Impact of Synthesis Conditions in Na-Rich Prussian Blue Analogues

Camacho, Paula Sanz; Wernert, Romain; Duttine, Mathieu; Wattiaux, Alain; Rudola, Ashish; Balaya, Palani; Fauth, François; Berthelot, Romain; Monconduit, Laure; Carlier, Dany; Croguennec, Laurence

doi:10.1021/acsami.1c09378

Cited by 40 publications

(22 citation statements)

References 26 publications

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“…In recent years, with the rapid development of a new energy industry, energy-saving, resource-rich, and environment-friendly energy storage devices are the necessary conditions for the sustainable development of modern human society. − Lithium-ion batteries (LIBs) have been increasingly applied in portable electronic products and electric vehicles due to their excellent performance, which makes it difficult for the Earth’s limited lithium resources to meet the needs of the explosive growth of the energy storage market . Therefore, people have begun to focus on sodium-ion batteries (SIBs).…”

Section: Introductionmentioning

confidence: 99%

Synergistic Modification of Fe-Based Prussian Blue Cathode Material Based on Structural Regulation and Surface Engineering

Chen

Zhang

et al. 2022

ACS Appl. Mater. Interfaces

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The Fe-based Prussian blue (Fe-PB) composite is considered as one of the most potential cathode materials for sodium-ion batteries because of its abundant iron resources and high theoretical capacity. However, the crystal water and vacancy in the Fe-PB structure will lead to poor capacity and cycle stability. In this work, a Cu-modified Fe-PB composite (FeCu-PB@CuO) is successfully prepared through regulating the Fe-PB structure by Cu doping and engineering the surface by CuO coating. The density functional theory calculation results confirm that Cu preferentially replaces FeHS in the Fe-PB lattice and Cu doping reduces the bandgap. Our experiment results reveal that CuO coating can provide more active sites, inhibit side reactions, and potentially enhance the activity of FeHS. Due to the synergistic effect of Cu doping and CuO coating, FeCu-PB@CuO has a considerable initial discharge capacity of 123.5 mAh g–1 at 0.1 A g–1. In particular, at 2 A g–1, it delivers an impressive initial capacity of 84.3 mAh g–1, and the capacity decreasing rate of each cycle is only 0.02% over 1500 cycles. Therefore, the synergistic modification strategy of metal ion doping and metal oxide coating has tremendous application potential and can be extended to other electrode materials.

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Section: Introductionmentioning

confidence: 99%

Synergistic Modification of Fe-Based Prussian Blue Cathode Material Based on Structural Regulation and Surface Engineering

Chen

Zhang

et al. 2022

ACS Appl. Mater. Interfaces

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“…Specifically for PW, there are inconsistencies regarding the structure of the hydrated phase. For example, Camacho et al reported a rhombohedral R 3 structure for Na 1.86 Fe[Fe(CN) 6 ]•1.92H 2 O with oxygen positioned on half of the faces of the subcube [13]. This paper also reported a new orthorhombic Na-rich PBA (Na 1.8 Fe[Fe(CN) 6 ]•0.7H 2 O) [13].…”

Section: Introductionmentioning

confidence: 61%

“…For example, Camacho et al reported a rhombohedral R 3 structure for Na 1.86 Fe[Fe(CN) 6 ]•1.92H 2 O with oxygen positioned on half of the faces of the subcube [13]. This paper also reported a new orthorhombic Na-rich PBA (Na 1.8 Fe[Fe(CN) 6 ]•0.7H 2 O) [13]. On the other hand, Rudola et al reported a monoclinic P2 1 /n structure for Na 2 Fe[Fe(CN) 6 ]•2H 2 O with only a single oxygen atom at the face of the subcube [7].…”

Section: Introductionmentioning

confidence: 99%

Water driven phase transitions in Prussian white cathode materials

Nielsen¹,

Dzodan²,

Ojwang³

et al. 2022

J. Phys. Energy

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Prussian White (PW, Na2Fe[Fe(CN)6]∙zH2O) is a promising cathode material for use in sodium-ion batteries (SIBs) for large-scale energy storage applications which demand long cycling life-times. For use in non-aqueous battery applications PW must not contain any water, and yet its removal induces a large volume change destabilizing the structure and reducing cycling life. Indeed, the material undergoes multiple phase transitions depending upon both the sodium and water content. Due to the extensive use of X ray diffraction, the mechanism behind the observed phase transitions is poorly understood. Here, we show a neutron diffraction study exploring the influence of water on the structure of PW. For the first time, two temperature dependent and composition independent structures were observed near room temperature which differ in the FeN6 and FeC6 octahedral tilting configurations. The fundamental nature of this distortion, which drives the large volume changes, was determined to be connected to water ordering in the framework. Further, using distortion mode analysis during the dehydration process, it was determined that water does not modify the nature of the distortions present. Rather, water was found to modulate the magnitude of pre-existing structural distortions. These results provide a robust fundamental understanding to the chemical driving forces impacting the nature and magnitude of structural distortions in PBAs. The insight provides guidance for designing and quantifying tilt-engineering in PBAs ultimately enabling new materials with enhanced long-term electrochemical performance in battery applications.

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“…Apparently, some XRD peaks of the lattice, such as (220) and (420) diffraction, split into a double peak structure, manifesting a rhombohedral PBA structure, which may be due to the high concentration of sodium ions in the PW-H lattice. 28,31,32 In comparison with the traditional washing method with water, the Na-enriched framework can be obtained with sodium ascorbate aqueous solution as the washing agent, and it is non-toxic, is obtained in high yield and is applicable for large scale production. The specific surface area of PW-H is 32.5 m 2 g −1 , which is larger than that of PW-L (15.0 m 2 g −1 ) (Fig.…”

Section: Resultsmentioning

confidence: 99%