A simple method to fabricate NiFe2O4/NiO@Fe2O3 core-shelled nanocubes based on Prussian blue analogues for lithium ion battery

doi:10.1016/j.jallcom.2020.153966

Journal of Alloys and Compounds

Volume 825, 5 June 2020, 153966

https://doi.org/10.1016/j.jallcom.2020.153966 Get rights and content

Highlights

•
Core-shelled structure is built through ion exchange process.
•
Ion concentrations in ion exchange process sever different surfaces.
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Complete Fe₂O₃ shell layer permits more stability during cycling.
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Suitable calcined temperature is detected for high performance material.

Abstract

Core-shelled NiFe₂O₄/NiO@Fe₂O₃ nanocubes were synthesized based on Prussian blue analogues. The core-shelled structure was built through ion-exchange process in aqueous solution, and was remained after calcination. Different concentrations of ferrous affect the size and surface states of PBA precursors and its successor. Fabricated core-shelled NiFe₂O₄/NiO@Fe₂O₃ nanocubes produced with the PBA precursor that soaked in the solution of ferrous ion with the highest concentration in this work appears the most stable capacity during cycles, because of its more homogeneous Fe₂O₃ layer surface and more complete crystal. At the current density of 100 mA/g, it offers an initial capacity of 1587.96 mA h/g, and the second capacity of 967.91 mA h/g, that was remained as 806.1 mA h/g after 50 cyles. At 500 mA/g, it performs a capacity of 472.5 mA h/g after 500 cycles with a strong stability.

Introduction

As the most attractive chemical power instrument, Li-ion batteries (LIBs) have many advantages such as high work voltage, low self-discharge, high capacity and energy density [1], and etc. With the development of technology, more and more equipment like private digital device and electric vehicle requires higher performance, especially higher capacity, for LIBs [[2], [3], [4]]. Constituted by metal foil, anode active material [5,6], cathode active material [7], separator, and electrolyte [8], LIBs was determined the capacity by anode/cathode active material [1,9]. Compared to graphite, which is the most widely used as anode material in LIBs, mental oxides have much higher capacity [[10], [11], [12], [13]]. For example, NiO has the theoretical capacity of 731 mA/g with conversion mechanism [14,15]. Furthermore, iron oxides including FeO, Fe₂O₃ [16], and Fe₃O₄ [17] would be the most suitable mental oxides as anode material of LIBs because of it is abundance and its low processing cost especially its environmental friendly [10]. However it is a serious barrier that the capacity of metal oxides behaves a severe fading during cycles because of volume expansion [5,18]. For remitting this disadvantage, it is a common solution to build a special nanostructures such as hollow [19], core-shell [20], nanotube [21], nanobelt [22] and so on, in which constructing core-shelled structure is a widely used approach [23]. (see Table 1)

Besides, ternary ferrites that donated as AFe₂O₄(A = Ni, Co, Mn, Cu) which has spinel structure are promising a series materials consisted of different element to possess multiple advantages [18]. Prussian blue analogues (PBAs) are always used as a fundamental materials applied in various fields such as electrochemical sensor [24], electro catalysis [25] because of its abundant active components and positions [26,27]. Therefore, a series metal oxide will be obtained after oxidizing different iron-based PBAs [28]. Meanwhile, because of there are many –C-N-Fe^Ⅲ units in iron-based PBAs, after oxidizing, the existences of C, N element will also be remained partly while the lost part will leave some holes that provide space to storage electrolyte, which means a good conductivity [25,29]. Moreover, PBAs are usually used as templates to build hollow, core-shell [30], nanocage [31], yolk structure [32] and so on throw dissolve-recrystallization process in solution, because of its metal species can be substituted by other transition metal elements to each other as Ni, Co, Mn, Zn, Cu, Fe [[33], [34], [35]]. This characteristic proves a convenience to construct core-shelled structure of metal oxides.

In this work, Ni₃[Fe(CN)₆]₂ was prepared as precursor, and then core-shelled Ni₃[Fe(CN)₆]₂@Fe₄[Fe(CN)₆]₃ were obtained after iron ion exchange in water solution. After oxidized in different temperatures, the corresponding obtained metal oxide was made into cathode electrode for half-cells with lithium tablet as anode to investigate electrochemical performances. The results reveal that metal oxides with core-shelled structure were synthesized successfully, and the corresponding cell behave cycle-life, rate performance, conductivity than the sample without core-shelled structure. Additionally, the mechanism and kinetics during cycles was also measured and analysis to show more information. The obtained NiFe₂O₄/NiO@Fe₂O₃ marked NFO@FO3-600 reveals specific capacity of 808.22 mA h/g after 50 cycles at the current density of 100 mA/g, and 472.5 mA h/g after 500 cycles at the current density of 500 mA/g.

