Tae Hoon Hwang

Electrospun Core-Shell Fibers for Robust Silicon Nanoparticle Based Lithium Ion Battery Anodes

Because of its unprecedented theoretical capacity near 4000 mAh/g, which is approximately 10-fold larger compared to those of the current commercial graphite anodes, silicon has been the most promising anode for lithium ion batteries, particularly targeting large-scale energy storage applications including electrical vehicles and utility grids. Nevertheless, Si suffers from its short cycle life as well as the limitation for scalable electrode fabrication. Herein, we develop an electrospinning process to produce core-shell fiber electrodes using a dual nozzle in a scalable manner. In the core-shell fibers, commercially available nanoparticles in the core are wrapped by the carbon shell. The unique core-shell structure resolves various issues of Si anode operations, such as pulverization, vulnerable contacts between Si and carbon conductors, and an unstable sold-electrolyte interphase, thereby exhibiting outstanding cell performance: a gravimetric capacity as high as 1384 mAh/g, a 5 min discharging rate capability while retaining 721 mAh/g, and cycle life of 300 cycles with almost no capacity loss. The electrospun core-shell one-dimensional fibers suggest a new design principle for robust and scalable lithium battery electrodes suffering from volume expansion.

Spray Drying Method for Large-Scale and High-Performance Silicon Negative Electrodes in Li-Ion Batteries

Nanostructured silicon electrodes have shown great potential as lithium ion battery anodes because they can address capacity fading mechanisms originating from large volume changes of silicon alloys while delivering extraordinarily large gravimetric capacities. Nonetheless, synthesis of well-defined silicon nanostructures in an industrially adaptable scale still remains as a challenge. Herein, we adopt an industrially established spray drying process to enable scalable synthesis of silicon-carbon composite particles in which silicon nanoparticles are embedded in porous carbon particles. The void space existing in the porous carbon accommodates the volume expansion of silicon and thus addresses the chronic fading mechanisms of silicon anodes. The composite electrodes exhibit excellent electrochemical performance, such as 1956 mAh/g at 0.05C rate and 91% capacity retention after 150 cycles. Moreover, the spray drying method requires only 2 s for the formation of each particle and allows a production capability of ~10 g/h even with an ultrasonic-based lab-scale equipment. This investigation suggests that established industrial processes could be adaptable to the production of battery active materials that require sophisticated nanostructures as well as large quantity syntheses.

One-dimensional carbon-sulfur composite fibers for Na-S rechargeable batteries operating at room temperature.

Na-S batteries are one type of molten salt battery and have been used to support stationary energy storage systems for several decades. Despite their successful applications based on long cycle lives and low cost of raw materials, Na-S cells require high temperatures above 300 °C for their operations, limiting their propagation into a wide range of applications. Herein, we demonstrate that Na-S cells with solid state active materials can perform well even at room temperature when sulfur-containing carbon composites generated from a simple thermal reaction were used as sulfur positive electrodes. Furthermore, this structure turned out to be robust during repeated (de)sodiation for ~500 cycles and enabled extraordinarily high rate performance when one-dimensional morphology is adopted using scalable electrospinning processes. The current study suggests that solid-state Na-S cells with appropriate atomic configurations of sulfur active materials could cover diverse battery applications where cost of raw materials is critical.

Extremely stable cycling of ultra-thin V2O5 nanowire–graphene electrodes for lithium rechargeable battery cathodes

Vanadium pentoxide (V2O5) has received considerable attention as a lithium battery cathode because its specific capacity (>250 mA h g−1) is higher than those (<170 mA h g−1) of most commercial cathode materials. Despite this conspicuous advantage, V2O5 has suffered from limited cycle life, typically below a couple of hundred cycles due to the agglomeration of its particles. Once V2O5 particles are agglomerated, the insulating phases continuously expand to an extent that ionic and electronic conduction is severely deteriorated, leading to the significant capacity decay. In this study, in order to overcome the agglomeration issue, the electrodes were uniquely designed such that ultrathin V2O5 nanowires were uniformly incorporated into graphene paper. In this composite structure, the dispersion of V2O5 nanowires was preserved in a robust manner, and, as a result, enabled substantially improved cycle life: decent specific capacities were preserved over 100000 cycles, which are 2–3 orders of magnitude larger than those of typical battery materials.

