Low Voltage Charge/Discharge Behavior of Manganese Hexacyanoferrate

Shibata, Takayuki; Takachi, Masamitsu; Moritomo, Y.

doi:10.3390/batteries3010007

Cited by 10 publications

(11 citation statements)

References 32 publications

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“…With a cut-off voltage at -1.65 V there is an additional voltage plateau centered at -1.45 V. This plateau has a large irreversible capacity and corresponds to the permanent breakdown of the crystalline structure. This is a similar response to other PBA compositions that have been discharged to low potentials in non-aqueous electrolytes and where reversible capacity arises from conversion-type mechanisms [10][11][12] . Finding the limit of stability of the MnHCCr crystalline structure, and of PBA compounds more generally, is significant and places fundamental limitations on the useable potential range of the material.…”

Section: Resultssupporting

confidence: 68%

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Low-Potential Prussian Blue Analogues for Sodium-Ion Batteries: Manganese Hexacyanochromate

et al. 2019

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Prussian blue analogues (PBAs) have recently shown outstanding electrochemical properties ascribable to their unique open-framework crystal structure that allows the reversible insertion of alkali ions with negligible perturbation to the framework itself. Many hexacyanoferrate materials have shown excellent properties and are some of the most promising sodium-and potassiumion cathode materials in both aqueous and organic electrolytes. However, there is a distinct lack of candidate PBA materials that operate at low potentials as their characteristic crystalline framework shows instability. In this article we characterise the structure and electrochemical behavior of manganese hexacyanochromate which exhibits reversible sodium insertion at-0.86 V vs. SHE (1.84 V vs. Na + /Na), whilst maintaining the characteristic PBA cubic structure. This is the lowest redox potential of reported PBA materials and shows fast kinetics in a high voltage water-in-salt electrolyte. Further reduction in potential in an organic electrolyte shows decomposition of the crystalline structure

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Section: Resultssupporting

confidence: 68%

“…There have been efforts to develop PBA materials that have active redox couples at more negative potentials, however attempts to date have resulted in loss of the crystal structure and high reversible capacities ascribable to conversion-type mechanisms [10][11][12] . These works highlight issues that arise when a b c d…”

Section: Introductionmentioning

confidence: 99%

Low-Potential Prussian Blue Analogues for Sodium-Ion Batteries: Manganese Hexacyanochromate

et al. 2019

View full text Add to dashboard Cite

show abstract

“…With a cut-off voltage at −1.65 V there is an additional voltage plateau centered at −1.45 V. This plateau has a large irreversible capacity and corresponds to the permanent breakdown of the crystalline structure. This is a similar response to other PBA compositions that have been discharged to low potentials in non-aqueous electrolytes and where reversible capacity arises from conversion-type mechanisms 10,11 . Finding the limit of stability of the MnHCCr crystalline structure, and of PBA compounds more generally, is significant and places fundamental limitations on the useable potential range of the material.…”

Section: Further Reduction In Potential In An Organic Electrolytesupporting

confidence: 68%

“…There have been efforts to develop PBA materials that have active redox couples at more negative potentials, however attempts to date have resulted in loss of the crystal structure and high reversible capacities ascribable to conversiontype mechanisms 10,11 . These works highlight issues that arise when operating PBAs at low potentials in non-aqueous electrolytes but offer no explanation of the cause of structural breakdown.…”

Section: Introductionmentioning

confidence: 99%

Low Potential Prussian Blue Analogs: Manganese Hexacyanochromate

Wheeler¹,

Capone²,

Day³

et al. 2019

Preprint

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Prussian blue analogues (PBAs) have recently shown outstanding electrochemical properties ascribable to their unique open-framework crystal structure that allows the reversible insertion of alkali ions with negligible perturbation to the framework itself. Many hexacyanoferrate materials have shown excellent properties and are some of the most promising sodium- and potassium-ion cathode materials in both aqueous and organic electrolytes. However, there is a distinct lack of candidate PBA materials that operate at low potentials as their characteristic crystalline framework shows instability. In this article we characterise the structure and electrochemical behavior of manganese hexacyanochromate which exhibits reversible sodium insertion at - 0.86 V vs. SHE (1.84 V vs. Na<sup>+</sup>/Na), whilst maintaining the characteristic PBA cubic structure. This is the lowest redox potential of reported PBA materials and shows fast kinetics in a high voltage water-in-salt electrolyte. Further reduction in potential in an organic electrolyte shows decomposition of the crystalline structure.

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“…64 Attempts have been made to develop other compositions that operate at even lower potentials and in an organic electrolyte, but success remains elusive. The hexacyanoferrates 65 and hexacyanocobaltates 66 have been explored as anodes for lithium-ion batteries, but they do not maintain their crystal structure at such low potentials. At present, the limits of the stability of water in the structure and of the structure itself are unknown.…”

Section: Critical Research Frontsmentioning

confidence: 99%

Prussian Blue Analogs as Battery Materials

Hurlbutt

Wheeler

Capone

et al. 2018

Joule

407

351

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Prussian blue analogs have significant promise as active materials for the next generation of battery electrodes with improved cycle life and rate capability. Their useful electrochemical properties include two independent redox centers per unit cell; a nanoporous, open framework for rapid ion conduction; high stability during ion (de)insertion; and structural and electrochemical tunability for diverse applications. Here we share insights into how control of the five main crystallographic features (two transition-metal ions, the inserting ion, defects, and water) imparts control over the ion-insertion reaction. We then identify five key opportunities to expand our understanding of these materials, including the role of water in their ion conduction, modeling, synthesis methods, use as anode materials, and technoeconomics. Further research in these areas will accelerate the development of new, high-performing battery electrodes.

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Low Voltage Charge/Discharge Behavior of Manganese Hexacyanoferrate

Cited by 10 publications

References 32 publications

Low-Potential Prussian Blue Analogues for Sodium-Ion Batteries: Manganese Hexacyanochromate

Low-Potential Prussian Blue Analogues for Sodium-Ion Batteries: Manganese Hexacyanochromate

Low Potential Prussian Blue Analogs: Manganese Hexacyanochromate

Prussian Blue Analogs as Battery Materials

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