Sn Nanoparticles Encapsulated in 3D Nanoporous Carbon Derived

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Sn nanoparticles encapsulated in 3D nanoporous carbon derived from a metal-organic framework for anode material in lithium-ion batteries Yuanyuan Guo, Xiaoqiao Zeng, Yu Zhang, Zhengfei Dai, Haosen Fan, Ying Huang, Weina Zhang, Hua Zhang, Jun Lu, Fengwei Huo, and Qingyu Yan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • Publication Date (Web): 04 May 2017 Downloaded from http://pubs.acs.org on May 5, 2017

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ACS Applied Materials & Interfaces

Sn nanoparticles encapsulated in 3D nanoporous carbon derived from a metal-organic framework for anode material in lithium-ion batteries Yuanyuan Guo2,3, Xiaoqiao Zeng3, Yu Zhang2, Zhengfei Dai2, Haosen Fan2, Ying Huang2, Weina Zhang1, Hua Zhang2, Jun Lu*3, Fengwei Huo*1 and Qingyu Yan*2

1 Key Laboratory of Flexible Electronics (KLOFE) & Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), 30 South Puzhu Road, Nanjing 211816, P.R. China 2 School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore 3 Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA

Abstract: Three-dimensional nanoporous carbon frameworks encapsulated Sn nanoparticles (Sn@3D-NPC) are developed by a facile method as an improved lithium ion battery anode. The Sn@3D-NPC delivers a reversible capacity of 740 mAh g-1 after 200 cycles at a current density of 200 mA g-1, corresponding to a capacity retention of 85% (against the 2nd capacity) and high rate capability (300 mAh g-1 at 5 A g-1). Compared to the Sn nanoparticles (SnNPs), such improvements are attributed to the 3D porous and conductive framework. The whole structure can not only provide the high electrical conductivity which facilities the electron transfer but also the elasticity which will suppress the volume expansion and aggregation of Sn nanoparticles during the charge and discharge process. This work opens up a new application of MOFs in energy storage.

Keywords: Sn, Carbon framework, Metal-organic framework, Anode, Li-ion battery

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Lithium ion batteries (LIBs) have been widely applied in portable electronic devices and shown great promise in hybrid electric vehicles, electric vehicles and power grids.[1,2] However, for high energy density and high power applications, high capacity anode materials are highly desired as the current graphite electrode delivers relatively low capacity (372 mA h g-1 for LiC6).[3,4] Alternative anode materials such as Si, Ge and Sn have been widely developed to boost battery capacity and power.[5-7] For instance, a Sn anode has a high theoretical capacity of 993 mA h g-1 for Li4.4Sn, almost 3 times higher than that of commercialized graphite. With good electrical conductivity and low Li+ intercalation voltage, Sn has been extensively explored as a promising alternative anode material for high power LIBs.[8,9] However, huge volume change (about 300%) of Sn electrode causes quick capacity fading upon Li ions intercalation and extraction,[10-12] which results in severe electrode pulverization.[8,9,13] To solve these issues, various strategies have been reported on the structural designing and volume change suppressing including designing the suitable nanostructure, adding the buffer and conductive materials.[5-7,

14, 15]

Among them, fabricating nano-Sn@carbon

composites by rational design is believed to be one of the most effective approaches.[16-18] In particular, the 3D-Sn@carbon composites have been demonstrated enhancement in the electrochemical performance. The embedded void space can accommodate the volume change, suppress the aggregation of Sn nanoparticles and allow lithium ions to easily penetrate into the composite.[19-24] Various kinds of Sn@carbon composites have been developed. For instance, graphene has been utilized to anchor Sn nanoparticles (including directly decoration Sn onto graphene, and sandwich like graphene anchored with Sn nanoparticles) and improved electrochemical performance has been reported.[25] However, the graphene nanosheets are very prone to irreversible aggregation or restacking due to the strong van der Waals forces among them.[26] Another way is to deposit Sn onto carbon nanotubes to accommodate the volume change during lithiation because carbon nanotubes possess good electrical conductivity and is mechanical robust.[27] However, Sn may detach from the carbon nanotubes because of the weak physical adsorption between them.[28] Fabricating a special carbon architecture instead of using a regular carbon matrix to host the Sn nanoparticles is still a big challenge. One possible strategy to address the challenges mentioned above is to build a three dimensional (3D) carbon framework with high mechanical stability and enough inner-pores to host the Sn nanoparticles.


