Devaraj Shanmukaraj

Redox-active polyimide–polyether block copolymers as electrode materials for lithium batteries

Redox-active polyimide–polyether multi-block copolymers were synthesized by polycondensation reaction of aromatic dianhydrides with α-ω-diamino poly(ethylene oxide). Polyimide-b-polyether block copolymers showed microphase separation between a hard-polyimide domain and a soft-polyether domain as observed by Atomic Force Microscopy. The block copolymers were investigated as cathodes for polymer/lithium metal batteries. Polymer cathodes were formulated where the block copolymer had a dual role as active material and binder, with a small amount of carbon black (15 wt%). Naphthalene polyimides showed higher discharge voltages, higher specific capacities as well as better cycling performance, compared to pyromellitic polyimides. The longest PEO blocks resulted in a better performance as electrodes. The best performing naphthalene polyimide-b-PEO2000 presented an excellent value of discharge capacity of 170 mA h g−1, stable after 100 cycles at a current density of 1Li+/5 h and considering the polyimide as the active material. The average discharge plateaus were 2.51 V and 2.37 V vs. Li+/Li.

New Redox Polymers that Exhibit Reversible Cleavage of Sulfur Bonds as Cathode Materials

Two new cathode materials based on redox organosulfur polymers were synthesized and investigated for rechargeable lithium batteries as a proof-of-concept study. These cathodes offered good cycling performance owing to the absence of polysulfide solubility, which plagues Li/S systems. Herein, an aliphatic polyamine or a conjugated polyazomethine was used as the base to tether the redox-active species. The activity comes from the cleavage and formation of S-S or N-S bonds, which is made possible by the rigid conjugated backbone. The synthesized polymers were characterized through FTIR spectroscopy and thermogravimetric analysis (TGA). Galvanostatic measurements were performed to evaluate the discharge/charge cycles and characterize the performance of the lithium-based cells, which displayed initial discharge capacities of approximately 300 mA h g-1 at C/5 over 100 cycles with approximately 98 % Coulombic efficiency.

Electrode Materials for Sodium-Ion Batteries: Considerations on Crystal Structures and Sodium Storage Mechanisms

Sodium-ion batteries have been emerging as attractive technologies for large-scale electrical energy storage and conversion, owing to the natural abundance and low cost of sodium resources. However, the development of sodium-ion batteries faces tremendous challenges, which is mainly due to the difficulty to identify appropriate cathode materials and anode materials. In this review, the research progresses on cathode and anode materials for sodium-ion batteries are comprehensively reviewed. We focus on the structural considerations for cathode materials and sodium storage mechanisms for anode materials. With the worldwide effort, high-performance sodium-ion batteries will be fully developed for practical applications.Graphical Abstract

Highly Efficient, Cost Effective, and Safe Sodiation Agent for High-Performance Sodium-Ion Batteries

The development of sodium-ion batteries has been hindered so far by the large irreversible capacity of hard carbon anodes and other anode materials in the initial few cycles, as sodium ions coming from cathode materials is consumed in the formation of the solid-electrolyte interface (SEI) and irreversibly trapped in anodes. Herein, the successful synthesis of an environmentally benign and cost-effective sodium salt (Na2 C4 O4 ) is reported that could be applied as additive in cathodes to solve the irreversible-capacity issues of anodes in sodium-ion batteries. When added to Na3 (VO)2 (PO4 )2 F cathode, the cathode delivered a highly stable capacity of 135 mAh g-1 and stable cycling performance. The water-stable Na3 (VO)2 (PO4 )2 F cathode in combination with a water-soluble sacrificial salt eliminates the need for using any toxic solvents for laminate preparation, thus paving way for greener electrode fabrication techniques. A 100 % increase in capacity of sodium cells (full-cell configuration) has been observed when using the new sodium salt at a C-rate of 2C. Regardless of the electrode fabrication technique, this new salt finds use in both aqueous and non-aqueous cathode-fabrication techniques for sodium-ion batteries.