Phase transformation of copper hexacyanoferrate (KCuFe(CN)6) during zinc insertion: Effect of co-ion intercalation

Trócoli, Rafael; Kasiri, Ghoncheh; Mantia, Fabio La

doi:10.1016/j.jpowsour.2018.08.015

Cited by 84 publications

(45 citation statements)

References 29 publications

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“…This evolution of binding energy resulted in the stronger bond of Fe (high‐spin)–N and thus the activity of high‐spin Fe was weakened to show a decrease of redox peak and capacity at low potential. Besides, XRD patterns of FeHCF cathodes recorded after various cycles of 0, 100, 250, 500, 750, and 1000 cycles, respectively, demonstrate high consistency in terms of both peak position and relative intensity, evidencing that the crystalline structure maintained stable and no ionic substitution phenomenon happened (Figure S7, Supporting Information) . In the XPS signals of Fe2p 3/2 , the fitting peaks located at 707.4 and 711.1 eV are attributed to Fe(III) while the ones at 709.0 and 713.1 eV belong to Fe(II) (Figure f) .…”

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confidence: 87%

Activating C‐Coordinated Iron of Iron Hexacyanoferrate for Zn Hybrid‐Ion Batteries with 10 000‐Cycle Lifespan and Superior Rate Capability

et al. 2019

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Prussian blue analogue (PBA)-type metal hexacyanoferrates are considered as significant cathodes for zinc batteries (ZBs). However, these PBA-type cathodes, such as cyanogroup iron hexacyanoferrate (FeHCF), suffer from ephemeral lifespan (≤1000 cycles), and inferior rate capability (1 A g −1 ). This is because the redox active sites of multivalent iron (Fe(III/II)) can only be very limited activated and thus utilized. This is attributed to the spatial resistance caused by the compact cooperation interaction between Fe and the surrounded cyanogroup, and the inferior conductivity. Here, it is found that high-voltage scanning can effectively activate the C-coordinated Fe in FeHCF cathode in ZBs. Thanks to this activation, the Zn-FeHCF hybrid-ion battery achieves a record-breaking cycling performance of 5000 (82% capacity retention) and 10 000 cycles (73% capacity retention), respectively, together with a superior rate capability of maintaining 53.2% capacity at superhigh current density of 8 A g −1 (≈97 C). The reversible distortion and recovery of the crystalline structure caused by the (de)insertion of zinc and lithium ions is revealed. It is believed that this work represents a substantial advance on PBA electrode materials and may essentially promote application of PBA materials. Zinc BatteriesThe ORCID identification number(s) for the author(s) of this article can be found under https://doi.Zinc batteries (ZBs) established on the storage of divalent zinc ion in cathodic hosts are being intensively studied because of the high energy density of metallic zinc anode and the intrinsic safety performance. [1][2][3][4] The appropriate plating/stripping voltage (≈-0.76 V vs SHE) of zinc makes it electrochemically stable in water, which enables ZBs to avoid the employment of toxic organic electrolytes and complex assembly processes in glovebox compared with the lithium and sodium counterparts. [5][6][7] This advantage of zinc anode enables researchers to pay more attention to develop cathodic host materials. [8][9][10][11][12] Among these materials, MnO 2based cathodes possess high specific capacity based on the single electron transfer reaction of Mn(IV)/Mn(III), while the

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confidence: 87%

Activating C‐Coordinated Iron of Iron Hexacyanoferrate for Zn Hybrid‐Ion Batteries with 10 000‐Cycle Lifespan and Superior Rate Capability

et al. 2019

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“…The degradation of CuHCF electrodes is more severe for high electrolyte concentration . Even though X‐ray diffraction (XRD) revealed phase changes of CuHCF during cycling, the underlying mechanism and its relation to decreasing Zn ion capacity are still not clear . Therefore, detailed structural investigation is essential.…”

