Rational Molecular Design of Benzoquinone‐Derived Cathode Materials for High‐Performance Lithium‐Ion Batteries

Abstract

p-Benzoquinone (BQ) is a promising cathode material for lithium-ion batteries (LIBs) due to its high theoretical specific capacity and voltage. However, it suffers from a serious dissolution problem in organic electrolytes, leading to poor electrochemical performance. Herein, two BQ-derived molecules with a near-plane structure and relative large skeleton: 1,4-bis(p-benzoquinonyl)benzene (BBQB) and 1,3,5-tris(p-benzoquinonyl)benzene (TBQB) are designed and synthesized. They show greatly decreased solubility as a result of strong intermolecular interactions. As cathode materials for LIBs, they exhibit high carbonyl utilizations of 100% with high initial capacities of 367 and 397 mAh g −1 , respectively. Especially, BBQB with better planarity presents remarkably improved cyclability, retaining a high capacity of 306 mAh g −1 after 100 cycles. The cycling stability of BBQB surpasses all reported BQ-derived small molecules and most polymers. This work provides a new molecular structure design strategy to suppress the dissolution of organic electrode materials for achieving high performance rechargeable batteries.

In-situ electropolymerized bipolar organic cathode for stable and high-rate lithium-ion batteries

“…Representative n-type materials are carbonyl organics [14,15], which are the most investigated organic electrode materials. For example, p-benzoquinone has a theoretical specific capacity of 496 mA h g −1 [16], and Lu et al [17] reported a cyclohexanehexone cathode material that exhibits a high capacity of 902 mA h g −1 . However, these organic molecules are highly soluble in organic liquid electrolytes, causing a fast capacity decay [16,17].…”

“…For example, p-benzoquinone has a theoretical specific capacity of 496 mA h g −1 [16], and Lu et al [17] reported a cyclohexanehexone cathode material that exhibits a high capacity of 902 mA h g −1 . However, these organic molecules are highly soluble in organic liquid electrolytes, causing a fast capacity decay [16,17]. In contrast, p-type materials can accept anions and transform from neutral to positively charged states [18,19].…”

2D Coordination Network of Trioxotriangulene with Multiple Redox Abilities and Its Rechargeable Battery Performance

“…On the other hand, in the case of 3 , in which molecules were connected by halogen bonds in the crystal, elution of the active material into the electrolyte was sufficiently suppressed, and cycle performance was greatly improved ( C TOT = 225 mA h g −1 at 1st cycle and C TOT = 159 mA h g −1 at 100th cycle). These results suggest that in addition to the chemical stability of the redox species, suppression of the solubility of active materials by intermolecular interactions is effective for improving cycle characteristics [ 51 , 52 , 53 , 54 , 55 ]. In this paper, we have designed and synthesized a novel TOT derivative 4 with three 4-pyridyl groups introduced at the 2-,6- and10-positions of the TOT skeleton, preserving the three-fold symmetry as the first ligand based on the TOT s for metal complexes ( Scheme 1 ).…”

Supramolecular Self‐Assembled Multi‐Electron‐Acceptor Organic Molecule as High‐Performance Cathode Material for Li‐Ion Batteries

“…So far, a number of diverse structural motifs have been investigated as organic cathode materials in rechargeable LIBs, namely, conjugated polycarbonyl compounds, [7][8][9][10][11] conducting polymers, [12] persistent radical derivatives, [13][14][15] organosulfur derivatives, [16][17][18][19] and redox-active heterocycles, [20][21][22] which have particularly shown great promise. However, in most organic electrodes, issues associated with low electronic conductivity and material dissolution in typical organic solvents, used in electrolytes alongside lithium salt, generally result in poor cycling performance, rapid capacity fading as well as low Coulombic efficiency.…”