Prussian Blue Analogues Revolutionize Affordable, Durable LIBs

Abstract

The increasing use of low-cost lithium iron phosphate cathodes in low-end electric vehicles has sparked interest in Prussian blue analogues (PBAs) for lithium-ion batteries. A major challenge with iron hexacyanoferrate (FeHCFe), particularly in lithium-ion systems, is its slow kinetics in organic electrolytes and valence state inactivation in aqueous ones. We have addressed these issues by developing a polymeric cathode electrolyte interphase (CEI) layer through a ring-opening reaction of ethylene carbonate triggered by OH- radicals from structural water. This facile approach considerably mitigates the sluggish electrochemical kinetics typically observed in organic electrolytes. As a result, FeHCFe has achieved a specific capacity of 125 mAh g-1 with a stable lifetime over 500 cycles, thanks to the effective activation of Fe low-spin states and the structural integrity of the CEI layers. These advancements shed light on the potential of PBAs to be viable, durable, and efficient cathode materials for commercial use.

Prussian blue (PB), a well-known pigment used to dye jeans, has been recognized as an emerging material for next-generation batteries. A team of researchers, led by Professor Hyun-Wook Lee in the School of Energy and Chemical Engineering at UNIST has made a significant breakthrough in the development of low-cost, high-performance lithium-ion batteries (LIBs) using PB, leading to significantly reduced battery prices.

The study, published in Nano Letters, demonstrates a new electrolyte system that overcomes the limitations of PB's slow kinetics and valence state inactivation, enabling stable and efficient battery operation.

In this study, the research team developed a novel polymeric cathode electrolyte interphase (CEI) layer through a ring-opening reaction of ethylene carbonate triggered by OH- radicals from structural water. This innovative approach significantly improves the electrochemical kinetics in organic electrolytes, achieving a specific capacity of 125 mAh/g with a stable lifetime over 500 cycles.

The team's achievement is a game-changer in the development of LIBs, which are crucial for the widespread adoption of electric vehicles (EVs) and other energy storage applications. However, traditional LIBs rely heavily on lithium-containing transition metal oxides as cathode materials, such as cobalt and nickel, leading to high production costs. As a result, the rising price of these resources has caused battery prices to soar. In contract, PB is a cost-effective and efficient material, comprising iron, carbon, and nitrogen. Its affordability and high ionic conductivity make it an attractive alternative for LIBs. However, not much research has been done on PB so far, partly due to the limitations imposed by the implications of lithium.

Their findings show that PB can be used as a durable and efficient cathode material, showing potential to significantly lower the price of LIBs. Through optimization of performance through electrolyte improvement, its applications are expected to span various battery fields.

"This study marks a significant paradigm shift in the development of cheap cathode materials," said Professor Lee. "We have successfully transformed PB from an attractive low-cost cathode material to a viable option for commercial use."

First author Tae-Ung Wi added, "Our research not only overcomes the limitations of existing PB, but also contributes to more efficient and stable battery development in the future."

This breakthrough has far-reaching implications for the battery industry, paving the way for the widespread adoption of PB as a next-generation cathode material.

The study was supported by the Korea Research Foundation's mid-sized follow-up project and was published on June 13 in Nano Letters, an international academic journal in the field of nanoscience.

Journal Reference

Tae-Ung Wi, Changhyun Park, Sangho Ko, et al., "Cathode Electrolyte Interphase Engineering for Prussian Blue Analogues in Lithium-Ion Batteries," Nano Letters, (2024).

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