrochemical stability of 4.6 V versus Li/Li+. Electrochemical investigations of a composite membrane of PAN-PVAc-PAN, with a LiFePO4 cathode synthesized in-house, showed a high initial discharge capacity of 145 mAh g-1, which corresponds to 85% utilization of the active material, and displayed stable cycle performance.

Rational Design of Low Cost and High Energy Lithium Batteries through Tailored Fluorine-free Electrolyte and Nanostructured S/C Composite

We report a new Li-S cell concept based on an optimized F-free catholyte solution and a high loading nanostructured C/S composite cathode. The Li2 S8 present in the electrolyte ensures both buffering against active material dissolution and Li+ conduction. The high S loading is obtained by confining elemental S (≈80 %) in the pores of a highly ordered mesopores carbon (CMK3). With this concept we demonstrate stabilization of a high energy density and excellent cycling performance over 500 cycles. This Li-S cell has a specific capacity that reaches over 1000 mA h g-1 , with an overall S loading of 3.6 mg cm-2 and low electrolyte volume (i.e., 10 μL cm-2 ), resulting in a practical energy density of 365 Wh kg-1 . The Li-S system proposed thus meets the requirements for large scale energy storage systems and is expected to be environmentally friendly and have lower cost compared with the commercial Li-ion battery thanks to the removal of both Co and F from the overall formulation.

An Electrospun Core-Shell Nanofiber Web as a High-Performance Cathode for Iron Disulfide-Based Rechargeable Lithium Batteries

FeS2 /C core-shell nanofiber webs were synthesized for the first time by a unique synthesis strategy that couples electrospinning and carbon coating of the nanofibers with sucrose. The design of the one-dimensional core-shell morphology was found to be greatly beneficial for accommodating the volume changes encountered during cycling, to induce shorter lithium ion diffusion pathways in the electrode, and to prevent sulfur dissolution during cycling. A high discharge capacity of 545 mAh g-1 was retained after 500 cycles at 1 C, exhibiting excellent stable cycling performance with 98.8 % capacity retention at the last cycle. High specific capacities of 854 mAh g-1 , 518 mAh g-1 , and 208 mAh g-1 were obtained at 0.1 C, 1 C, and 10 C rates, respectively, demonstrating the exceptional rate capability of this nanofiber web cathode.

Free-Standing 3D-Sponged Nanofiber Electrodes for Ultrahigh-Rate Energy-Storage Devices

We have designed a self-standing anode built-up from highly conductive 3D-sponged nanofibers, that is, with no current collectors, binders, or additional conductive agents. The small diameter of the fibers combined with an internal spongelike porosity results in short distances for lithium-ion diffusion and 3D pathways that facilitate the electronic conduction. Moreover, functional groups at the fiber surfaces lead to the formation of a stable solid-electrolyte interphase. We demonstrate that this anode enables the operation of Li-cells at specific currents as high as 20 A g-1 (approx. 50C) with excellent cycling stability and an energy density which is >50% higher than what is obtained with a commercial graphite anode.

Coin-cell Supercapacitors Based on CVD Grown and Vertically Aligned Carbon Nanofibers (VACNFs)

Complete supercapacitors (SCs) comprising vertically aligned carbon nanofibers (VACNFs) as electrode materials have been assembled as coin-cells. The VACNFs were grown directly onto the current collector by direct current plasma enhanced chemical vapor deposition (DC-PECVD), thereby providing excellent contact with the current collector, but also eliminating the need of any binder. The vertical alignment facilitates fast ion transport and the electrolyte to access the entire surface of the CNFs. The morphology of the VACNFs was evaluated by scanning electron microscopy (SEM), while the performance was assessed by several methods: cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and device related cycling by galvanostatic charge/discharge. The capacitance, 3.64 mF/cm2 , is >15 times higher than the capacitance of a coin-cell without CNFs and the cyclic performance shows these proof-of-concept SCs to retain >80% of the capacitance after 2000 full charge/discharge cycles. The direct growth of VACNFs as electrodes at the current collector opens pathways for SC production using existing coin-cell battery production technology.