Eunjun Park

Highly Cyclable Lithium-Sulfur Batteries with a Dual-Type Sulfur Cathode and a Lithiated Si/SiOx Nanosphere Anode.

Lithium-sulfur batteries could become an excellent alternative to replace the currently used lithium-ion batteries due to their higher energy density and lower production cost; however, commercialization of lithium-sulfur batteries has so far been limited due to the cyclability problems associated with both the sulfur cathode and the lithium-metal anode. Herein, we demonstrate a highly reliable lithium-sulfur battery showing cycle performance comparable to that of lithium-ion batteries; our design uses a highly reversible dual-type sulfur cathode (solid sulfur electrode and polysulfide catholyte) and a lithiated Si/SiOx nanosphere anode. Our lithium-sulfur cell shows superior battery performance in terms of high specific capacity, excellent charge-discharge efficiency, and remarkable cycle life, delivering a specific capacity of ∼750 mAh g(-1) over 500 cycles (85% of the initial capacity). These promising behaviors may arise from a synergistic effect of the enhanced electrochemical performance of the newly designed anode and the optimized layout of the cathode.

Dual-Size Silicon Nanocrystal-Embedded SiOx Nanocomposite as a High-Capacity Lithium Storage Material

SiOx-based materials attracted a great deal of attention as high-capacity Li(+) storage materials for lithium-ion batteries due to their high reversible capacity and good cycle performance. However, these materials still suffer from low initial Coulombic efficiency as well as high production cost, which are associated with the complicated synthesis process. Here, we propose a dual-size Si nanocrystal-embedded SiOx nanocomposite as a high-capacity Li(+) storage material prepared via cost-effective sol-gel reaction of triethoxysilane with commercially available Si nanoparticles. In the proposed nanocomposite, dual-size Si nanocrystals are incorporated into the amorphous SiOx matrix, providing a high capacity (1914 mAh g(-1)) with a notably improved initial efficiency (73.6%) and stable cycle performance over 100 cycles. The highly robust electrochemical and mechanical properties of the dual-size Si nanocrystal-embedded SiOx nanocomposite presented here are mainly attributed to its peculiar nanoarchitecture. This study represents one of the most promising routes for advancing SiOx-based Li(+) storage materials for practical use.

Hydrogen Silsequioxane-Derived Si/SiOx Nanospheres for High-Capacity Lithium Storage Materials

Si/SiOx composite materials have been explored for their commercial possibility as high-performance anode materials for lithium ion batteries, but suffer from the complexity of and limited synthetic routes for their preparation. In this study, Si/SiOx nanospheres were developed using a nontoxic and precious-metal-free preparation method based on hydrogen silsesquioxane obtained from sol-gel reaction of triethoxysilane. The resulting Si/SiOx nanospheres with a uniform carbon coating layer show excellent cycle performance and rate capability with high-dimensional stability. This approach based on a scalable sol-gel reaction enables not only the development of Si/SiOx with various nanostructured forms, but also reduced production cost for mass production of nanostructured Si/SiOx.

Discovery of abnormal lithium-storage sites in molybdenum dioxide electrodes

Developing electrode materials with high-energy densities is important for the development of lithium-ion batteries. Here, we demonstrate a mesoporous molybdenum dioxide material with abnormal lithium-storage sites, which exhibits a discharge capacity of 1,814 mAh g−1 for the first cycle, more than twice its theoretical value, and maintains its initial capacity after 50 cycles. Contrary to previous reports, we find that a mechanism for the high and reversible lithium-storage capacity of the mesoporous molybdenum dioxide electrode is not based on a conversion reaction. Insight into the electrochemical results, obtained by in situ X-ray absorption, scanning transmission electron microscopy analysis combined with electron energy loss spectroscopy and computational modelling indicates that the nanoscale pore engineering of this transition metal oxide enables an unexpected electrochemical mass storage reaction mechanism, and may provide a strategy for the design of cation storage materials for battery systems.

Aerosol-Assisted Extraction of Silicon Nanoparticles from Wafer Slicing Waste for Lithium Ion Batteries

A large amount of silicon debris particles are generated during the slicing of silicon ingots into thin wafers for the fabrication of integrated-circuit chips and solar cells. This results in a significant loss of valuable materials at about 40% of the mass of ingots. In addition, a hazardous silicon sludge waste is produced containing largely debris of silicon, and silicon carbide, which is a common cutting material on the slicing saw. Efforts in material recovery from the sludge and recycling have been largely directed towards converting silicon or silicon carbide into other chemicals. Here, we report an aerosol-assisted method to extract silicon nanoparticles from such sludge wastes and their use in lithium ion battery applications. Using an ultrasonic spray-drying method, silicon nanoparticles can be directly recovered from the mixture with high efficiency and high purity for making lithium ion battery anode. The work here demonstrated a relatively low cost approach to turn wafer slicing wastes into much higher value-added materials for energy applications, which also helps to increase the sustainability of semiconductor material and device manufacturing.

