A Ni-doping-induced phase transition and electron evolution in cobalt hexacyanoferrate as a stable cathode for sodium-ion batteries

Quan, Junjie; Xu, Enze; Zhu, Hanwen; Chang, Yajing; Zhu, Yi; Li, Pengcheng; Sun, Zhenjie; Yu, Deng‐Guang; Jiang, Yang

doi:10.1039/d0cp05665k

Cited by 20 publications

(25 citation statements)

References 34 publications

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“…Among them, metal-ion doping is currently one of the most effective modification methods. The metal ions are usually doped at the M-site or Na-site. − K + are usually doped at the Na-site, while transition-metal ions such as Co 2+ , Ni 2+ , and Mn 2+ are usually doped at the M-site. − In contrast, there are more studies on doping at the M-site. Since You et al , found the “zero-strain” characteristics of NiHCF during the desodiation/sodiation process, Ni is often used as a doping element to improve the cycle stability of MHCF.…”

Section: Introductionmentioning

confidence: 99%

High-Performance Fe-Based Prussian Blue Cathode Material for Enhancing the Activity of Low-Spin Fe by Cu Doping

Chen

Zhang

et al. 2022

ACS Appl. Mater. Interfaces

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Iron-based Prussian blue (FeHCF) has great application potential in the large-scale production of sodium-ion (Na + ) batteries because of its high theoretical capacity and abundant Fe ore resources. However, the Fe(CN) 6 vacancies and crystal water seriously affect the electrochemical performance. Herein, a Cu-doped FeHCF (Cu−FeHCF) cathode material is successfully prepared directly by a coprecipitation method. After Cu doping, the monoclinic structure and the quasi-cubic morphology are retained, but the electrochemical performance is significantly improved. In addition to few Fe(CN) 6 vacancies and low crystal water, the improved performance is also related to the enhanced electrochemical activity of low-spin Fe and the stabilizing effect of Cu on the crystal structure. Moreover, Cu doping also controls the side reaction to a certain extent. As a result, after Cu doping, the initial discharge capacity is enhanced from 107.9 to 127.4 mA h g −1 at 100 mA g −1 , especially the capacities contributed by low-spin Fe increase from 30.0, 21.7, and 16.7 mA h g −1 to 48.8, 45.4, and 43.7 mA h g −1 for the first three cycles, respectively. Even at 2 A g −1 , Cu−FeHCF still has a promising initial capacity of 82.3 mA h g −1 and only a 0.047% capacity decay rate for each cycle over 500 cycles. Therefore, Cu−FeHCF shows excellent application potential in the field of Na + energy storage batteries.

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Section: Introductionmentioning

confidence: 99%

High-Performance Fe-Based Prussian Blue Cathode Material for Enhancing the Activity of Low-Spin Fe by Cu Doping

Chen

Zhang

et al. 2022

ACS Appl. Mater. Interfaces

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“…Correspondingly, the low‐voltage plateau corresponding to a redox reaction on FeN 6 center and the high‐voltage plateau corresponding to a redox reaction on FeC 6 octahedra that occurred during the cycling of FeHCF@VCSC also undergo reversible evolution in XPS spectra, accompanied by the changes of peak shift and peak area of Fe 2p, reflecting the reversible Na‐ions insertion/extraction processes. [ 20,37 ]…”

Section: Resultsmentioning

confidence: 99%

Na_1.51Fe[Fe(CN)₆]_0.87·1.83H₂O Hollow Nanospheres via Non‐Aqueous Ball‐Milling Route to Achieve High Initial Coulombic Efficiency and High Rate Capability in Sodium‐Ion Batteries

Peng

Liu

et al. 2022

Small Methods

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Prussian blue analogues (PBAs) have attracted extensive attention as cathode materials in sodium‐ion batteries (SIBs) due to their low cost, high theoretical capacity, and facile synthesis process. However, it is of great challenge to control the crystal vacancies and interstitial water formed during the aqueous co‐precipitation method, which are also the key factors in determining the electrochemical performance. Herein, an antioxidant and chelating agent co‐assisted non‐aqueous ball‐milling method to generate highly‐crystallized Na2‐xFe[Fe(CN)6]y with hollow structure is proposed by suppressing the speed and space of crystal growth. The as‐prepared Na2‐xFe[Fe(CN)6]y hollow nanospheres show low vacancies and interstitial water content, leading to a high sodium content. As a result, the Na‐rich Na1.51Fe[Fe(CN)6]0.87·1.83H2O hollow nanospheres exhibit a high initial Coulombic efficiency, excellent cycling stability, and rate performance via a highly reversible two‐phase transition reaction confirmed by in situ X‐ray diffraction. It delivers a specific capacity of 124.2 mAh g−1 at 17 mA g−1, presenting ultra‐high rate capability (84.1 mAh g−1 at 3400 mA g−1) and cycling stability (65.3% capacity retention after 1000 cycles at 170 mA g−1). Furthermore, the as‐reported non‐aqueous ball‐milling method could be regarded as a promising method for the scalable production of PBAs as cathode materials for high‐performance SIBs.

