Ionically Conducting Li- and Na-phosphonates As Organic Electrode Materials for Rechargeable Batteries

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2024 Dec 25

PMID 39720142

Authors

Yan Zhang

Petru Apostol

Darsi Rambabu

Xiaolong Guo

Xuelian Liu

Xiaodong Lin

Haijiao Xie

Xiaohua Chen

Koen Robeyns

Jiande Wang

Junzhong Wang

Alexandru Vlad

Affiliations

Soon will be listed here.

Abstract

Facilitating rapid charge transfer in electrode materials necessitates the optimization of their ionic transport properties. Currently, only a limited number of Li/Na-ion organic cathode materials have been identified, and those exhibiting intrinsic solid-phase ionic conductivity are even rarer. In this study, we present tetra-lithium and sodium salts with the generic formulae: A-Ph-CHP and A-Ph-PhP, wherein A = Li, Na; Ph-CHP = 2,5-dioxido-1,4-phenylene bis(methylphosphinate); Ph-PhP = 2,5-dioxido-1,4-phenylene bis(phenylphosphinate), as novel alkali-ion reservoir cathode materials. Notably, A-Ph-PhP exhibits impressive Li-ion and Na-ion conductivities, measured at 2.6 × 10 and 1.4 × 10 S cm, respectively, in a dry state at 30 °C. To the best of our knowledge, these represent the first example of small-molecule organic cathode materials with intrinsic Li and Na conductivity. Theoretical calculations provide further insight into the electrochemical activity of the Li/Na-phenolate groups, as well as the enhanced electron affinity resulting from -phenyl and -Na substitutions. Additionally, Na-Ph-PhP displays two distinct charge-discharge plateaus at approximately 2.2 V and 2.7 V, and 2.0 V and 2.5 V Na/Na, respectively, and demonstrates stable cycling performance, with 100 cycles at a rate of 0.1C and an impressive 1000 cycles at 1C. This study not only expands the portfolio of phenolate-based organic salts for use in metal-ion batteries but also underscores the potential of phosphonate-based organic materials in advancing energy storage technologies.

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