A Highly Resilient Mesoporous SiOx Lithium Storage Material Engineered by Oil–Water Templating

Mesoporous silicon-based materials gained considerable attention as high-capacity lithium-storage materials. However, the practical use is still limited by the complexity and limited number of available synthetic routes. Here, we report carbon-coated porous SiOx as high capacity lithium storage material prepared by using a sol-gel reaction of hydrogen silsesquioxane and oil-water templating. A hydrophobic oil is employed as a pore former inside the SiOx matrix and a precursor for carbon coating on the SiOx . The anode exhibits a high capacity of 730 mAh g(-1) and outstanding cycling performance over 100 cycles without significant dimensional changes. Carbon-coated porous SiOx also showed highly stable thermal reliability comparable to that of graphite. These promising properties come from the mesopores in the SiOx matrix, which ensures reliable operation of lithium storage in SiOx . The scalable sol-gel process presented here can open up a new avenue for the versatile preparation of porous SiOx lithium storage materials.

In Operando Monitoring of the Pore Dynamics in Ordered Mesoporous Electrode Materials by Small Angle X-ray Scattering.

To monitor dynamic volume changes of electrode materials during electrochemical lithium storage and removal process is of utmost importance for developing high performance lithium storage materials. We herein report an in operando probing of mesoscopic structural changes in ordered mesoporous electrode materials during cycling with synchrotron-based small angel X-ray scattering (SAXS) technique. In operando SAXS studies combined with electrochemical and other physical characterizations straightforwardly show how porous electrode materials underwent volume changes during the whole process of charge and discharge, with respect to their own reaction mechanism with lithium. This comprehensive information on the pore dynamics as well as volume changes of the electrode materials will not only be critical in further understanding of lithium ion storage reaction mechanism of materials, but also enable the innovative design of high performance nanostructured materials for next generation batteries.

High-Performance Si/SiOx Nanosphere Anode Material by Multipurpose Interfacial Engineering with Black TiO2-x

Silicon oxides (SiOx) have attracted recent attention for their great potential as promising anode materials for lithium ion batteries as a result of their high energy density and excellent cycle performance. Despite these advantages, the commercial use of these materials is still impeded by low initial Coulombic efficiency and high production cost associated with a complicated synthesis process. Here, we demonstrate that Si/SiOx nanosphere anode materials show much improved performance enabled by electroconductive black TiO(2-x) coating in terms of reversible capacity, Coulombic efficiency, and thermal reliability. The resulting anode material exhibits a high reversible capacity of 1200 mAh g(-1) with an excellent cycle performance of up to 100 cycles. The introduction of a TiO(2-x) layer induces further reduction of the Si species in the SiOx matrix phase, thereby increasing the reversible capacity and initial Coulombic efficiency. Besides the improved electrochemical performance, the TiO(2-x) coating layer plays a key role in improving the thermal reliability of the Si/SiOx nanosphere anode material at the same time. We believe that this multipurpose interfacial engineering approach provides another route toward high-performance Si-based anode materials on a commercial scale.

Si/SiOx-conductive polymer core-shell nanospheres with an improved conducting path preservation for lithium-ion battery

Non-stoichiometric SiOx based materials have gained much attention as high capacity lithium storage materials. However, their anode performance of these materials should be further improved for their commercial success. A conductive polymer, poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS), is employed as a flexible electrical interconnector to improve the electrochemical performance of Si/SiOx nanosphere anode materials for lithium ion batteries (LIBs). The resulting Si/SiOx -PEDOT:PSS core-shell structured material with the small amount (1 wt %) of PEDOT:PSS shows the improved initial reversible capacity of 968.2 mA h g-1 with excellent long-term cycle performance over 200 cycles. These promising properties can be attributed to the use of the electroconductive and flexible PEDOT:PSS shell layer, which protects the electrical conduction pathways in the electrode from the large volume changes of silicon during cycling.

Multiscale Engineered Si/SiOx Nanocomposite Electrodes for Lithium-Ion Batteries Using Layer-by-Layer Spray Deposition

Si-based high-capacity materials have gained much attention as an alternative to graphite in Li-ion battery anodes. Although Si additions to graphite anodes are now commercialized, the fraction of Si that can be usefully exploited is restricted due to its poor cyclability arising from the large volume changes during charge/discharge. Si/SiO x nanocomposites have also shown promising behavior, such as better capacity retention than Si alone because the amorphous SiO x helps to accommodate the volume changes of the Si. Here, we demonstrate a new electrode architecture for further advancing the performance of Si/SiO x nanocomposite anodes using a scalable layer-by-layer atomization spray deposition technique. We show that particulate C interlayers between the current collector and the Si/SiO x layer and between the separator and the Si/SiO x layer improved electrical contact and reduced irreversible pulverization of the Si/SiO x significantly. Overall, the multiscale approach based on microstructuring at the electrode level combined with nanoengineering at the material level improved the capacity, rate capability, and cycling stability compared to that of an anode comprising a random mixture of the same materials.