Electronic density distribution of Mn–N bonds by a tuning effect through partial replacement of Mn by Co or Ni in a sodium-rich hexacyanoferrate and its influence on the stability as a cathode for Na-ion batteries

Oliver-Tolentino, Miguel A.; González, M.; Osiry, H.; Ramos-Sánchez, Guadalupe; González, Ignacio

doi:10.1039/c8dt03595d

Cited by 34 publications

(26 citation statements)

References 56 publications

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“…The N‐coordinated TMs can be partially substituted by a single element or multiple elements in order to adjust the lattice parameters and redox property. Owing to the “zero‐strain” character and higher conductivity of NiHCFs, [ 25,178 ] Ni‐substitution has been widely employed to optimize the performances of NaFeHCFs, [ 179–181 ] KFeHCFs, [ 182,183 ] NaMnHCFs, [ 121,184,185 ] NaCoHCFs, [ 124,186 ] and NaCuHCFs. [ 19,187 ] In addition, the redox‐active Co and Fe have also been used to modify NaMnHCFs [ 102,185,188 ] and KMnHCFs.…”

Section: Elemental Substitutionmentioning

confidence: 99%

“…It is observed that the Fe‐substitution is most desired in terms of capacity and stability, while the Ni‐substitution can best promote the electrode kinetics. Similarly, Oliver‐Tolentino et al reported a superior effect of Ni‐substitution on NaMnHCF by comparing the structures and electrochemical behaviors of Na M x Mn 1‒ x HCF ( x = 0.55) with M = Ni, Co. [ 185 ] Detailed analyses indicate that both Co‐ and Ni‐substitution can improve the covalent character of MnN bonds, which will increase the separation between the bonding and antibonding orbitals. The charge density around Fe is also modulated by the polarizing power of Co and Ni, which induces decreased energy of Fe t 2g orbitals.…”

Section: Elemental Substitutionmentioning

confidence: 99%

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Hexacyanoferrate‐Type Prussian Blue Analogs: Principles and Advances Toward High‐Performance Sodium and Potassium Ion Batteries

Zhou

Cheng

Wang

et al. 2020

Advanced Energy Materials

295

209

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Na‐ion batteries (NIBs) and K‐ion batteries (KIBs) are promising candidates for next‐generation electric energy storage applications due to their low costs and appreciable energy/power density compared to Li‐ion batteries. In the search for viable electrode materials for NIBs and KIBs, Prussian blue analogs (PBAs) with inherent rigid and open frameworks and large interstitial voids have shown an impressive ability to accommodate big alkali‐metal ions without structure collapse. In particular, hexacyanoferrates (HCFs) utilizing abundant Fe(CN)6 resources are the most interesting subgroup of PBAs, being able to deliver a specific capacity of 70–170 mAh g‒1 and a voltage of 2.5‒3.8 V in NIBs/KIBs. In this Review, a comprehensive discussion of the HCF‐type cathode materials in terms of their structural features, redox mechanisms, synthesis control, and modification strategies based on research advances over the last ten years. The methodologies and achievements in improving the material properties of HCFs including the compositional stoichiometry, crystal water, crystallinity, morphology, and electrical conductivity are outlined, with the aim to promote understanding of these materials and provide new insights into future design of PBAs for advanced rechargeable batteries.

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Section: Elemental Substitutionmentioning

confidence: 99%

Section: Elemental Substitutionmentioning

confidence: 99%

Hexacyanoferrate‐Type Prussian Blue Analogs: Principles and Advances Toward High‐Performance Sodium and Potassium Ion Batteries

Zhou

Cheng

Wang

et al. 2020

Advanced Energy Materials

295

209

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“…PBAs can be utilized as cathode and anode materials for alkaline ion storage (Li + /Na + /K + ), due to their open frameworks, which offer large spaces for alkaline ion insertion and extraction . The mechanism for the use of PBAs for alkaline ion storage can be expressed by Equation :

{normalA}_{x} T ([], normalM {(CN)}_{6}) \leftrightarrow x {normalA}^{+} + T {([], normalM {(CN)}_{6})}^{x}^{-}

…”

