Structural and Interfacial Engineering of 2,5-Dihydroxy-1,4-Benzoquinone Coordination-Polymer Cathodes for Sustainable Lithium-Ion Batteries

Abstract

Carbonyl-based organic compounds are one of the most promising sustainable cathode materials for next-generation lithium-ion batteries due to their highly reversible C=O redox center, high theoretical capacity, structural tunability, and potential derivation from abundant or biomass-related feedstocks. However, their practical deployment has been limited by intrinsically high solubility in conventional carbonate- and ether-based electrolytes. Dissolution-driven loss of active material not only leads to rapid capacity fading but also induces serious shuttle effect, self-discharge, and parasitic reactions. Therefore, suppressing dissolution is an essential prerequisite for achieving long-term stability and practical energy density in organic cathodes. Among various carbonyl-based candidates, 2,5-dihydroxy-1,4-benzoquinone (DHBQ) is attractive because of its high theoretical capacity (383 mAh g⁻¹), simple structure, and potential renewability. Yet DHBQ is highly soluble in common organic electrolytes, preventing stable cycling. In this thesis, coordination polymer (CP) synthesis was employed as the primary strategy to reduce the solubility of carbonyl-based cathodes. By incorporating redox-active quinone units into coordination frameworks, CP structures increase the energetic barrier for molecular detachment and solvation, thereby effectively suppressing dissolution. Moreover, CPs can be synthesized through relatively simple coordination reactions using accessible precursors, offering practical feasibility and potential scalability. In Chapter 3, a metastable quinone-based coordination polymer, Co-DHBQ·2H₂O, was investigated as a transition-metal-redox cathode. When cycled between 0.7–3.0 V, the electrodes undergo a reversible four-electron transfer process involving both DHBQ and Co redox reactions. Initial side reactions, including SEI formation and benzene-ring lithiation, lead to a high first-cycle capacity of 783 mAh g⁻¹. After stabilization, the cathode delivers 199 mAh g⁻¹ after 750 cycles, with 84% capacity retention between the 100th and 750th cycles. Structural analyses reveal that coordinated water molecules form strong hydrogen bonds (up to -40.5 kJ mol⁻¹) that stabilize the layered framework and preserve structural integrity during cycling. However, excessive lithiation at low voltages induces structural damage due to the metastable nature of the hydrogen-bonded layers. Comparative studies with anhydrous Co-DHBQ confirm that coordinated water is critical for maintaining structural integrity, enabling reversible Li⁺ accommodation, and achieving long-term electrochemical stability. In Chapter 4, a lithium-based, transition-metal-free Li₂DHBQ cathode was investigated to reduce mass penalty while maintaining low solubility. Although Li₂DHBQ exhibits extremely low solubility in the electrolyte, severe morphological degradation of the active material was identified as the primary origin of poor cycling stability. Repeated lithiation and delithiation induce particle fracture and progressive disruption of electronic percolation pathways, leading to capacity fading independent of dissolution effects. To address this issue, the discharge cutoff voltage was lowered to 0.5 V to promote electrolyte reduction and in situ formation of a protective solid electrolyte interphase (SEI) layer on the Li₂DHBQ surface. This strategy significantly enhanced morphological stability and improved electrochemical performance. When cycled between 0.5–3.0 V at 500 mA g⁻¹, the cathode maintained a capacity of 170 mAh g⁻¹ after 200 cycles, with a low decay rate of 0.16% per cycle. Furthermore, a preconditioning strategy in which the electrode was first cycled at 0.5 V for 20 cycles to form the SEI layer, followed by cycling within the normal 1.5–3.0 V range at 500 mA g⁻¹, resulted in even better performance, retaining 187 mAh g⁻¹ at the 200th cycle. In contrast, a cell cycled only within 1.5–3.0 V retained merely 87 mAh g⁻¹ after 200 cycles. These results demonstrate that controlled SEI formation effectively reinforces morphological stability, mitigates structural degradation, and substantially improves long-term cycling performance once dissolution has been suppressed. In Chapter 5, we build upon Chapter 4 and introduce a more controlled strategy for cathode surface stabilization through the incorporation of fluoroethylene carbonate (FEC) as a CEI-forming additive. The addition of 1 wt.% FEC promotes the formation of a robust CEI layer that significantly suppresses particle pulverization and enhances structural integrity during cycling. SEM and TEM analyses reveal that the optimized CEI layer is relatively uniform and approximately 30 nm thick, effectively mitigating active material degradation. As a result, the Li₂DHBQ cathode with 1% FEC exhibits substantially improved electrochemical performance. When cycled at 500 mA g⁻¹, the electrode retains 185 mAh g⁻¹ after 200 cycles with a low-capacity decay rate of 0.049% per cycle, compared to 81 mAh g⁻¹ and a decay rate of 0.302% per cycle for the FEC-free battery. In addition to enhanced cycling stability, the FEC-containing cell demonstrates superior rate capability, supported by a dominant capacitive contribution of up to 93.7%, indicating accelerated surface-controlled charge storage behavior. These findings confirm that CEI engineering via controlled additive incorporation effectively stabilizes the electrode structure, suppresses interfacial degradation, and optimizes charge storage kinetics once dissolution has been mitigated. The results highlight the importance of interphase design in enabling stable and high-rate organic cathode systems. Beyond electrochemical stability, in Chapter 6 this work also addresses sustainability and end-of-life considerations. A proof-of-concept recycling strategy for Li₂DHBQ-based cathodes was developed using solubility-selective disassembly. By exploiting the solubility contrast among active material, conductive additive, binder, and current collector, approximately 95% of Li₂DHBQ could be recovered under mild conditions. This result highlights the intrinsic compatibility of organic cathode systems with low-energy and environmentally benign recycling pathways. Overall, through coordination polymer immobilization, interfacial engineering, and recyclability-oriented electrode design, this work provides coherent design principles for developing stable, insoluble, and recyclable carbonyl-based cathodes toward sustainable lithium-ion battery technologies.