Prussian blue analogues for potassium-ion batteries: insights into the electrochemical mechanisms

Ab, Phuong Nam Le Pham; Wernert, Romain; Cahu, Maëlle; Sougrati, Moulay Tahar; Aquilanti, Giuliana; Johansson, Patrik; Monconduit, Laure; Stievano, Lorenzo

doi:10.1039/d2ta08439b

Cited by 21 publications

(11 citation statements)

References 66 publications

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“…Literally, it turns the redox potential upside down with respect to KMF. Considering the operando XAS investigation of the K 1.67 Mn 0.65 Fe 0.35 [Fe(CN) 6 ] 0.92 ·0.45H 2 O cathode material reported in the recent paper, we have to notice that the Mn-to-Fe substitution in the o-TM site also changes the sequence of TM-redoxes (as compared to that observed for KMF). The structural evolution of the KMF cathode upon (de)potassiation was reported previously.…”

Section: Resultsmentioning

confidence: 92%

Unexpected Chain of Redox Events in Co-Based Prussian Blue Analogues

et al. 2023

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The electronic structure of electrode materials for metal-ion batteries has a great impact on their charge compensation mechanism and, consequently, electrochemical behavior. In this paper, we report on the cobalt doping in the potassium manganese hexacyanoferrate positive electrode material for potassium-ion batteries, resulting in the formation of a system of K2−δCo x Mn1–x [Fe(CN)6] compounds with x = 0...1 and provide their comprehensive characterization including crystal structure evolution and charge compensation mechanisms upon K de/intercalation. Synthesized by a coprecipitation method, K2−δCo x Mn1–x [Fe(CN)6] forms two series of solid solutions with monoclinic (Co-poor) and cubic (Co-rich) structures. According to energy-dispersive X-ray analysis, the K content diminishes with increasing x value. Electrochemical properties of electrode materials based on K2−δCo x Mn1–x [Fe(CN)6] in K-metal half cells are also strongly dependent on Co doping regarding both specific capacity and redox potential. Attempts to interpret the results led to an unexpected conclusion that cobalt has influence on iron and manganese redox potentials, forming the following oxidation sequence: Co2+/3+, Mn2+/3+, and Fe2+/3+ in K2−δCo x Mn1–x [Fe(CN)6], which is inverse to that of Co-free K2−δMn[Fe(CN)6] (Fe2+/3+, Mn2+/3+), as validated by ex situ, operando X-ray absorption spectroscopy, and 57Fe Mössbauer spectroscopy.

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Section: Resultsmentioning

confidence: 92%

Unexpected Chain of Redox Events in Co-Based Prussian Blue Analogues

et al. 2023

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“…Stievano et al. [ 76 ] via non‐in situ 57 Fe Mössbauer spectroscopy and in situ Fe and Mn K‐edge X‐ray absorption spectroscopy, validated that the oxidation of Mn 2+ precedes that of LS Fe 2+ . This sequence instigates a shift in the crystal system from monoclinic to cubic, spurred by the coordination distortions triggered by Jahn–Teller effect.…”

Section: Optimization Strategiesmentioning

confidence: 96%

Prussian Blue Analogues Cathodes for Nonaqueous Potassium‐Ion Batteries: Past, Present, and Future

Shu,

Han,

Wang

2023

Adv Funct Materials

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Recently, potassium‐ion batteries (PIBs) have emerged as a new energy storage system, offering a complementary solution to lithium‐ion batteries due to their cost‐effectiveness and significantly high theoretical energy density, making them suitable for large‐scale grid energy storage applications. The critical challenge PIBs face is the scarcity of appropriate high‐capacity cathode materials. Among the various contenders, Prussian blue analogs (PBAs) stand out. The appeal of PBAs arises from their simple synthesis, economic viability, and a stable, open framework conducive to the insertion/extraction of large‐size K+. This review aims to provide an overview of current research progress on PBAs as cathode materials in nonaqueous PIBs. A comprehensive examination of the crystal structure and electrochemical reaction mechanisms of PBAs is undertaken, with a focus on prevalent optimization strategies in PIBs. Subsequent sections delve into designing and developing potassium‐based full cells architectures incorporating PBAs. The discourse culminates in a discussion on the requirements for transitioning PBAs PIBs from a laboratory setting to commercial production, aiming to chart a course for the development of advanced PIBs.

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“…Some notable structures can be mentioned, such as K x MO 2 layered oxides, 62-64 KVPO 4 F polyanion, [65][66][67] and Prussian blue analogues. [68][69][70] In this study, the {Fe(DSBDC)} n -layered network was identied as a new and promising structure that can allow a selective and fast K + diffusion process upon long-term cycling. Even though the redox potential and reversible capacity of this new compound are still limited, this discovery opens new opportunities for the development of analogous materials with better electrochemical performance through optimization of the cation and ligand composition.…”

Section: Optical Electronic and Magnetic Propertiesmentioning

confidence: 99%

Fe(iii)-carboxythiolate layered metal–organic frameworks with interest as active materials for rechargeable alkali-ion batteries

Gedikoglu,

Salcedo-Abraira,

Nguyen

et al. 2023

J. Mater. Chem. A

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Prussian blue analogues for potassium-ion batteries: insights into the electrochemical mechanisms

Abstract: A comprehensive description of the electrochemical mechanisms of the Prussian blue analogue (PBA) K1.67Mn0.65Fe0.35[Fe(CN)6]0.92·0.45H2O is obtained by combining several complementary ex situ and operando physico-chemical characterisation techniques. This particular PBA,...

Cited by 21 publications

References 66 publications

Unexpected Chain of Redox Events in Co-Based Prussian Blue Analogues

Unexpected Chain of Redox Events in Co-Based Prussian Blue Analogues

Prussian Blue Analogues Cathodes for Nonaqueous Potassium‐Ion Batteries: Past, Present, and Future

Fe(iii)-carboxythiolate layered metal–organic frameworks with interest as active materials for rechargeable alkali-ion batteries

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