Metal–Organic Framework Derived Ultrafine Sb@Porous Carbon Octahedron via In Situ Substitution for High-Performance Sodium-Ion Batteries

Abstract

Alloying-type anode materials are regarded as promising alternatives beyond intercalation-type carbonaceous materials for sodium storage owing to the high specific capacities. The rapid capacity decay arising from the huge volume change during Na+-ion insertion/extraction, however, impedes the practical application. Herein, we report an ultrafine antimony embedded in a porous carbon nanocomposite (Sb@PC) synthesized via facile in situ substitution of the Cu nanoparticles in a metal–organic framework (MOF)-derived octahedron carbon framework for sodium storage. The Sb@PC composite displays an appropriate redox potential (0.5–0.8 V vs Na/Na+) and excellent specific capacities of 634.6, 474.5, and 451.9 mAh g–1 at 0.1, 0.2, and 0.5 A g–1 after 200, 500, and 250 cycles, respectively. Such superior sodium storage performance is primarily ascribed to the MOF-derived three-dimensional porous carbon framework and ultrafine Sb nanoparticles, which not only provides a penetrating network for rapid transfer of charge carriers but also alleviates the agglomeration and volume expansion of Sb during cycling. Ex situ X-ray diffraction and in situ Raman analysis clearly reveal a five-stage reaction mechanism during sodiation and desodiation and demonstrate the excellent reversibility of Sb@PC for sodium storage. Furthermore, post-mortem analysis reveals that the robust structural integrity of Sb@PC can withstand continuous Na+-ion insertion/extraction. This work may provide insight into the effective design of high-capacity alloying-type anode materials for advanced secondary batteries.

Engineering Nanostructured Antimony-Based Anode Materials for Sodium Ion Batteries

“…Similar work involving of electrospun Sb/C as an SIBs anode was accomplished by Cao et al almost at the same time [46]. Afterwards, a variety of 1D Sb/C composite anodes have been established including Sb/CNT composite [38], peapod-like Sb@C [47], Sb@C coaxial nanotubes (Figure 2f) [48], N-doped carbon nanonecklaces with encapsulated Sb [49] and 1D yolk-shell Sb@Ti-O-P nanostructures [50]. Impressively, the full battery of Sb@Ti-O-P//Na 3 V 2 (PO 4 ) 3 -C presents a high output voltage (~2.7 V) and a capacity of 392 mAh g −1 after 150 cycles at 1 A g −1 .…”

“…In this way, the accurate structural information on the core-particle size, the void space and the complex structure can be systemically established (Figure 3b-e). Recently, metal-organic-framework (MOF) derived carbon has shown great capability to realize precise carbon-confined nanostructures with diverse compositions and delicate morphologies [38,39]. For example, Li et al reported an ultrafine Sb embedded in a porous carbon nanocomposite (Sb@PC) synthesized via a facile in situ substitution of the Cu nanoparticles in an MOF-derived octahedron carbon framework for sodium storage (Figure 3f).…”

“…From the molecular level, compared to pure Sb anode, chalcogenides contain an S or Se atom, which sometimes act as chemical bonding sites to fabricate high-performance Sb 2 S 3 or Sb 2 Se 3 anode. The strong chemical bonding of nanostructured Sb 2 S 3 on heteroatom-doped graphene or carbon matrix have been disclosed by electrochemical analysis as well as computational calculations [38,163]. It has been found that heteroatoms-doped graphene or carbon usually accounts for the improvement of electronic and ionic conductivity [164,165] or improve the adsorption of Sb 2 S 3 on the matrix [166,167].…”

Metal–organic framework-derived nitrogen-doped carbon-confined CoSe2 anchored on multiwalled carbon nanotube networks as an anode for high-rate sodium-ion batteries

“…44 Huang et al fabricated an ultrafine Sb@PC octahedron through an in situ substitution using Cu(btc) 3 MOF as the templates. 2 When evaluated as the electrode for SIBs, the composite delivers a high reversible capacity of 634.6 mA h g −1 under a current density of 100 mA g −1 and prominent rate capability (298.2 mA h g −1 at 2.0 A g −1 ). Li et al reported CoSe 2 /N-doped carbon box from the sacrificial ZIF-67 templates, which shows excellent cycling performance (390.2 mA h g −1 at a current density of 5 A g −1 for 4000 cycles).…”

“…In view of the limited lithium resources, uneven global distribution, and high manufacturing cost, lithium-ion batteries (LIBs) cannot meet the increasing demand for large-grid and renewable energy markets. [1][2][3][4] This compels scientists to explore alternative metal-ion batteries. In the past decade, sodium-ion batteries (SIBs) have been deemed as highly potential substitutes by virtue of their inexpensiveness and rich Na resources.…”