Hee-Dae Lim

Superior Rechargeability and Efficiency of Lithium–Oxygen Batteries: Hierarchical Air Electrode Architecture Combined with a Soluble Catalyst†

The lithium-oxygen battery has the potential to deliver extremely high energy densities; however, the practical use of Li-O2 batteries has been restricted because of their poor cyclability and low energy efficiency. In this work, we report a novel Li-O2 battery with high reversibility and good energy efficiency using a soluble catalyst combined with a hierarchical nanoporous air electrode. Through the porous three-dimensional network of the air electrode, not only lithium ions and oxygen but also soluble catalysts can be rapidly transported, enabling ultra-efficient electrode reactions and significantly enhanced catalytic activity. The novel Li-O2 battery, combining an ideal air electrode and a soluble catalyst, can deliver a high reversible capacity (1000 mAh g(-1) ) up to 900 cycles with reduced polarization (about 0.25 V).

Enhanced power and rechargeability of a Li-O2 battery based on a hierarchical-fibril CNT electrode

Recently Li-air batteries have been considered to be a promising candidate for EV and HEV applications due to their exceptionally high energy density. A key factor for the practical application of Li-air batteries is to solve the poor reversibility of nonconductive discharge products, which remains a significant limiting factor for Li-air batteries. Therefore, the air electrode needs to be designed such that it minimizes the undesirable clogging and promotes the electrochemical reactivity. As the control of the morphology and porosity of the electrode greatly affects on the capacity and rate capability, various nanostructured air electrodes have been reported using carbon nanoparticles, graphene, graphene oxide, or carbon nanotubes (CNTs). However, the poor cyclability and low rate capability remain as critical drawbacks of the Li−O2 batteries, and the ideally designed electrode architecture is still awaited.

Graphene for advanced Li/S and Li/air batteries

Li/S and Li/air cells have attracted much recent attention as potential successors to lithium ion batteries because of their exceptionally high energy density compared with current battery technology. Although the two new battery systems have the potential to satisfy the demand for a significant leap forward in energy storage technology, there remain significant problems to be addressed, including poor cycle stability and low rate capability for practical applications. To address these issues, much research effort has been invested. In particular, graphene, with its high surface area combined with catalytic properties, is considered to be a key potential material to advance Li/S and Li/air battery technology. Indeed, recent research into graphene has led to substantial performance improvements of Li/S and Li/air batteries. In this review, we describe recent achievements in Li/S and Li/air cells that have been facilitated by the application of graphene, together with the electrochemical reaction mechanisms and major issues facing both Li/S and Li/air batteries.

Organic nanohybrids for fast and sustainable energy storage.

A nanohybridization strategy is presented for the fabrication of high performance lithium ion batteries based on redox-active organic molecules. The rearrangement of electroactive aromatic molecules from bulk crystalline particles into molecular layers is achieved by non-covalent nanohybridization of active molecules with conductive scaffolds. As a result, nano-hybrid organic electrodes in the form of a flexible self-standing paper-free of binder/additive and current collector-are synthesized, which exhibit high energy and power densities combined with excellent cyclic stability.

A new catalyst-embedded hierarchical air electrode for high-performance Li–O2 batteries

The Li–O2 battery holds great promise as an ultra-high-energy-density device. However, its limited rechargeability and low energy efficiency remain key barriers to its practical application. Herein, we demonstrate that the ideal electrode morphology design combined with effective catalyst decoration can enhance the rechargeability of the Li–O2 battery over 100 cycles with full discharge and charge. An aligned carbon structure with a hierarchical micro-nano-mesh ensures facile accessibility of reaction products and provides the optimal catalytic conditions for the Pt catalyst. The new electrode is highly reversible even at the extremely high current rate of 2 A g−1. Moreover, we observed clearly distinct morphologies of discharge products when the catalyst is used. The effect of catalysts on the cycle stability is discussed.

Scalable Functionalized Graphene Nano-platelets as Tunable Cathodes for High-performance Lithium Rechargeable Batteries

High-performance and cost-effective rechargeable batteries are key to the success of electric vehicles and large-scale energy storage systems. Extensive research has focused on the development of (i) new high-energy electrodes that can store more lithium or (ii) high-power nano-structured electrodes hybridized with carbonaceous materials. However, the current status of lithium batteries based on redox reactions of heavy transition metals still remains far below the demands required for the proposed applications. Herein, we present a novel approach using tunable functional groups on graphene nano-platelets as redox centers. The electrode can deliver high capacity of ~250 mAh g−1, power of ~20 kW kg−1 in an acceptable cathode voltage range, and provide excellent cyclability up to thousands of repeated charge/discharge cycles. The simple, mass-scalable synthetic route for the functionalized graphene nano-platelets proposed in this work suggests that the graphene cathode can be a promising new class of electrode.

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.

Anomalous Jahn–Teller behavior in a manganese-based mixed-phosphate cathode for sodium ion batteries

We report a 3.8 V manganese-based mixed-phosphate cathode material for applications in sodium rechargeable batteries; i.e., Na4Mn3(PO4)2(P2O7). This material exhibits a largest Mn2+/Mn3+ redox potential of 3.84 V vs. Na+/Na yet reported for a manganese-based cathode, together with the largest energy density of 416 W h kg−1. We describe first-principles calculations and experimental results which show that three-dimensional Na diffusion pathways with low-activation-energy barriers enable the rapid sodium insertion and extraction at various states of charge of the Na4−xMn3(PO4)2(P2O7) electrode (where x = 0, 1, 3). Furthermore, we show that the sodium ion mobility in this crystal structure is not decreased by the structural changes induced by Jahn–Teller distortion (Mn3+), in contrast to most manganese-based electrodes, rather it is increased due to distortion, which opens up sodium diffusion channels. This feature stabilizes the material, providing high cycle stability and high power performance for sodium rechargeable batteries. The high voltage, large energy density, cycle stability and the use of low-cost Mn give Na4Mn3(PO4)2(P2O7) significant potential for applications as a cathode material for large-scale Na-ion batteries.

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.