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“…Nowadays, the applications on PBAs of ex situ XPS are mainly for the analysis of pristine powder and disassembled electrode sheets after cycles for PBAs. Jiang et al [131] studied the evolution of the electronic state information under different charge/discharge states via ex situ XPS. As shown in Figure 9B, the Fe peaks retain consistent shapes but are shifted to higher binding energies.…”

Section: (14 Of 19)mentioning

confidence: 99%

Section: Advanced Techniques For Pbas Cathodesmentioning

confidence: 99%

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Advanced Characterization Techniques Paving the Way for Commercialization of Low‐Cost Prussian Blue Analog Cathodes

Liu

Peng

Lai

et al. 2021

Adv Funct Materials

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Prussian blue analogs (PBAs), as promising cathode materials for sodium-ion batteries (SIBs), have received extensive research interest due to their appealing characteristics, e.g., the low cost of their raw materials, easy manufacturing, open frameworks, and high theoretical specific capacity. There are some challenges for PBAs cathodes, however, hindering their performance output, making them currently unacceptable for practical applications. To improve the performance and cycling stability of PBAs, a clear in-depth understanding of the relationship of their electrochemical reaction process to their ion insertion/extraction mechanisms and structural evolution is extremely important. Nowadays, advanced characterization techniques have become an important tool to guide the construction of high-performance PBAs cathodes. In this review, the various advances by using advanced characterization techniques to reveal the reaction mechanisms for PBAs cathodes are summarized and discussed. By appreciating how the advanced characterization techniques to guide fabrication of high-performance PBAs or reveal their detailed reaction mechanisms, it is hoped that this review can assist readers to find more valuable and advanced technologies to help to resolve some key problems and enhance their performance so as to accelerate the practical application of PBAs cathode for SIBs.

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A Ni-doping-induced phase transition and electron evolution in cobalt hexacyanoferrate as a stable cathode for sodium-ion batteries

Abstract: The charge density differences in different charge states reflect the contributions of each transition-metal atom to the electron transfer process, fundamentally revealing the formation mechanism of the three pairs of redox peaks shown by NCHCF.

Cited by 20 publications

References 34 publications

High-Performance Fe-Based Prussian Blue Cathode Material for Enhancing the Activity of Low-Spin Fe by Cu Doping

High-Performance Fe-Based Prussian Blue Cathode Material for Enhancing the Activity of Low-Spin Fe by Cu Doping

Na_1.51Fe[Fe(CN)₆]_0.87·1.83H₂O Hollow Nanospheres via Non‐Aqueous Ball‐Milling Route to Achieve High Initial Coulombic Efficiency and High Rate Capability in Sodium‐Ion Batteries

Advanced Characterization Techniques Paving the Way for Commercialization of Low‐Cost Prussian Blue Analog Cathodes

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A Ni-doping-induced phase transition and electron evolution in cobalt hexacyanoferrate as a stable cathode for sodium-ion batteries

Abstract: The charge density differences in different charge states reflect the contributions of each transition-metal atom to the electron transfer process, fundamentally revealing the formation mechanism of the three pairs of redox peaks shown by NCHCF.

Cited by 20 publications

References 34 publications

High-Performance Fe-Based Prussian Blue Cathode Material for Enhancing the Activity of Low-Spin Fe by Cu Doping

High-Performance Fe-Based Prussian Blue Cathode Material for Enhancing the Activity of Low-Spin Fe by Cu Doping

Na1.51Fe[Fe(CN)6]0.87·1.83H2O Hollow Nanospheres via Non‐Aqueous Ball‐Milling Route to Achieve High Initial Coulombic Efficiency and High Rate Capability in Sodium‐Ion Batteries

Advanced Characterization Techniques Paving the Way for Commercialization of Low‐Cost Prussian Blue Analog Cathodes

Contact Info

Product

Resources

About

Na_1.51Fe[Fe(CN)₆]_0.87·1.83H₂O Hollow Nanospheres via Non‐Aqueous Ball‐Milling Route to Achieve High Initial Coulombic Efficiency and High Rate Capability in Sodium‐Ion Batteries