Elsevier

Electrochimica Acta

Volume 399, 10 December 2021, 139429
Electrochimica Acta

Enhanced rate performance of nanoporous nickel-antimony anode for sodium ion batteries

https://doi.org/10.1016/j.electacta.2021.139429Get rights and content

Highlights

  • Nanoporous NiSb (np-NiSb) alloy was fabricated by a facile dealloying strategy.

  • The np-NiSb anode exhibits good cycling stability and superior rate capability.

  • Operando XRD reveals the sodiation/desodiation mechanism of the np-NiSb anode.

  • On-line DEMS verifies the gas release of half cells with NiSb anode during cycling.

Abstract

Engineering Sb-based anode materials is the key to enhance their electrochemical performance for sodium ion batteries (SIBs) by solving the issues of the rapid capacity decay and poor rate capability. In this work, a nanoporous NiSb alloy (np-NiSb) with a three-dimensionally interconnected ligament-channel structure was synthesized by a facile dealloying strategy. As an anode for SIBs, the np-NiSb alloy exhibits excellent cycling performance, rate capability and stability with a reversible capacity of 334.6 mAh g  1 at 0.2 A g  1 after 100 cycles, 155.6 mAh g  1 at 20 A g  1 and a capacity retention rate of 97% after 100 cycles at 1 A g  1. The nanoporous structure and the introduction of inactive Ni effectively tolerate the dramatic volume changes during the charge/discharge processes, restraining the pulverization of np-NiSb. The unique ligament-channel network structure with an average size of about 30 nm significantly shortens the ion transmission distance, ensuring the fast charge transfer at high rates. Operando X-ray diffraction reveals the sodiation/desodiation mechanism of the np-NiSb anode during the discharge/charge processes. In addition, on-line differential electrochemical mass spectrometry further explores the reaction mechanism of np-NiSb. This work highlights constructing nanoporous Sb-based alloys as an effective strategy to improve the performance of SIBs.

Graphical abstract

Image, graphical abstract
  1. Download : Download high-res image (220KB)
  2. Download : Download full-size image
As an anode for SIBs, the np-NiSb alloy with bicontinuous ligament-channel structure exhibits good cycling stability with capacity retention rate of 97% over 100 cycles at 1 A g  1 (279.7 mAh g  1).

Introduction

In large-scale energy storage systems, sodium ion batteries (SIBs) have emerged as one of the most promising alternatives to lithium ion batteries (LIBs) owing to the advantages of low cost, non-toxicity and natural abundant resource [1]. However, Na ions have a lager radius (1.02 Å) than that of Li ions, which results in slow reaction kinetics as well as huge volume changes during the sodiation/desodiation processes. Commercial graphite, which is widely used in LIBs, has shown limited sodium storage capacity owing to its narrow interlayer spacing. Therefore, the key of practical application of SIBs is the development of suitable anode materials with high specific capacity and good cycle stability. According to previous work, carbonaceous materials, metal oxides, chalcogenides, intercalation-based and alloy-based materials have been investigated extensively as anode materials for SIBs [2], [3], [4], [5], [6]. In addition, alloy-type anodes, such as Sn, Sb, Bi, Pb, have gained considerable attention as anode materials for SIBs, owing to their high gravimetric (volumetric) specific capacities and suitable sodiation potentials. Among them, Sb with a high specific capacity (660 mAh g  1) and appropriate operational potential (0.5 - 0.6 V (vs. Na+/Na)) was proposed as a promising candidate for anode materials in SIBs [7], [8], [9], [10], [11], [12]. Unfortunately, the rapid capacity decay caused by the large volume expansion and continuous phase transition behavior severely hinders the practical application of Sb anodes [13].

A promising approach of addressing this issue of volume changes is to design M-Sb based alloys and intermetallic phases where M is an active (Sn, Zn, Bi) or inactive (Mo, Fe, Cu, Co, Ni) materials [14], [15], [16], [17]. The M metal generated by the M-Sb alloy in the first cycle can act as a buffer matrix to accommodate the volume change, thereby improving the structural stability and cycle performance. Meanwhile, the M-Sb based materials with unique structures, such as nanoporous, hollow nanoarchitectures and nanoarrays, represent many inbuilt advantages. Such materials can effectively improve the ability to tolerate the volume change, shorten the ion transport distance and enhance the reaction kinetics. For example, NiSb intermetallic hollow nanospheres have been prepared by a low-temperature strategy, which displayed a capacity as high as 500 mAh g  1 after 70 cycles [18]. Hollow NiSb alloy confined in carbon matrix as the anode for SIBs exhibited a reversible capacity of 345 mAh g  1 after 400 cycles [19]. Despite the great progress in the design of anode materials for SIBs, high costs, complicated methods and the inability to mass production, still hinder the practical application of alloy-type anodes for SIBs. Therefore, it is crucial to fabricate the rational structure of alloy-type anodes via a feasible and inexpensive strategy.

Herein, based on a facile dealloying strategy, an Mg-Ni-Sb alloy was used as a precursor to fabricate a nanoporous NiSb (np-NiSb) alloy with nano-scale ligaments (about 30 nm) as a high-performance anode for SIBs. The nanoporous structure significantly alleviates the volume changes during the alloying/dealloying processes and shortens the electric and ionic transport pathways. Meanwhile, the component of Ni could serve as a buffer matrix and greatly improve the electrical conductivity. Moreover, operando X-ray diffraction (XRD) and on-line differential electrochemical mass spectrometry (DEMS) further revealed the reaction mechanisms of np-NiSb during the discharge/charge processes.

