Lithium-Ion Dynamic and Storage of Atomically Precise Halogenated Nanographene Assemblies via Bottom-Up Chemical Synthesis.

Graphene has received much scientific attention as an electrode material for lithium-ion batteries because of its extraordinary physical and electrical properties. However, the lack of structural control and restacking issues have hindered its application as carbon-based anode materials for next generation lithium-ion batteries. To improve its performance, several modification approaches such as edge-functionalization and electron-donating/withdrawing substitution have been considered as promising strategies. In addition, group 7A elements have been recognized as critical elements due to their electronegativity and electron-withdrawing character, which are able to further improve the electronic and structural properties of materials. Herein, we elucidated the chemistry of nanographenes with edge-substituted group 7A elements as lithium-ion battery anodes. The halogenated nanographenes were synthesized via bottom-up organic synthesis to ensure the structural control. Our study reveals that the presence of halogens on the edge of nanographenes not only tunes the structural and electronic properties but also impacts the material stability, reactivity, and Li+ storage capability. Further systematic spectroscopic studies indicate that the charge polarization caused by halogen atoms could regulate the Li+ transport, charge transfer energy, and charge storage behavior in nanographenes. Overall, this study provides a new molecular design for nanographene anodes aiming for next-generation lithium-ion batteries.

Redox-Active High-Performance Polyimides as Versatile Electrode Materials for Organic Lithium- and Sodium-Ion Batteries.

Organic electrode materials for rechargeable batteries show great promise for improving the storage capacity, reducing production costs, and minimizing environmental impact toward sustainability. In this study, we report a series of newly synthesized arylamine-based polyimides, TPPA-PIs, with three different bridge functionalizations on the imide rings and isomeric constituents that can work as versatile battery electrodes. As a lithium-ion battery cathode, a maximum energy density of 248 Wh kg-1 with high voltage operation up to 4.0 V can be achieved. As a lithium-ion battery anode, the TPPA-PIs showed a reversible storage capacity of 806 mA h g-1 at 100 mA g-1 current density with good rate capability up to a current density of 2000 mA g-1. Moreover, when applied as sodium-ion battery anodes, TPPA-PIs delivered an optimum specific capacity of up to 218 mA h g-1 after 50 cycles at a 50 mA g-1 current density and revealed a long cycling stability up to 1000 cycles under a high current density of 1000 mA g-1. More importantly, these electrochemical performances of TPPA-PIs are among the best compared with other reported polymer-based electrodes. The mechanistic studies show that both bridge functionalization on the imide units and isomerism impact the electrochemical performance by regulating their intrinsic properties such as charge storage behavior, ion diffusivity, and activation energy. We believe that such a detailed study of the structural design to electrochemical performance of these polymeric electrodes will offer insights into materials development and optimization for next-generation multifunctional energy storage devices in a wide range of applications.

Dicyanotriphenylamine-Based Polyimides as High-Performance Electrodes for Next Generation Organic Lithium-Ion Batteries.

Aromatic polyimide (PI) derivatives have recently been investigated as redox-active electrode materials for Li-ion batteries because of their high thermal stability and thermo-oxidative stability complemented by excellent solvent resistance, good electrical and mechanical properties, and chemical resistance. In this work, we report two PI derivatives from a newly synthesized 4,4'-diamino-3″,4″-dicyanotriphenylamine (DiCN-TPA) monomer and two dianhydrides, pyromellitic dianhydride (PMDA) and 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTCDA); designated as TPA-PMPI and TPA-NTCPI, respectively, as electrode materials for Li-ion batteries. Characterizations of the PIs reveal excellent thermal stability and bipolar property. The incorporation of DiCN-TPA into the polymer structure resulted to a disordered chain arrangement, thus giving high glass transition temperatures (Tg). Electrochemical performance tests reveal that TPA-NTCPI cathode delivered a reversible specific capacity of 150 mAh g-1 at 0.1 A g-1 and exhibited a stability up to 1000 cycles. On the other hand, TPA-PMPI anode delivered a high specific capacity of up to 1600 mAh g-1 at 0.1 A g-1 after 100 cycles. The electrochemical performance of TPA-NTCPI cathode and TPA-PMPI anode are both among the best compared with other reported aromatic PI-based electrodes. The long cycle lifetime and excellent battery performance further suggest that TPA-NTCPI and TPA-PMPI are promising organic electrode materials for next generation Li-ion batteries.