Section: Figurementioning

confidence: 99%

Irreversible Structural Changes of Copper Hexacyanoferrate Used as a Cathode in Zn‐Ion Batteries

Lim

Kasiri

Sahu

et al. 2020

Chemistry A European J

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The structural changes of copper hexacyanoferrate (CuHCF), a Prussian blue analogue, which occur when used as a cathode in an aqueous Zn‐ion battery, are investigated using electron microscopy techniques. The evolution of ZnxCu1−xHCF phases possessing wire and cubic morphologies from initial CuHCF nanoparticles are monitored after hundreds of cycles. Irreversible introduction of Zn ions to CuHCF is revealed locally using scanning transmission electron microscopy. A substitution mechanism is proposed to explain the increasing Zn content within the cathode material while simultaneously the Cu content is lowered during Zn‐ion battery cycling. The present study demonstrates that the irreversible introduction of Zn ions is responsible for the decreasing Zn ion capacity of the CuHCF cathode in high electrolyte concentration.

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“…Notably, during the chemical conversion reaction, the cathode reversibly change in composition and structure, accompanied by dissolution/deposition of Zn x SO 4 (OH) 2 x + 2 ·yH 2 O on its surface (Figure C, D). Up to now, reversible Zn‐ion storage in various host materials has been identified, such as manganese‐based oxides, vanadium‐based materials, and Prussian blue analogs . Among them, manganese‐based electrode materials with low cost, abundant resource, and pronounced structural stability, exhibit high specific capacity and operating voltage, rendering them most promising for Zn‐ion storage.…”

Section: Introductionmentioning

confidence: 99%

“…Up to now, reversible Zn-ion storage in various host materials has been identified, such as manganese-based oxides, vanadium-based materials, 37,63,[65][66][67] and Prussian blue analogs. [68][69][70][71] Among them, manganese-based electrode materials with low cost, abundant resource, and pronounced structural stability, exhibit high specific capacity and operating voltage, rendering them most promising for Zn-ion storage.…”

Section: Introductionmentioning

confidence: 99%

Challenges and perspectives for manganese‐based oxides for advanced aqueous zinc‐ion batteries

Zhao

Zhu

Zhang

2019

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Li‐ion batteries (LIBs) with excellent cycling stability and high‐energy densities have already occupied the commercial rechargeable battery market. Unfortunately, the high cost and intrinsic insecurity induced by organic electrolyte severely hinder their applications in large‐scale energy storage. In contrast, aqueous Zn‐ion batteries (ZIBs) are being developed as an ideal candidate because of their cheapness and high security. Benefiting from high operating voltage and acceptable specific capacity, recently, manganese‐based oxides with different various crystal structures have been extensively studied as cathode materials for aqueous ZIBs. This review presents research progress of manganese‐based cathodes in aqueous ZIBs, including various manganese‐based oxides and their zinc storage mechanisms. In addition, we also discuss some optimization strategies that aim at improving the electrochemical performance of manganese‐based cathodes, and the design of flexible aqueous ZIBs based on manganese‐based cathodes (MZIBs). Finally, this review summarizes some valuable research directions, which will promote the further development of aqueous MZIBs.

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Phase transformation of copper hexacyanoferrate (KCuFe(CN)6) during zinc insertion: Effect of co-ion intercalation

Cited by 84 publications

References 29 publications

Activating C‐Coordinated Iron of Iron Hexacyanoferrate for Zn Hybrid‐Ion Batteries with 10 000‐Cycle Lifespan and Superior Rate Capability

Activating C‐Coordinated Iron of Iron Hexacyanoferrate for Zn Hybrid‐Ion Batteries with 10 000‐Cycle Lifespan and Superior Rate Capability

Irreversible Structural Changes of Copper Hexacyanoferrate Used as a Cathode in Zn‐Ion Batteries

Challenges and perspectives for manganese‐based oxides for advanced aqueous zinc‐ion batteries

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