Abstract

The rapid progress in mass-market applications of metal-ion batteries intensifies the development of economically feasible electrode materials based on earth-abundant elements. Here, we report on a record-breaking titanium-based positive electrode material, KTiPO4F, exhibiting a superior electrode potential of 3.6 V in a potassium-ion cell, which is extraordinarily high for titanium redox transitions. We hypothesize that such an unexpectedly major boost of the electrode potential benefits from the synergy of the cumulative inductive effect of two anions and charge/vacancy ordering. Carbon-coated electrode materials display no capacity fading when cycled at 5C rate for 100 cycles, which coupled with extremely low energy barriers for potassium-ion migration of 0.2 eV anticipates high-power applications. Our contribution shows that the titanium redox activity traditionally considered as “reducing” can be upshifted to near-4V electrode potentials thus providing a playground to design sustainable and cost-effective titanium-containing positive electrode materials with promising electrochemical characteristics.

Highlights

  • The rapid progress in mass-market applications of metal-ion batteries intensifies the development of economically feasible electrode materials based on earth-abundant elements

  • The highest electrode potential attributed to the Ti4+/Ti3+ redox couple was achieved in the titanium nitridophosphate, Na3Ti[(PO3)3N]30 exhibiting a voltage plateau centered at 2.7 V vs. Na+/Na (~2.95 V vs. Li+/Li or K+/K) which is explained by a colossal inductive effect of the complex nitridophosphate group [(PO3)3N]6−

  • We report on a promising KTiPO4F fluoride phosphate as a positive electrode material for K-ion batteries (KIBs)

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Summary

Introduction

The rapid progress in mass-market applications of metal-ion batteries intensifies the development of economically feasible electrode materials based on earth-abundant elements. We report on a record-breaking titanium-based positive electrode material, KTiPO4F, exhibiting a superior electrode potential of 3.6 V in a potassium-ion cell, which is extraordinarily high for titanium redox transitions. We hypothesize that such an unexpectedly major boost of the electrode potential benefits from the synergy of the cumulative inductive effect of two anions and charge/vacancy ordering. We report on a promising KTiPO4F fluoride phosphate as a positive electrode material for K-ion batteries (KIBs) It adopts a KTiOPO4-(KTP)-type crystal structure that boosts the Ti4+/Ti3+ transition to extraordinarily high electrode potentials approaching 3.6–3.7 V vs K+/K. This earth-abundant, synthetically scalable, and thermally stable KTiPO4F material shows steady cycling at high rates challenging and outperforming many benchmarked potassium-ion cathode materials

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