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Strategies for synthesis of Prussian blue analogues.

ABSTRACT: We report a comparison of different common synthetic strategies for preparation of Prussian blue analogues (PBA). PBA are promising as cathode material for a number of different battery types, including K-ion and Na-ion batteries with both aqueous and non-aqueous electrolytes. PBA exhibit a significant degree of structural variation. The structure of the PBA determines the electrochemical performance, and it is, therefore, important to understand how synthesis parameters affect the structure of the obtained product. PBA are often synthesized by co-precipitation of a metal salt and a hexacyanoferrate complex, and parameters such as concentration and oxidation state of the precursors, flow rate, temperature and additional salts can all potentially affect the structure of the product. Here, we report 12 different syntheses and compare the structure of the obtained PBA materials.

SUBMITTER: Kjeldgaard S

PROVIDER: S-EPMC7890497 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

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Strategies for synthesis of Prussian blue analogues.

Kjeldgaard Solveig S Dugulan Iulian I Mamakhel Aref A Wagemaker Marnix M Iversen Bo Brummerstedt BB Bentien Anders A

Royal Society open science 20210113 1

We report a comparison of different common synthetic strategies for preparation of Prussian blue analogues (PBA). PBA are promising as cathode material for a number of different battery types, including K-ion and Na-ion batteries with both aqueous and non-aqueous electrolytes. PBA exhibit a significant degree of structural variation. The structure of the PBA determines the electrochemical performance, and it is, therefore, important to understand how synthesis parameters affect the structure of ...[more]

PMID: 33614096

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Structural complexity in Prussian blue analogues.

Project description:We survey the most important kinds of structural complexity in Prussian blue analogues, their implications for materials function, and how they might be controlled through judicious choice of composition. We focus on six particular aspects: octahedral tilts, A-site 'slides', Jahn-Teller distortions, A-site species and occupancy, hexacyanometallate vacancies, and framework hydration. The promising K-ion cathode material KxMn[Fe(CN)6]y serves as a recurrent example that illustrates many of these different types of complexity. Our article concludes with a discussion of how the interplay of various distortion mechanisms might be exploited to optimise the performance of this and other related systems, so as to aid in the design of next-generation PBA materials.

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Project description:Prussian blue analogues (PBAs) are a diverse family of microporous inorganic solids, known for their gas storage ability1, metal-ion immobilization2, proton conduction3, and stimuli-dependent magnetic4,5, electronic6 and optical7 properties. This family of materials includes the double-metal cyanide catalysts8,9 and the hexacyanoferrate/hexacyanomanganate battery materials10,11. Central to the various physical properties of PBAs is their ability to reversibly transport mass, a process enabled by structural vacancies. Conventionally presumed to be random12,13, vacancy arrangements are crucial because they control micropore-network characteristics, and hence the diffusivity and adsorption profiles14,15. The long-standing obstacle to characterizing the vacancy networks of PBAs is the inaccessibility of single crystals16. Here we report the growth of single crystals of various PBAs and the measurement and interpretation of their X-ray diffuse scattering patterns. We identify a diversity of non-random vacancy arrangements that is hidden from conventional crystallographic powder analysis. Moreover, we explain this unexpected phase complexity in terms of a simple microscopic model that is based on local rules of electroneutrality and centrosymmetry. The hidden phase boundaries that emerge demarcate vacancy-network polymorphs with very different micropore characteristics. Our results establish a foundation for correlated defect engineering in PBAs as a means of controlling storage capacity, anisotropy and transport efficiency.

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Thermal efficiency of a thermocell made of Prussian blue analogues.

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Y-tube assisted coprecipitation synthesis of iron-based Prussian blue analogues cathode materials for sodium-ion batteries.

Project description:Prussian blue analogues possess numerous advantages as cathode materials for sodium-ion batteries, including high energy density, low cost, sustainability, and straightforward synthesis processes, making them highly promising for practical applications. However, during the synthesis, crystal defects such as vacancies and the incorporation of crystal water can lead to issues such as diminished capacity and suboptimal cycling stability. In the current study, a Y-tube assisted coprecipitation method was used to synthesize iron-based Prussian blue analogues, and the optimized feed flow rate during synthesis contributed to the successful preparation of the material with a formula of Na1.56Fe[Fe(CN)6]0.90□0.10·2.42H2O, representing a low-defect cathode material. This approach cleverly utilizes the Y-tube component to enhance the micro-mixing of materials in the co-precipitation reaction, featuring simplicity, low cost, user-friendly, and the ability to be used in continuous production. Electrochemical performance tests show that the sample retains 69.8% of its capacity after 200 cycles at a current density of 0.5C (1C = 140 mA g-1) and delivers a capacity of 71.9 mA h g-1 at a high rate of 10C. The findings of this research provide important insights for the development of high-performance Prussian blue analogues cathode materials for sodium-ion batteries.

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The structures of ordered defects in thiocyanate analogues of Prussian Blue.

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