Section snippets

Material preparation

The np-NiSb alloy was prepared with a one-step dealloying method using an Mg90Ni5Sb5 (nominal composition, at.%) alloy as the precursor. Typically, pure metals (Mg, Sb, Ni block, purity: 99.9 wt.%) were melted in an electric resistance furnace with the protection of covering agent. The melting temperature was set to 750 °C to ensure the formation of a uniform precursor alloy. Afterward, the Mg90Ni5Sb5 ingots were remelted and sprayed on a high-speed rotating copper roller (1000 rpm) to obtain

Results and discussion

As shown in Fig. S1, the diffraction peaks of the rapidly solidified Mg90Ni5Sb5 ribbons indicate three phases which are consistent with the Mg phase (JCPDS # 65–3365), Mg6Ni phase (JCPDS # 51–1179) and Mg3Sb2 phase (JCPDS # 65–3458). The EDX results indicate that the proportion of Mg-Ni-Sb in the master alloy is close to the designed composition (Fig. S2). In the early stage of dealloying, the Mg phase was selectively dissolved to form Mg2+. As the dealloying proceeded, Mg atoms in the Mg3Sb2

Conclusions

In summary, a single-phase np-NiSb alloy with bicontinuous ligament-channel structure was fabricated via a facile dealloying strategy. As an anode for SIBs, the np-NiSb alloy exhibits good cycling stability with capacity retention rate of 97% over 100 cycles at 1 A g  1 (279.7 mAh g  1) and excellent rate performance (155.6 mAh g  1 at 20 A g  1). Based upon the results of various electrochemical techniques (CV, EIS and GITT), the np-NiSb alloy presents outstanding Na+ diffusion and

CRediT authorship contribution statement

Wensheng Ma: Investigation, Data curation, Formal analysis, Writing – original draft. Zhiyuan Guo: Validation. Yanzhao Xu: Resources. Qingguo Bai: Formal analysis, Validation. Hui Gao: Formal analysis. Weimin Wang: Supervision. Wanfeng Yang: Writing – review & editing, Project administration. Zhonghua Zhang: Conceptualization, Writing – review & editing, Funding acquisition.

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.

Acknowledgments

The authors gratefully acknowledge financial support by National Natural Science Foundation of China (51871133), Taishan Scholar Foundation of Shandong Province, and the program of Jinan Science and Technology Bureau (2019GXRC001).

References (51)

  • J.C. Kim et al.

    Synthesis of multiphase SnSb nanoparticles-on-SnO2/Sn/C nanofibers for use in Li and Na ion battery electrodes

    Electrochem. Commun.

    (2014)
  • Z. Wang et al.

    Constructing N-Doped porous carbon confined FeSb alloy nanocomposite with Fe-N-C coordination as a universal anode for advanced Na/K-ion batteries

    Chem. Eng. J.

    (2020)
  • W. Li et al.

    Carbon-coated Mo3Sb7 composite as anode material for sodium ion batteries with long cycle life

    J. Power Source.

    (2016)
  • Y.D. Cho et al.

    The effect of carbon coating thickness on the capacity of LiFePO4/C composite cathodes

    J. Power Source.

    (2009)
  • Z. Jusys et al.

    A novel DEMS approach for studying gas evolution at battery-type electrode|electrolyte interfaces: high-voltage LiNi0.5Mn1.5O4 cathode in ethylene and dimethyl carbonate electrolytes

    Electrochim. Acta

    (2019)
  • N. Yabuuchi et al.

    Research development on sodium-ion batteries

    Chem. Rev.

    (2014)
  • L. Li et al.

    Recent progress on sodium ion batteries: potential high-performance anodes

    Energy Environ. Sci.

    (2018)
  • H. Kim et al.

    Recent progress in electrode materials for sodium-ion batteries

    Adv. Energy Mater.

    (2016)
  • J. Ni et al.

    Superior sodium storage in Na2Ti3O7 nanotube arrays through surface engineering

    Adv. Energy Mater.

    (2016)
  • M. Fan et al.

    Synergistic effect of nitrogen and sulfur dual-doping endows TiO2 with exceptional sodium storage performance

    Adv. Energy Mater.

    (2020)
  • H. Tan et al.

    Peering into alloy anodes for sodium-ion batteries: current trends, challenges, and opportunities

    Adv. Funct. Mater.

    (2019)
  • X. Li et al.

    Template-free construction of self-supported Sb prisms with stable sodium storage

    Adv. Energy Mater.

    (2019)
  • J. Ni et al.

    Durian-inspired design of bismuth-antimony alloy arrays for robust sodium storage

    ACS Nano

    (2020)
  • S. Sarkar et al.

    An overview on Sb-based intermetallics and alloys for sodium-ion batteries: trends, challenges and future prospects from material synthesis to battery performance

    J. Mater. Chem. A

    (2021)
  • W. Luo et al.

    Antimony-based intermetallic compounds for lithium-ion and sodium-ion batteries: synthesis, construction and application

    Rare Met.

    (2017)
  • Cited by (0)

    View full text