A scalable formation of nano-SnO₂ anode derived from tin metal–organic frameworks for lithium-ion battery

Abstract

In this work, for the first time, we synthesize a SnO 2 nanomaterial through the calcination of tin metal-organic framework (MOF) precursors. X-ray diffraction, field emission scanning electron microscope, transmission electron microscopy, and the Brunauer-Emmett-Teller specific surface area are used to characterize the phases and to observe surface morphologies. This anode material exhibits good electrochemical performance in LIBs with high reversible capacity and cycling stability. The good electrochemical properties could be ascribed to the short transport/diffusion path of electrons and lithium ions and the high contact area between the electrode and electrolyte that results from the nanostructured SnO 2 . This is low-cost, 3 templates to synthesize nanoparticles and high specific surface area materials. There have also been many reports of the synthesis of metal oxide nanoparticles by direct calcination of MOFs, which exhibit excellent electrochemical performance. [19][20][21] 23 Nevertheless, to the best of our knowledge, there has been no report on synthesis of SnO 2 nanoparticles with homogeneous morphology using MOFs as template. Herein we report a simple, scalable and low-cost synthesis of SnO 2 nanoparticles via the conversion of the Sn-MOF. When evaluated as an anode material for LIB, the as-prepared SnO 2 nanoparticles exhibit good electrochemical performance of a high reversible capacity and excellent stability of up to 100 charge/discharge cycles. Experimental details2.1 Reagents and Chemicals. Tin (II) sulfate (SnSO 4 ) and p-Phthalic acid (C 8 H 6 O 4 ) were purchased from Sinopharm Chemical Reagent Co. Ltd. Sodium hydroxide (NaOH, AR) was purchased from Aladdin Chemistry Co. Ltd. All chemicals were used as received without further purification. Synthesis of Sn-MOF.In a typical procedure, 0.012 mol C 8 H 6 O 4 and 0.024 mol NaOH were dissolved in a 300 ml deionized water under stirring. After that, 60 mL of a 0.25 M SnSO 4 aqueous solution was simultaneously added dropwise into the above solution under constant stirring. The mixture was stirred for 5 h at room temperature until MOF precipitation was formed. The product was collected and washed with ethanol and deionized water for several times. At last, the white powder of Sn-MOF was dried in vacuum at 50 ℃. SnO 2 nanoparticles synthesis.The Sn-MOF was thermally treated at 400 ℃ for 2 h under air atmosphere with a ramping rate of 5 ℃ min -1 and then naturally cooled down to room temperature. Finally, the product was taken out and it was found that the color of the material changed from white to gray. 7 formation of a SEI film, which disappeared under the subsequent cycles, 30 and finally the alloying reaction between Sn and Li + , respectively. In the case of the first anodic process, two broader anodic peaks at 0.48 and 0.60 V corresponded to the extraction of lithium ion from Li-Sn alloys. Note that another oxidation peak at 1.25 V was also observed, which was most likely due to the partially reversible reaction of SnO 2 to Sn and Li 2 O. 31 C...

Hollow Multi‐Shelled Structure with Metal–Organic‐Framework‐Derived Coatings for Enhanced Lithium Storage

“…Forthe first cycle,the obtained higher specific discharge capacities of TS-SnO 2 -HoMSs,T S-SnO 2 @FeO x -C(MOF) and TS-SnO 2 @Fe 2 O 3 (MOF) were 1304, 1700, and 1908 mAh g À1 , respectively.T he higher experimental capacity than theoretical capacity and the lower coulombic efficiencies (60.2 %, 61.6 %and 62.1 %, respectively) in the first few cycles can be ascribed to decomposition of electrolyte and formation of the SEI film. As shown in Figure 3c,the TS-SnO 2 -HoMSs exhibit higher capacity and better cycling performance than SnO 2 electrodes with other morphologies which have been reported under similar test conditions, [23] this is because HoMS can buffer the volume expansion caused by Sn alloying with Li ( Figure S16). However,i nt he pure TS-SnO 2 electrodes,t he electrochemical reaction of Li with SnO 2 is an irreversible process accompanied by the volume expansion.…”

Rambutan‐like hollow carbon spheres decorated with vacancy‐rich nickel oxide for energy conversion and storage

“…With the ever‐increasing energy demand and prominent environmental concerns, seeking promising storage, and conversion systems with high efficiency, low cost, robust stability, and environmental friendliness is urgent but challenging . Lithium‐ion batteries (LIBs) and water electrolyzer, deemed to be attractive electrochemical storage and conversion devices, have been extensively studied because they are efficient, stable, and environmentally friendly .…”

Application of MOF-derived transition metal oxides and composites as anodes for lithium-ion batteries

“…Transition metal oxides (TMOs) are a category of anode material candidates for LIBs owing to their larger theoretical capacity than that of the commercial graphite anode. By using 1,4-benzenedicarboxylic acid (H 2 BDC) as an organic ligand, many MOF-derived TMOs, such as NiO, 18 SnO 2 , 19 TiO 2 , 20,21 and Fe 2 O 3 , 22,23 have been brought forward as promising anodes with high capacity and better cycling performance. Among various MOF-derived TMOs, Co 3 O 4 is one of the most potential p-type semiconductor materials because of its high theoretical capacity (890 mA h g −1 ), environmentally friendly nature and low cost.…”