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

Mullaliu, Angelo; Aquilanti, Giuliana; Conti, Paolo; Giorgetti, Marco; Passerini, Stefano

doi:10.1002/cssc.201902802

Cited by 16 publications

(27 citation statements)

References 39 publications

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“…Operando Mn and Fe K-edge XANES spectra for the electrode at D 0 , C 1 , and D 1 states of charge are presented in Figure 2. The high variability in the Mn K-edge spectral shape and the low modifications occurring at the Fe K-edge are in line with previous work done on this material [11,12]. The Mn edge shifts towards higher energies during charge (C 1 ) as the Mn ions are oxidized from the divalent to the trivalent oxidation state.…”

Section: X-ray Absorption Near Edge Spectroscopy (Xanes)supporting

confidence: 88%

“…The unique components describing the whole cycling process are presented in Figure 5a,b for Mn and Fe, respectively, while the corresponding concentration profile plots are reported in Figure 5c,d. Contrary to what has been already reported for the same system under the conventional charge/discharge cycling protocol [12], the initial state Mn (D 0 ) is not uniquely described by a single component, i.e., "Component 1", but also by an additional contribution, labeled "Component 2", which accounts for 10% in D 0 (cf. Panels a,c).…”

Section: Operando Xanes and Mcr-als Data Analysiscontrasting

confidence: 77%

“…The operando experiment was performed during one galvanostatic cycle at C/15 current rate (corresponding to a current density equal to 0.01 A g MnHCF −1 ), starting with the charge and by recording a full set of spectra from number 4 to number 123. Before the operando experiment, the cell was subjected to an anomalous cycle test, consisting of five cycles with current density set at ±10 A g MnHCF −1 (i.e., 67 C), to simulate BMS malfunctioning and ill-usage of the device, followed by a discharge with current density equal to −0.1 A g MnHCF (see Figure S1) [11,12].…”

Section: Methodsmentioning

confidence: 99%

“…PBAs have also been demonstrated to be robust host materials; therefore, the stability and lifetime of the batteries may be enhanced [10]. MnHCF features a high specific capacity based on the redox activity at two species, i.e., Mn and Fe, and displays a large local structural effect following the Mn(II) oxidation to the Jahn-Teller (JT) active Mn(III) (Mn-N equatorial bond lengths are contracted by 10%) [11,12], which is, however, buffered in the long-range by the PBA open-framework. Indeed, MnHCF shows a non-cooperative JT effect and low volume change (2% only) during cycling [13].…”

Section: Introductionmentioning

confidence: 99%

“…Here, the applied protocol causes the formation of an additional spectral component compared to the previous study [12], as retrieved by multivariate curve resolution analysis with an alternating least squares algorithm (MCR-ALS). Although the loss in coulombic efficiency in the first cycle is drastic, the local structure analyzed by X-ray absorption fine structure (XAFS) spectroscopy is not significantly affected at the full state of charge and underlines the fair structural stability of the host, even after the applied electrochemical protocol.…”

Section: Introductionmentioning

confidence: 99%

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Structural Effects of Anomalous Current Densities on Manganese Hexacyanoferrate for Li-Ion Batteries

et al. 2020

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A battery management system (BMS) plays a pivotal role in providing optimal performance of lithium-ion batteries (LIBs). However, the eventual malfunction of the BMS may lead to safety hazards or reduce the remaining useful life of LIBs. Manganese hexacyanoferrate (MnHCF) was employed as the positive electrode material in a Li-ion half-cell and subjected to five cycles at high current densities (10 A gMnHCF−1) and to discharge at 0.1 A gMnHCF−1, instead of classical charge/discharge cycling with initial positive polarization at 0.01 A gMnHCF−1, to simulate a current sensor malfunctioning and to evaluate the electrochemical and structural effects on MnHCF. The operando set of spectra at the Mn and Fe K-edges was further analyzed through multivariate curve resolution analysis with an alternating least squares algorithm (MCR–ALS) and extended X-ray absorption fine structure (EXAFS) spectroscopy to investigate the structural modifications arising during cycling after the applied electrochemical protocol. The coulombic efficiency in the first cycle was dramatically affected; however, the local structural environment around each photo absorber recovered during charging. The identification of an additional spectral contribution in the electrochemical process was achieved through MCR-ALS analysis, and the Mn-local asymmetry was thoroughly explored via EXAFS analysis.

