Manganese–cobalt hexacyanoferrate cathodes for sodium-ion batteries

Pasta, Mauro; Wang, Richard Y.; Ruffο, Riccardo; Qiao, Ruimin; Lee, Hyun‐Wook; Shyam, Badri; Guo, Minghua; Wang, Yayu; Wray, L. Andrew; Yang, Wanli; Toney, Michael F.; Cui, Yi

doi:10.1039/c5ta10571d

Cited by 202 publications

(176 citation statements)

References 45 publications

(51 reference statements)

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“…Both Fe and Mn display electroactivity, that is, they are oxidized to compensate the release of Na + ions during charge, as the thresholds shift toward higher energies, and their reduction occurs upon the uptake of Li + ions during discharge, in concomitance of an edge shift to lower energies. This confirms the mechanism already proposed from ex situ measurements, in particular the Fe III /Fe II and Mn III /Mn II redox activity, which is valid not only for Li + but also for Na + exchange. However, it adds further information on the effect of structural/interstitial/adsorbed water in the material.…”

Section: Resultsmentioning

confidence: 99%

Effect of Water and Alkali‐Ion Content on the Structure of Manganese(II) Hexacyanoferrate(II) by a Joint Operando X‐ray Absorption Spectroscopy and Chemometric Approach

et al. 2019

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Manganese hexacyanoferrate (MnHCF) is made of earth‐abundant elements by a safe and easy synthesis. The material features a higher specific capacity at a higher potential than other Prussian blue analogs. However, the effect of hydration is critical to determine the electrochemical performance as both the electrochemical behavior and the reaction dynamics are affected by interstitial/structural water and adsorbed water. In this study, the electrochemical activity of MnHCF is investigated by varying the interstitial ion content through a joint operando X‐ray absorption spectroscopy and chemometric approach, with the intent to assess the structural and electronic modifications that occur during Na release and Li insertion, as well as the overall dynamic evolution of the system. In MnHCF, both the Fe and Mn centers are electrochemically active and undergo reversible oxidation during the interstitial ion extraction (Fe2+/Fe3+ and Mn2+/Mn3+). The adsorption of water results in irreversible capacity during charge but only on the Fe site, which is suggested by our chemometric analysis. The local environment of Mn experiences a substantial yet reversible Jahn–Teller effect upon interstitial ion removal because of the formation of trivalent Mn, which is associated with a decrease of the equatorial Mn−N bond lengths by 10 %.

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Section: Resultsmentioning

confidence: 99%

Effect of Water and Alkali‐Ion Content on the Structure of Manganese(II) Hexacyanoferrate(II) by a Joint Operando X‐ray Absorption Spectroscopy and Chemometric Approach

et al. 2019

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“…As highly concentrated electrolytes of aqueous Na electrolytes, 2 M Na 2 SO 4 aq., 7 5 M NaNO 3 aq., 8 and 10 M NaClO 4 aq. 9,10 have been already reported. Among them, 2 M Na 2 SO 4 aq.…”

Section: Introductionmentioning

confidence: 93%

Effect of Concentrated Electrolyte on Aqueous Sodium-ion Battery with Sodium Manganese Hexacyanoferrate Cathode

et al. 2017

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From the viewpoint of the cost and safety, aqueous sodium-ion batteries are attractive candidate for large-scale energy storage. Although the operating voltage range of the aqueous battery is theoretically limited to 1.23 V by the electrochemical decomposition of water, the voltage restriction is a little bit eased in real aqueous battery system by the charge/discharge overvoltage. Effect of the concentrated electrolyte on the operation voltage was studied in aqueous Na-ion battery with Na 2 MnFe(CN) 6 hexacyanoferrates cathode and NaTi 2 (PO 4 ) 3 NASICON-type anode, in order to increase the discharge voltage. According to the cyclic voltammetry, the electrochemical window of diluted 1 mol kg −1 NaClO 4 aqueous electrolyte is only 1.9 V, whereas the corresponding electrochemical window of concentrated 17 mol kg −1 NaClO 4 aqueous electrolyte is widen to 2.8 V. This wide electrochemical window of the concentrated aqueous electrolyte allows the Na 2 MnFe(CN) 6 //NaTi 2 (PO 4 ) 3 aqueous sodium-ion system to work reversibly. By contrast, the framework of Na 2 MnFe(CN) 6 cathode was destroyed by the hydroxide anion generated in diluted 1 mol kg −1 electrolyte.

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“…The lattice parameter in a solid-solution (manganese, cobalt) hexacyanoferrate has been shown to be simply the average of the lattice parameters of the two pure compounds, weighted by atomic fraction. 27 Similarly, the voltage and capacity of a PBA can be tuned in a (copper, nickel) hexacyanoferrate by controlling composition. 28 This mixing strategy has the potential to ameliorate the disadvantages of the most promising materials by, for instance, preventing phase transitions on cycling.…”

Section: Effect Of Lattice Architecture On Electrochemistrymentioning

confidence: 99%

Prussian Blue Analogs as Battery Materials

Hurlbutt

Wheeler

Capone

et al. 2018

Joule

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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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Manganese–cobalt hexacyanoferrate cathodes for sodium-ion batteries

Abstract: The interplay between electrochemical properties, crystal structure, and chemical bonding of Prussian Blue analogues determines their suitability for grid-scale aqueous batteries.

Cited by 202 publications

References 45 publications

Effect of Water and Alkali‐Ion Content on the Structure of Manganese(II) Hexacyanoferrate(II) by a Joint Operando X‐ray Absorption Spectroscopy and Chemometric Approach

Effect of Water and Alkali‐Ion Content on the Structure of Manganese(II) Hexacyanoferrate(II) by a Joint Operando X‐ray Absorption Spectroscopy and Chemometric Approach

Effect of Concentrated Electrolyte on Aqueous Sodium-ion Battery with Sodium Manganese Hexacyanoferrate Cathode

Prussian Blue Analogs as Battery Materials

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