Electrochemical Complexation of Polyatomic Aluminum Cations in Quinone-Type Organic Battery Electrodes Revealed By Solid-State NMR

Abstract

Rechargeable aluminum batteries represent a significant area of opportunity for beyond-lithium-ion energy storage due to the high theoretical capacity (2980 mA∙h∙g-1, 8046 mA∙h∙mL-1), large earth abundance (8.23 wt.%), low cost, and safety of aluminum metal. Due to the stable native oxide layer that forms on aluminum, very few electrolytes are able to reversibly plate and strip aluminum at room temperature. Lewis acidic chloroaluminate ionic liquid electrolytes have demonstrated success in this regard; however, any cathode materials must also be (electro)chemical stable in this electrolyte. Electrode materials based on organic molecules have garnered attention due to their tunable structures and properties, enabling optimization for specific energy storage systems. Furthermore, diverse functional groups enable a range of possible charge storage mechanisms, many of which have yet to be explored in these systems. Like aluminum, organic materials are highly abundant and can be derived from various sources without geopolitical constraints. However, few Al-organic battery studies exist, and none so far have performed mechanistic analyses based on experimental data to identify conclusively the electroactive ions and their binding sites.Here, we present a rigorous analysis of charge storage mechanisms in quinone-type organic molecules for the first time, established through multi-dimensional solid-state nuclear magnetic resonance (ssNMR) spectroscopy in concert with quantum chemical calculations and electrochemical measurements. Indanthrone quinone (INDQ) is investigated for the first time as a model system due to its two distinct quinone functionalities and low solubility in many solvents. Through-space 27Al{1H} and 13C{1H} dipolar-mediated ssNMR techniques are used to establish the sub-nanometer proximities between polyatomic aluminum cations and specific moieties in the organic frameworks. Furthermore, dipolar-mediated ssNMR measurements are sensitive to both molecular dynamics and internuclear distances, which enables us to selectively filter out signals from residual liquid electrolyte, eliminating the need for solvent rinsing that can perturb the sample. Al-INDQ cells achieve reversible capacities of up to 240 mA∙h∙g-1 and maintain capacities >100 mA∙h∙g-1 at rates up to 2400 mA∙g-1. The enolization reaction and charge-balancing AlCl2 + cation complexation was established via dipolar-mediated ssNMR, findings that are corroborated through density functional theory (DFT) calculations. Other quinone-based organic structures with modified structures and compositions were also investigated using similar methods and will briefly be compared to INDQ. In aggregate, the quinone-based model systems serve as a basis to better understand how different functional groups, heteroatoms, and organic structures affect the electrochemical properties of rechargeable Al-organic batteries. The results yield strategies towards creating ‘designer’ organic electrode materials for rechargeable aluminum batteries.