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Metal-organic frameworks (MOFs) have been considered as a new carbon sources for the carbon architecture design. With both inorganic and organic components, the skeleton builds up various architectures (cubic, rod, octahedral and plate) with high specific surface area and large pore volume.[29-32] Porous MOFs have been used as an easily adjustable template to synthesize 3D nanoporous carbon frameworks, which have nanoscaled cavities for the small particles to be anchored.[33-41] In this communication, we introduce a novel Sn@3D nanoporous carbon hybrid (denoted as Sn@3D-NPC). This hybrid is firstly synthesized by directly annealing MOFs to get 3D nanoporous carbon frameworks (3D-NPC), followed by the process of Sn4+ to Sn nanoparticles reduction within the matrix. In this unique 3D composite architecture, Sn nanoparticles are defined in the pores or cavities of porous carbon framework. The isolated units will provide interspaces between Sn nanoparticles to suppress the volume variation and aggregation. Meanwhile, the electrode showed enhanced conductivity and mechanical integrity due to 3D interconnected carbon networks structure. Therefore, the assembled cells exhibit improved electrochemical properties compared to those with densely structured nano-Sn anode. By using such Sn@3D-NPC anode, the corresponding half-cell is able to deliver a good reversible capacity of 740 mAh g-1 after 200 cycles at a current density of 200 mA g-1, corresponding to an improved capacity retention of 85% and a high rate capability of 300 mAh g-1 at 5 A g-1. The preparation process of Sn@3D-NPC composite was illustrated in Scheme 1. In brief, the process mainly involved two steps. Firstly, the as-prepared ZIF-67 with dodecahedral structure was carbonized in argon gas to obtain the carbon framework, inside which the reduced metallic Co was embedded. Then the framework was treated with hydrochloric acid to remove the metallic Co. The as-obtained carbon frameworks reserved the pristine structure of ZIF-67 with micro-, meso- and macropores.[42,43] After treatment, the porous carbon frameworks were immersed into the SnCl4 · 5H2O methanol solution and sonicated for 3 h. By dropping NaBH4 methanol solution quickly into the above solution, the Sn4+ ions was reduced into Sn nanoparticles and uniformly dispersed into the carbon networks, and the Sn@3D-NPC composite was formed.[44,45] The Sn nanoparticles (Sn NPs) for control study were synthesized in the same way without involving the porous carbon.



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The morphology of the original ZIF-67 was characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM) as shown in Figure 1a and 1d. All ZIF-67 crystals are uniform polyhedral structure with smooth surface. The particle size is around 600 nm on average. The XRD peaks of the synthesized ZIF-67 match well with the simulated results (Figure S1a, Supporting Information). After annealing and metallic cobalt removal, the homogenous dodecahedral structures are retained although the surface became rough (Figure 1b and 1e). Weak XRD diffraction peaks of 3D-NPC are attributed to the cobalt residuals in the frameworks (Figure S1b, Supporting Information). After the Sn4+ reduction reaction, the product of Sn@3D-NPC exhibits the similar morphology of pure carbon framework with Sn nanoparticles (within 20 nm) closely anchored within the pores (Figure 1c and f). The lattice distances of 0.28 and 0.34 nm as shown in Figure 1g correspond to the (101) plane of the Sn crystal (JCPDS No. 65-0296) and the interplane spacing of the graphitic carbon from the annealing of ZIF-67, respectively. Figure 2a shows the x-ray diffraction (XRD) pattern of the sample, the peaks at 30.65º, 32.04º, 43.90º and 44.93º can be indexed to the (200), (101), (220) and (211) planes of crystalline Sn (JCPDS No. 65-0296), and the broad peak at 25° belongs to the carbon.[46,47] The elemental mapping in Figure 1h further confirms the uniform distribution of Sn over the whole carbon frameworks. The carbon frameworks contain both graphitic and disordered carbon as observed in the Raman Spectra (Figure 2b) with IG/ID ~1.[48] The amount of induced Sn is estimated by thermogravimetric analysis (TGA) (Figure 2c). The Sn weight ratio in Sn@3DNPC composite is determined to be approximately 31% (Supporting Information, last paragraph).[19] The pore size distribution and the specific surface area of carbon frameworks with/without Sn loading were determined by the nitrogen sorption experiments with a Brunauer–Emmett–Teller (BET) analyzer (Figure 2d, e). The adsorption-desorption isotherms of the two samples correspond to a typical type-IV isotherm with a hysteresis loop in the P/P0 range of 0.45-0.98, indicating both Sn@3D-NPC and 3D-NPC are mainly mesoporous structure. The BET specific surface area changes from 547 m2 g−1 to 134 m2 g−1 after inducing Sn into 3D-NPC, and the corresponding BJH average pore diameter switches from 4.2 to 13.4 nm. The pore volume is