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Section: X-ray Absorption Near Edge Spectroscopy (Xanes)supporting

confidence: 88%

Section: Operando Xanes and Mcr-als Data Analysiscontrasting

confidence: 77%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structural Effects of Anomalous Current Densities on Manganese Hexacyanoferrate for Li-Ion Batteries

et al. 2020

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Mitigating Jahn–Teller Effects by Fast Electrode Kinetics Inducing Charge Redistribution

Choi

Kim

et al. 2022

Adv Funct Materials

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Manganese hexacyanomanganates have attracted significant attention as promising cathode materials for sodium‐ion batteries owing to the high theoretical capacity and low cost of Mn resources. Because of the strong Jahn–Teller effect, causing unstable local phase transition and distortion, the redox reactions of the high‐spin state of Mn(III) are considered to be a conundrum. Herein, it is reported that the charge‐redistribution mechanism of low‐spin MnIII + high‐spin MnIII → low‐spin MnII + high‐spin MnIV in manganese hexacyanomanganates can decrease unstable high‐spin MnIII, leading to the mitigation of Jahn–Teller distortion. X‐ray absorption near‐edge spectroscopy and X‐ray photoelectron spectroscopy suggest that the fast reaction rate activates charge redistribution. Moreover, different crystal structures, reported using post‐mortem synchrotron X‐ray diffraction analysis, confirm a large orthorhombic structure, thus verifying the presence of charge redistribution based on the superexchange rule. These results demonstrate that manganese hexacyanomanganate in an aqueous electrolyte can achieve long‐term cyclability, thus paving the way for high‐performance batteries.

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Prussian Blue Analogues for Sodium‐Ion Batteries: Past, Present, and Future

et al. 2022

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photocopying process took nearly a century from 1843 until the early 1940s, while the detailed crystal structure of PB was first confirmed as cubic by Ludi and co-workers in 1977, which is now widely accepted. [6] Remarkably, the past four decades have witnessed the exploration of PB in more and more new and totally different, but very promising application areas, reaching from rechargeable batteries [7] to catalysis [8] and biosensors, [9] from optically switchable films in electrochromic devices (smart windows) [10] to a helpful nanomaterial for cancer therapy. [11] Due to their excellent redox activity, low cost, and highly reversible phase transitions during the insertion/extraction process of certain cations, PB and PBAs have also been widely investigated as promising active materials for energy storage devices, especially for commercial sodium-ion batteries (SIBs) beyond other batteries system (potassium-ion batteries, [12,13] lithium-ion batteries (LIBs), [14] lithium-sulfur batteries (LI-S), [15] lithium-air batteries, [16] zinc-air batteries, [17] solid-state batteries, [18] etc.) in large-scale stationary energy storage systems in the near future. [19,20] The chemical formulas of PBAs could be represented asHere, A represents a single alkali metal or alkaline earth metal, or a mixture of these metals, while M 1 and M 2 typically are transition metals bonded by CN − bonds to form a 3D open structure with the capability to host element(s) A inside the crystal structure. □ represents the vacancy that is caused by the loss of an M 2 (CN) 6 group and the occupation by coordination water and interstitial water, the species and ionic radii of which are shown in Figure 2a. [21] With the different species and various ratios of A/M 1 /M 2 , the number of family members could reach more than 100, sharing different crystal phases, including monoclinic, [22,23] rhombohedral, [24,25] cubic, [26,27] tetragonal, [28] hexagonal, [29] etc. According to the amount of redox-active sites for battery application, PB and PBAs could be divided into dual-electron transfer type (DE-PBAs: M 1 and M 2 = Mn, Fe, Co) and single-electron transfer type (SE-PBAs: M 1 = Zn, Ni and M 2 = Fe, Co, Mn) with theoretical specific capacity of 170 and 85 mAh g −1 , respectively. [21] Taking the high average voltage and capacity of the DE-PBAs into consideration, they are promising and competitive, even to the level of LiFePO 4 (a well-known cathode material for the LIBs), for high energy density devices (≈450 Wh kg −1 on the material level). On the other hand, the negligible structural distortion and high conductivity of SE-PBAs make them desirable choices for fast-charging and long-life devices. [20,30] Prussian blue analogues (PBAs) have attracted wide attention for their application in the energy storage and conversion field due to their low cost, facile synthesis, and appreciable electrochemical performance. At the present stage, most research on PBAs is focused on their material-level optimization, whereas their properties in practical b...

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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

Cited by 16 publications

References 39 publications

Structural Effects of Anomalous Current Densities on Manganese Hexacyanoferrate for Li-Ion Batteries

Structural Effects of Anomalous Current Densities on Manganese Hexacyanoferrate for Li-Ion Batteries

Mitigating Jahn–Teller Effects by Fast Electrode Kinetics Inducing Charge Redistribution

Prussian Blue Analogues for Sodium‐Ion Batteries: Past, Present, and Future

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