Hyeokjun Park

Dissolution and ionization of sodium superoxide in sodium-oxygen batteries.

With the demand for high-energy-storage devices, the rechargeable metal–oxygen battery has attracted attention recently. Sodium–oxygen batteries have been regarded as the most promising candidates because of their lower-charge overpotential compared with that of lithium–oxygen system. However, conflicting observations with different discharge products have inhibited the understanding of precise reactions in the battery. Here we demonstrate that the competition between the electrochemical and chemical reactions in sodium–oxygen batteries leads to the dissolution and ionization of sodium superoxide, liberating superoxide anion and triggering the formation of sodium peroxide dihydrate (Na2O2·2H2O). On the formation of Na2O2·2H2O, the charge overpotential of sodium–oxygen cells significantly increases. This verification addresses the origin of conflicting discharge products and overpotentials observed in sodium–oxygen systems. Our proposed model provides guidelines to help direct the reactions in sodium–oxygen batteries to achieve high efficiency and rechargeability.

A New Perspective on Li–SO2 Batteries for Rechargeable Systems

Primary Li-SO2 batteries offer a high energy density in a wide operating temperature range with exceptionally long shelf life and have thus been frequently used in military and aerospace applications. Although these batteries have never been demonstrated as a rechargeable system, herein, we show that the reversible formation of Li2S2O4, the major discharge product of Li-SO2 battery, is possible with a remarkably smaller charging polarization than that of a Li-O2 battery without the use of catalysts. The rechargeable Li-SO2 battery can deliver approximately 5400 mAh g(-1) at 3.1 V, which is slightly higher than the performance of a Li-O2 battery. In addition, the Li-SO2 battery can be operated with the aid of a redox mediator, exhibiting an overall polarization of less than 0.3 V, which results in one of the highest energy efficiencies achieved for Li-gas battery systems.

High-efficiency and high-power rechargeable lithium–sulfur dioxide batteries exploiting conventional carbonate-based electrolytes

Shedding new light on conventional batteries sometimes inspires a chemistry adoptable for rechargeable batteries. Recently, the primary lithium-sulfur dioxide battery, which offers a high energy density and long shelf-life, is successfully renewed as a promising rechargeable system exhibiting small polarization and good reversibility. Here, we demonstrate for the first time that reversible operation of the lithium-sulfur dioxide battery is also possible by exploiting conventional carbonate-based electrolytes. Theoretical and experimental studies reveal that the sulfur dioxide electrochemistry is highly stable in carbonate-based electrolytes, enabling the reversible formation of lithium dithionite. The use of the carbonate-based electrolyte leads to a remarkable enhancement of power and reversibility; furthermore, the optimized lithium-sulfur dioxide battery with catalysts achieves outstanding cycle stability for over 450 cycles with 0.2 V polarization. This study highlights the potential promise of lithium-sulfur dioxide chemistry along with the viability of conventional carbonate-based electrolytes in metal-gas rechargeable systems.

Abnormal self-discharge in lithium-ion batteries

Lithium-ion batteries are expected to serve as a key technology for large-scale energy storage systems (ESSs), which will help satisfy recent increasing demands for renewable energy utilization. Besides their promising electrochemical performance, the low self-discharge rate (<5% of the stored capacity over 1 month) of lithium-ion batteries is one of their most significant advantages for ESSs. Herein, contrary to conventional belief, we report that the self-discharge of LIBs can be abnormally accelerated when the battery has been exposed even to a routine short-term thermal exposure. We demonstrate that this thermal ‘history’ in addition to the temperature itself is memorized in the battery and accelerates the self-discharge rate. The series of characterizations performed in our work reveal that the electrolyte salt acts as a strong oxidizing agent by vigorously damaging the surface of the cathode, producing an internal ‘parasitic’ lithium source that continuously supplies lithium for the self-discharge. Although it is widely known that battery operation at elevated temperature generally induces faster degradation of capacity over multiple cycles, the key finding here is that not only the operation temperature but also the ‘thermal history’ of the battery should be carefully considered because this history remains and continues to affect the self-discharge rate afterwards. The self-discharge of LIBs has remained largely neglected; however, our findings suggest that close attention must be paid to the self-discharge of LIBs applied to large-scale ESSs, which, unlike mobile electronic devices, will be exposed to various outdoor temperature conditions.

Roll-to-Roll Laser-Printed Graphene–Graphitic Carbon Electrodes for High-Performance Supercapacitors

Carbon electrodes including graphene and thin graphite films have been utilized for various energy and sensor applications, where the patterning of electrodes is essentially included. Laser scribing in a DVD writer and inkjet printing were used to pattern the graphene-like materials, but the size and speed of fabrication has been limited for practical applications. In this work, we devise a simple strategy to use conventional laser-printer toner materials as precursors for graphitic carbon electrodes. The toner was laser-printed on metal foils, followed by thermal annealing in hydrogen environment, finally resulting in the patterned thin graphitic carbon or graphene electrodes for supercapacitors. The electrochemical cells made of the graphene-graphitic carbon electrodes show remarkably higher energy and power performance compared to conventional supercapacitors. Furthermore, considering the simplicity and scalability of roll-to-roll (R2R) electrode patterning processes, the proposed method would enable cheaper and larger-scale synthesis and patterning of graphene-graphitic carbon electrodes for various energy applications in the future.