Structural-electrochemical relations in the aqueous copper hexacyanoferrate-zinc system examined by synchrotron X-ray diffraction

Renman, Viktor; Ojwang, Dickson O.; Valvo, Mario; Gómez, Cesar Pay; Gustafsson, Torbjörn; Svensson, Gunnar

doi:10.1016/j.jpowsour.2017.09.079

Cited by 71 publications

(66 citation statements)

References 27 publications

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“…CuHCF seems to transform in a form of Zn x Cu 1− x HCF. To explain the additional insertion of Zn ions from the interstitial site to the substitutional site, Zn ion hopping to Fe(CN) 6 vacancy sites was suggested using synchrotron XRD measurements . However, this hopping mechanism was observed only at the first ZIB cycle without Cu ion loss and cannot be related to the morphology change and ZIB capacity decrease here.…”

Section: Figurementioning

confidence: 90%

“…A new peak at ≈2 θ =27° visible as a shoulder and a sharp peak at ≈2 θ =33° cannot be assigned. It seems that Zn ions are introduced to CuHCF and change the local crystal structure, regarding the fast cation and water exchange ability of CuHCF in electrolytes . Other new peaks with higher intensity are found in 500‐ and 1000 cycled cathodes, which can be assigned to the (200), (220), (400), and (420) planes of the cubic ZnHCF phase and others to the (024), (116), (300), and (119) planes of the rhombohedral ZnHCF structure.…”

Section: Figurementioning

confidence: 97%

“…We propose that this substitution of Cu ions by electrochemically inactive Zn ions leads to a phase transformation and is the main reason of capacity degradation of CuHCF cathode in aqueous ZIB. This is because CuHCF loses the Cu 2+/1+ redox couple which also plays a role for charge compensating of divalent metal cation during intercalation, and consequently a lower Fe 3+/2+ redox efficiency is present in the wire and cubic morphologies. The severe capacity loss of the cathode is found after around 500 cycles (Figure ), where many wires and cubes are formed.…”

Section: Figurementioning

confidence: 99%

See 2 more Smart Citations

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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Section: Figurementioning

confidence: 90%

Section: Figurementioning

confidence: 97%

Section: Figurementioning

confidence: 99%

See 1 more Smart Citation

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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“…Despite these outstanding features, only single transition metal ions, that is, Fe ions in most cases, are believed to be electrochemically activated under aqueous electrolyte systems, leading to that the specific capacity of PBAs delivered in aqueous Zn-ion system is limited to ≈60 mAhg −1 , and moreover the voltage of most is still low (≈1.2 V vs Zn/Zn 2+ ), leading to a low energy density. [19][20][21][22][23][24][25][26][27] On the other hand, most reported works using PBAs cathode show poor cyclic stability (<1000 cycles).…”

Section: Introductionmentioning

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

386

296

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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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“…The complexity of a battery, which consists of different components and various contributions to the overall redox process, could be untangled by using a combined complementary multitechnique approach. X-ray diffraction (XRD) is commonly used to identify crystalline phases, and to follow their modification during cycling [26][27][28]. X-ray absorption fine structure (XAFS) is the technique of choice for retrieving electronic and short-range structural information in transition-metal-based systems [29,30], by analyzing both X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) portions.…”

Section: Introductionmentioning

confidence: 99%

Operando XAFS and XRD Study of a Prussian Blue Analogue Cathode Material: Iron Hexacyanocobaltate

et al. 2018

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The reversible electrochemical lithiation of potassium iron hexacyanocobaltate (FeCo) was studied by operando X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) assisted by chemometric techniques. In this way, it was possible to follow the system dynamics and retrieve structural and electronic transformations along cycling at both Fe and Co sites. These analyses confirmed that FeCo features iron as the main electroactive site. Even though the release of potassium ions causes a local disorder around the iron site, the material exhibits an excellent structural stability during the alkali ion deinsertion/insertion processes. An independent but interrelated analysis approach offers a good strategy for data treatment and provides a time-resolved picture of the studied system.

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Structural-electrochemical relations in the aqueous copper hexacyanoferrate-zinc system examined by synchrotron X-ray diffraction

Cited by 71 publications

References 27 publications

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

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

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

Operando XAFS and XRD Study of a Prussian Blue Analogue Cathode Material: Iron Hexacyanocobaltate

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