Enhanced rate performance of nanoporous nickel-antimony anode for sodium ion batteries
Graphical abstract
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).
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