N-doped graphitic self-encapsulation for high performance silicon anodes in lithium-ion batteries

N-doped sites at CNT and graphene trigger spontaneous encapsulation of Si particles by simple pH control at room temperature. Significantly, N-doped CNT encapsulated Si composite electrode materials show remarkable cycle life and rate performance in battery operations. Superior capacity retention of 79.4% is obtained after 200 cycles and excellent rate capability of 914 mA h g−1 is observed at a 10 C rate.

Elemental-Sulfur-Mediated Facile Synthesis of a Covalent Triazine Framework for High-Performance Lithium–Sulfur Batteries

A covalent triazine framework (CTF) with embedded polymeric sulfur and a high sulfur content of 62 wt % was synthesized under catalyst- and solvent-free reaction conditions from 1,4-dicyanobenzene and elemental sulfur. Our synthetic approach introduces a new way of preparing CTFs under environmentally benign conditions by the direct utilization of elemental sulfur. The homogeneous sulfur distribution is due to the in situ formation of the framework structure, and chemical sulfur impregnation within the micropores of CTF effectively suppresses the dissolution of polysulfides into the electrolyte. Furthermore, the triazine framework facilitates electron and ion transport, which leads to a high-performance lithium-sulfur battery.

Silicon@porous nitrogen-doped carbon spheres through a bottom-up approach are highly robust lithium-ion battery anodes

Due to its excellent capacity, around 4000 mA h g−1, silicon has been recognized as one of the most promising lithium-ion battery anodes, especially for future large-scale applications including electrical vehicles and utility power grids. Nevertheless, Si suffers from a short cycle life as well as limitations for scalable electrode fabrication. Herein, we report a novel design for highly robust and scalable Si anodes: Si nanoparticles embedded in porous nitrogen-doped carbon spheres (NCSs). The porous nature of NCSs buffers the volume changes of Si nanoparticles and thus resolves critical issues of Si anode operations, such as pulverization, vulnerable contacts between Si and carbon conductors, and an unstable solid-electrolyte interphase. The unique electrode structure exhibits outstanding performance with a gravimetric capacity as high as 1579 mA h g−1 at a C/10 rate based on the mass of both Si and C, a cycle life of 300 cycles with 94% capacity retention, as well as a discharge rate capability of 6 min while retaining a capacity of 702 mA h g−1. Significantly, the coulombic efficiencies of this structure reach 99.99%. The assembled structure suggests a design principle for high capacity alloying electrodes that suffer from volume changes during battery operations.

Delicate Structural Control of Si–SiOx–C Composite via High-Speed Spray Pyrolysis for Li-Ion Battery Anodes

Despite the high theoretical capacity, silicon (Si) anodes in lithium-ion batteries have difficulty in meeting the commercial standards in various aspects. In particular, the huge volume change of Si makes it very challenging to simultaneously achieve high initial Coulombic efficiency (ICE) and long-term cycle life. Herein, we report spray pyrolysis to prepare Si-SiOx composite using an aqueous precursor solution containing Si nanoparticles, citric acid, and sodium hydroxide (NaOH). In the precursor solution, Si nanoparticles are etched by NaOH with the production of [SiO4]4-. During the dynamic course of spray pyrolysis, [SiO4]4- transforms to SiOx matrix and citric acid decomposes to carbon surface layer with the assistance of NaOH that serves as a decomposition catalyst. As a result, a Si-SiOx composite, in which Si nanodomains are homogeneously embedded in the SiOx matrix with carbon surface layer, is generated by a one-pot process with a residence time of only 3.5 s in a flow reactor. The optimal composite structure in terms of Si domain size and Si-to-O ratio exhibited excellent electrochemical performance, such as reversible capacity of 1561.9 mAh g-1 at 0.06C rate and ICE of 80.2% and 87.9% capacity retention after 100 cycles at 1C rate.

Atomic Thin Titania Nanosheet-Coupled Reduced Graphene Oxide 2D Heterostructures for Enhanced Photocatalytic Activity and Fast Lithium Storage

Realizing practical high performance materials and devices using the properties of 2D materials is of key research interest in the materials science field. In particular, building well-defined heterostructures using more than two different 2D components in a rational way is highly desirable. In this paper, a 2D heterostructure consisting of atomic thin titania nanosheets densely grown on reduced graphene oxide surface is successfully prepared through incorporating polymer functionalized graphene oxide into the novel TiO2 nanosheets synthesis scheme. As a result of the synergistic combination of a highly accessible surface area and abundant interface, which can modulate the physicochemical properties, the resultant heterostructure can be used in high efficiency visible light photocatalysis as well as fast energy storage with a long lifecycle.