Section snippets

Chemicals

Nickel Acetate (Ni(CH₃COO)₂・4H₂O), Potassium Ferricyanide (K₃Fe(CN)₆), Ferrous Sulfate(FeSO₄·7H₂O), Tri sodium Citrate (Na₃C₆H₅O₇·2H₂O) were purchased from Sinopharm Chemical Reagent Co., Ltd., China and used without any further purification. Deionized water and absolute ethanol were used for all experiments.

Synthesis of Ni₃[Fe(CN)₆]₂ nanocubes

1.2 mmol of Nickel Acetate and 1.6 mmol of Tri sodium Citrate was dissolved in 40 ml DI water marked solution A. 0.8 mmol of Potassium Ferricyanide was dissolved in 40 ml DI water marked

Characterization analysis

At ambient temperature, Ni₃[Fe(CN)₆]₂ nanocube was prepared at first, as bases for preparation of Ni₃[Fe(CN)₆]₂@Fe₄[Fe(CN)₆]₃. As SF1 shown, the X-ray diffraction (XRD) pattern of obtained NPB sample was matched well with that of Ni₃[Fe(CN)₆]₂ (PDF#46-0906). It was an obvious characteristic that the three strongest peaks of NPB at 2θ = 24.92°, 17.55° and 35.60° were the same position and the same intensity order as the peaks of PDF card. The XRD pattern peaks of NPB@PB1 at 2θ = 24.92° was the

Conclusion

In summary, based on a simple anodic ion exchange process and Prussian blue analogues, a series of the precursors named Ni₃[Fe(CN)₆]₂@Fe₄[Fe(CN)₆]₃ nanocubes were successfully built in a large number with core-shelled structure and certain size. And then, the corresponding metal oxides were obtained with core-shelled structure after calcinated, and were prepared as cathode material for lithium ion half-cell to investigate its electrochemical performance. The sample marked NFO@FO3-600 exhibits

CRediT authorship contribution statement

Zhao Xue: Writing - review & editing. Wei Yang: Writing - review & editing.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgement

This research is funded by the National Natural Science Foundation of China (21776051), the Natural Science Foundation of Guangdong (2018A030313423), and the Science and Technology Project of Guangzhou (201802020029).

References (57)

A. Eftekhari
Low voltage anode materials for lithium-ion batteries
Energy Storage Mater.
(2017)
A. Mishra et al.
Electrode materials for lithium-ion batteries
Mater. Sci. Energy Technol.
(2018)
L.Z. Song et al.
Metal–organic framework-assisted synthesis of compact Fe₂O₃ nanotubes in Co₃O₄ host with enhanced lithium storage properties
Nano-Micro Lett.
(2018)
J. Tian et al.
Bio-template synthesized NiO/C hollow microspheres with enhanced Li-ion battery electrochemical performance
Electrochim. Acta
(2018)
Z. Wang et al.
Fe₂O₃@C core@shell nanotubes: porous Fe₂O₃ nanotubes derived from MIL-88A as cores and carbon as shells for high power lithium ion batteries
J. Alloys Compd.
(2018)
W. Shi et al.
Three-dimensional graphene sheets with NiO nanobelt outgrowths for enhanced capacity and long term high rate cycling Li-ion battery anode material
J. Power Sources
(2018)
W. Lu et al.
Core-shell materials for advanced batteries
Chem. Eng. J.
(2019)
K.A. Lin et al.
Prussian blue analogue derived magnetic carbon/cobalt/iron nanocomposite as an efficient and recyclable catalyst for activation of peroxymonosulfate
Chemosphere
(2017)
J.Q. Li et al.
FeMnO₃ porous nanocubes/Mn₂O₃ nanotubes hybrids derived from Mn₃[Fe(CN)₆]₂ · nH₂O Prussian Blue Analogues as an anode material for lithium-ion batteries
J. Alloys Compd.
(2018)
F. Zhang et al.
Synthesis of Sn-MnO@nitrogen-doped carbon yolk-shelled three-dimensional interconnected networks as a high-performance anode material for lithium-ion batteries
Chem. Eng. J.
(2019)

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A simple method to fabricate NiFe2O4/NiO@Fe2O3 core-shelled nanocubes based on Prussian blue analogues for lithium ion battery

Highlights

Abstract

Introduction

Section snippets

Chemicals

Synthesis of Ni3[Fe(CN)6]2 nanocubes

Characterization analysis

Conclusion

CRediT authorship contribution statement

Declaration of competing interest

Acknowledgement

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A simple method to fabricate NiFe₂O₄/NiO@Fe₂O₃ core-shelled nanocubes based on Prussian blue analogues for lithium ion battery

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