Encapsulation of zinc hexacyanoferrate nanocubes with manganese oxide nanosheets for high-performance rechargeable zinc ion batteries

Lu, Ke; Song, Bin; Zhang, Yuxin; Ma, Houyi; Zhang, Jintao

doi:10.1039/c7ta07834j

Cited by 201 publications

(137 citation statements)

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“…Besides, the electrochemically stable plating/stripping during the repeated charging/discharging processes of Zn electrode also plays a significant role in this ultralong‐term cycling, which was convincingly demonstrated by the voltage–time curve with long lifespan yet low polarization at both low and high current densities (1 and 10 mA cm −2 , corresponding to 60 and 6 min per cycle, respectively), and dendrite‐free surface (Figure S14, Supporting Information) . This ultralong lifespan of 10 000 cycles with a high capacity retention of 73% outperforms all of the Zn–PBA batteries reported before (Figure h), demonstrating the enormous potential of the high‐voltage‐induced activation strategy …”

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confidence: 64%

“…The GCD profiles in Figure b show the combination of the voltage platform at about 1.5 V and the sloping profiles in the whole range of rates, implying both the battery‐ and capacitance‐type capacity contribute to this excellent rate performance . The Zn–FeHCF battery with a high capacity contributions from voltage region above 0.5 V (60 mAh g ‐1 at 1 A g −1 , 56.8 mAh g –1 at 1.5 A g −1 , 52.8 mAh g –1 at 2 A g −1 ) which is better than or comparative to many other PBA‐type cathodes reported in aqueous Zn batteries . Furthermore, the larger or comparative capacities in this work were obtained at 10‐fold to 100‐fold current densities of the previous works (≈0.01–0.2 A g −1 ) (Figure c).…”

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confidence: 95%

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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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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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“…Moreover, even at superhigh tenfold current densities of its corrival counterparts, the battery still maintains high capacity of over 109 mAh g −1 (Figure 2). [21,22,24,25,[38][39][40] This high capacity is attributed to the two redox reaction sites of Fe and Co in CoFe(CN) 6 active material. The cycling performance is investigated at 3 A g −1 , which exhibits remarkable cyclic stability with nearly no capacity decline and 100% coulombic efficiency after 2200 cycles (Figure 2h).…”

Section: Electrochemical Performance Of Zn/cofe(cn) 6 Battery Using 4mentioning

confidence: 99%

Achieving High‐Voltage and High‐Capacity Aqueous Rechargeable Zinc Ion Battery by Incorporating Two‐Species Redox Reaction

Chen

Long

et al. 2019

Advanced Energy Materials

364

292

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safety, and low cost. [1][2][3][4][5] However, the strong electrostatic interaction with host materials originating from divalent chemistry leads to low output voltage, poor reversibility, and especially sluggish kinetics. Various cathode materials have been developed to navigate these challenges. Currently, the most studied cathode active materials are manganesebased [6][7][8][9] and vanadium-based [10][11][12][13] composites. Nonetheless, relative low operating voltage and poor rate performance remains as issues. To reach the operating voltage of electronic devices, multiple batteries must be connected in series. This practice increases the volume of battery and causes energy loss. Furthermore, poor rate capability limits application of Zn-ion batteries in high-power appliances.The Prussian blue analogues (PBAs) possessing a 3D open framework with large interstitial sites, [4][5][6][7][8][9][10][11][12][13][14][15][16] are considered as a promising host material for reversible Zn-ion intercalation/deintercalation with fast charge/discharge properties and high operational voltage, which is ascribed to its ideal crystal structure and desirable electrochemical properties. [17] Recently, hexacyanometallates with a typical formula of A x M′[M″(CN) 6 ] y ⋅nH 2 O (simply denoted as M′/M″ PBA) are investigated as cathode active materials for aqueous batteries including Li-, Na-, Mg-, Ca-, and Zn-ion batteries, where the A Herein, a two-species redox reaction of Co(II)/Co(III) and Fe(II)/Fe(III) incorporated in cobalt hexacyanoferrate (CoFe(CN) 6 ) is proposed as a breakthrough to achieve jointly high-capacity and high-voltage aqueous Zn-ion battery. The Zn/CoFe(CN) 6 battery provides a highly operational voltage plateau of 1.75 V (vs metallic Zn) and a high capacity of 173.4 mAh g −1 at current density of 0.3 A g −1 , taking advantage of the two-species redox reaction of Co(II)/Co(III) and Fe(II)/Fe(III) couples.Even under extremely fast charge/discharge rate of 6 A g −1 , the battery delivers a sufficiently high discharge capacity of 109.5 mAh g −1 with its 3D opened structure framework. This is the highest capacity delivered among all the batteries using Prussian blue analogs (PBAs) cathode up to now. Furthermore, Zn/CoFe(CN) 6 battery achieves an excellent cycling performance of 2200 cycles without any capacity decay at coulombic efficiency of nearly 100%. One further step, a sol-gel transition strategy for hydrogel electrolyte is developed to construct high-performance flexible cable-type battery. With the strategy, the active materials can adequately contact with electrolyte, resulting in improved electrochemical performance (≈18.73% capacity increase) and mechanical robustness of the solid-state device. It is believed that this study optimizes electrodes by incorporating multi redox reaction species for high-voltage and high-capacity batteries.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.

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“…MnO x ‐based hybrid nanomaterials are also studied for Zn ion batteries. For example, 3D Zn hexacyanoferrate (ZnHCF) encapsulated within MnO 2 nanosheets . This hybrid material combines the intercalation of Zn 2+ inside the ZnHCF cores and the pseudocapacitive reactions for Zn‐ion storage on MnO 2 shells.…”

Section: Mnox‐based Materials For Battery Applicationsmentioning

confidence: 99%

Manganese‐Oxide‐Based Electrode Materials for Energy Storage Applications: How Close Are We to the Theoretical Capacitance?

Wang

2018

Advanced Materials

100

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Of the transition metals, Mn has the greatest number of different oxides, most of which have a special tunnel structure that enables bulk redox reactions. The high theoretical capacitance and capacity results from a greater number of accessible oxidation states than other transition metals, wide potential window, and the high natural abundance make MnO species promising electrode materials for energy storage applications. Although MnO electrode materials have been intensely studied over the past decade, their electrochemical performance is still insufficient for practical applications. Currently, there is a trade-off between specific capacitance and loading mass. MnO species have intrinsically poor electrical conductivity, and current structural designs are not sophisticated enough to accommodate enough redox-active sites. Recent studies have certainly made progress in increasing capacitance through making use of electrically conductive components and controlling the morphology of the MnO species to expose more surface area. To increase the capacitance of MnO electrodes to the largest extent without limiting loading mass, further structural design at the nanoscale and manipulation of the electrically conductive component are required. An ideal nanostructure is proposed to guide future research toward closing the gap between achieved and theoretical capacitance, without limiting the loading mass.

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Encapsulation of zinc hexacyanoferrate nanocubes with manganese oxide nanosheets for high-performance rechargeable zinc ion batteries

Abstract: The encapsulation of zinc hexacyanoferrate nanocubes with manganese oxide nanosheets enables the combination of intercalative core nanocube and capacitive shell together with reversible redox reactions for enhancing performance of Zn-ion batteries.

Cited by 201 publications

References 39 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

Achieving High‐Voltage and High‐Capacity Aqueous Rechargeable Zinc Ion Battery by Incorporating Two‐Species Redox Reaction

Manganese‐Oxide‐Based Electrode Materials for Energy Storage Applications: How Close Are We to the Theoretical Capacitance?

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