Unraveling the multivalent aluminium-ion redox mechanism in 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA)

Literature Information

Publication Date 2022-02-14
DOI 10.1039/D1CP05716B
Impact Factor 3.676
Authors

Nicolò Canever, Thomas Nann


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Abstract

Rechargeable Aluminium-organic batteries are an exciting emerging energy storage technology owing to their low cost and promising high performance, thanks to the ability to allow multiple-electron redox chemistry and multivalent Al-ion intercalation. In this work, we use a combination of Density Functional Theory (DFT) calculations and experimental methods to examine the mechanism behind the charge–discharge reaction of the organic dye 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) in the 1,3-ethylmethylimidazolium (EMIm+) chloroaluminate electrolyte. We conclude that, contrary to previous reports claiming the intercalation of trivalent Al3+, the actual ionic species involved in the redox reaction is the divalent AlCl2+. While a less-than-ideal scenario, this mechanism still allows a theoretical transfer of four electrons per formula unit, corresponding to a remarkable specific capacity of 273 mA h g−1. However, the poor reversibility of the reaction and low cycle life of the PTCDA-based cathode, due to its solubility in the electrolyte, make it an unlikely candidate for a commercial application.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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