Heterogeneous intercalated metal-organic framework active materials for fast-charging non-aqueous Li-ion capacitors

Abstract

Intercalated metal-organic frameworks (iMOFs) based on aromatic dicarboxylate are appealing negative electrode active materials for Li-based electrochemical energy storage devices. They store Li ions at approximately 0.8 V vs. Li/Li+ and, thus, avoid Li metal plating during cell operation. However, their fast-charging capability is limited. Here, to circumvent this issue, we propose iMOFs with multi-aromatic units selected using machine learning and synthesized via solution spray drying. A naphthalene-based multivariate material with nanometric thickness allows the reversible storage of Li-ions in non-aqueous Li metal cell configuration reaching 85% capacity retention at 400 mA g−1 (i.e., 30 min for full charge) and 20 °C compared to cycling at 20 mA g−1 (i.e., 10 h for full charge). The same material, tested in combination with an activated carbon-based positive electrode, enables a discharge capacity retention of about 91% after 1000 cycles at 0.15 mA cm−2 (i.e., 2 h for full charge) and 20 °C. We elucidate the charge storage mechanism and demonstrate that during Li intercalation, the distorted crystal structure promotes electron delocalization by controlling the frame vibration. As a result, a phase transition suppresses phase separation, thus, benefitting the electrode’s fast charging behavior.

Developments in conducting polymer-, metal oxide-, and carbon nanotube-based composite electrode materials for supercapacitors: a review

“…Ogihara et al reported an intercalated MOF-based active electrode material for Li-ion-based ESDs. 253 They used 0.8 V potential for intercalation of Li-ions in the MOF matrix. This hybrid ESD shows an 85% retention capacity at 400 mA g −1 .…”

Crystal structure of dilithium biphenyl-4,4′-disulfonate dihydrate

“…These materials offer several advantages such as being non-toxic, abundant on the planet, and cheap and provide good results when gravimetric methods are used (Banerjee & Parise 2011). Li-dicarboxylates may be good candidates as electrode materials for eco-friendly alternatives to other inorganic materials, and have been reported for use in battery applications (Armand et al, 2009;Ogihara et al, 2014Ogihara et al, , 2023Mikita et al, 2020). To improve our chemistry and electrode applications, we investigated CNs using disulfonate ligands.…”

Herringbone packed contorted aromatics with ordered three-dimensional channels as fast-charging and low-temperature lithium-ion battery anodes

“…When used as lithium-ion anodes, well-ordered 3D channels can lead to improved rate performances and capacity. 35–39 Although obtaining stable MOF or COF anodes for fast-charging LIBs is still challenging, the construction of ordered 3D ordered lithium-ion diffusion channels is instructive for high-rate organic anode materials.…”