Section: Applicationsmentioning

confidence: 99%

“…Owing to its open framework, the alkaline ions can be extracted/intercalated reversibly from/into the PBAs, making them suitable as cathode materials for alkaline ion batteries (Li + , Na + , K + , etc.) and as electrodes for supercapacitors with organic or aqueous electrolytes . Some defects and crystal water inevitably remain in PBAs due to their preparation in aqueous solution, meaning that they can be used as the host for hydrogen storage .…”

Section: Introductionmentioning

confidence: 99%

Chemical Properties, Structural Properties, and Energy Storage Applications of Prussian Blue Analogues

Han

Cheng

et al. 2019

Small

279

191

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Prussian blue analogues (PBAs, A2T[M(CN)6], A = Li, K, Na; T = Fe, Co, Ni, Mn, Cu, etc.; M = Fe, Mn, Co, etc.) are a large family of materials with an open framework structure. In recent years, they have been intensively investigated as active materials in the field of energy conversion and storage, such as for alkaline‐ion batteries (lithium‐ion, LIBs; sodium‐ion, NIB; and potassium‐ion, KIBs), and as electrochemical catalysts. Nevertheless, few review papers have focused on the intrinsic chemical and structural properties of Prussian blue (PB) and its analogues. In this Review, a comprehensive insight into the PBAs in terms of their structural and chemical properties, and the effects of these properties on their materials synthesis and corresponding performance is provided.

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“…Infrared spectra are sensitive to the coordinate environment of the chemical bond. In the PBA synthesis process, when the Fe(CN) 6 3–/4– group coordinates with the transition metal, the charge density at the N end shifts towards the transition metal, the CN binding energy shifts to higher values, , and the CN group vibration band should shift to higher wavenumbers in infrared spectroscopy. According to the sensitivity of CN to its bonding environment, in situ Fourier transform infrared (FTIR) spectroscopy characterization is an effective way to monitor the formation process of PBA frameworks.…”

Section: Introductionmentioning

confidence: 99%

In Situ FTIR-Assisted Synthesis of Nickel Hexacyanoferrate Cathodes for Long-Life Sodium-Ion Batteries

Miao

Fang

et al. 2019

ACS Appl. Mater. Interfaces

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Prussian blue analogs (PBAs) with stable framework structures are ideal cathodes for rechargeable sodium-ion batteries. The chelating agent-assisted coprecipitate method is an effective way to obtain low-defect PBAs that can limit the appearance of too many vacancies and water molecules and achieve an optimized Na-storage performance. However, for this method, the mechanism of chelating agent-assisted synthesis is still unclear. Herein, the synthesis process of nickel hexacyanoferrate (NiHCF) has been investigated by in situ infrared spectroscopy detection. The results show that the chelating agent oxalate slows down the nucleation process and effectively inhibits the formation of the Fe–CN–Ni frame in the aging process, producing highly crystallized and low-defect NiHCF samples. High-quality NiHCF presents a high specific capacity of 86.3 mAh g–1 (a theoretical value of ∼85 mAh g–1), an ultrastable cyclic retention of 90% over 800 cycles, and a remarkable high capacity retention of 74.6% at a current density of 4250 mA g–1 (50C). Particularly, the NiHCF//hard carbon full cell presents a high specific energy density of over 210 Wh kg–1 and an outstanding cyclic stability without obvious capacity attenuation over 1000 cycles.

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Electronic density distribution of Mn–N bonds by a tuning effect through partial replacement of Mn by Co or Ni in a sodium-rich hexacyanoferrate and its influence on the stability as a cathode for Na-ion batteries

Abstract: This study evaluates the effect of equimolar substitution of manganese by cobalt or nickel in hexacyanoferrate open frameworks as electrode for Na-ion batteries.

Cited by 34 publications

References 56 publications

Hexacyanoferrate‐Type Prussian Blue Analogs: Principles and Advances Toward High‐Performance Sodium and Potassium Ion Batteries

Hexacyanoferrate‐Type Prussian Blue Analogs: Principles and Advances Toward High‐Performance Sodium and Potassium Ion Batteries

Chemical Properties, Structural Properties, and Energy Storage Applications of Prussian Blue Analogues

In Situ FTIR-Assisted Synthesis of Nickel Hexacyanoferrate Cathodes for Long-Life Sodium-Ion Batteries

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