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reduced from 0.36 m3 g−1 in 3D-NPC to 0.11 m3 g−1 in Sn@3D-NPC due to the incorporation of Sn. The Li storage properties of the samples were measured in coin-type half cells with Li metal as counter-electrode. The typical cyclic voltammograms (CVs) of Sn@3D-NPC, 3D-NPC and Sn NPs electrodes were scanned from 0 to 3V at a rate of 0.1 mV s-1 and are concluded in Figure 3a-c. During the initial 5 cycles, the 3D-NPC anodes show a smooth current response (Figure 3b). There is no obvious peak observed after the first cycle, revealing that the current peaks occurring in Sn@3D-NPC sample (Figure 3a) are mainly attributed to the lithiation (alloying) and delithiation (de-alloying) of Sn: the three reduction peaks at 0.2, 0.33 and 0.62 V during the first catholic sweep are assigned to the alloying reaction between Sn and lithium forming LixSn as well as the formation of solid-electrolyte interface (SEI) layers;[22,23,49] the corresponding oxidation peaks at 0.51, 0.61 and 0.73 V during the anodic sweep are attributed to the LixSn dealloying reactions;[22,23,49] the broad oxidation peak at 1.2 V corresponds to the lithium extraction from carbon.[21,49] The difference between the first and second scan is mainly because of the gradual SEI layer formation.[49] Specially, compared to SnNPs (Figure 3c), the initial five overlapped anodic scans of Sn@3D-NPC (Figure 3a) indicates the enhanced cycling stability. Also, the stronger peak intensities of Sn@3D-NPC indicate the extended reversible electrochemical reactions. The galvanostatic charge-discharge profiles of the samples were measured at a constant current density of 200 mA g-1 from 0.001 to 3 V. For both Sn@3D-NPC and Sn NPs electrodes, the voltage plateaus occur at the similar voltage range (Figure 3d and f). During the initial discharge, the plateaus of both Sn@3D-NPC and Sn NPs between 0.2 to 0.7 V are assigned to the formation of LixSn alloys. Consistently, the initial charge plateaus between 0.2 and 0.8 V correspond to the de-alloying reactions, which is in agreement with the CV results. Since a smooth discharge-charge curve is observed for the 3D-NPC electrode (Figure 3e), the observed plateaus in Sn based electrode can be indicative of typical voltage characteristics of the Sn electrode. The Sn@3D-NPC electrode is able to deliver the first discharge and charge capacities of 1440 mA h g-1 and 818 mA h g-1, respectively, which are much higher than 3D-NPC and SnNPs based electrodes. During the third cycle, the Sn@3D-NPC electrode exhibits a higher reversible capacity of 818 mA h g-1 with a Coulombic efficiency of 94%. In contrast, the



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capacity of Sn NPs electrode rapidly drops to 631 mA h g-1 with a lower Coulombic efficiency of 89% during the third cycle. Compared to the Sn@3D-NPC and Sn electrodes, the 3D-NPC electrode shows lower reversible capacity during the first three cycles (Table S1, Supporting Information). More importantly, the Sn@3D-NPC composite exhibits enhanced cycling performance than 3D-NPC and SnNPs (Figure 3g). In detail, the composite displays significant improvement on cycling retention than SnNPs and higher reversible capacity than the 3D-NPC. The discharge capacities of Sn@3D-NPC in 2th and 200th cycles are 870 and 741 mAh g-1 respectively with the capacity retention of 85%, while SnNPs only delivers capacities of 767 and 103 mAh g-1 for the 2th and 200th cycles with the capacity retention of 13%. The Sn@3D-NPC based cell exhibits high Coulombic efficiency between 97%-99% after 10 cycles, showing excellent reversible cycling. The enhanced cycling performance is ascribed to the unique structure of Sn@3D-NPC. The 3D architecture can reduce the aggregation of Sn nanoparticles and help Sn stay at an ultrasmall level to suppress the volume changes during charge/discharge. Also, the graphitic carbon matrix can act as a bi-functional content to buffer the stress and improve the electric conductivity of the system.[19,21] In addition, Sn@3D-NPC electrode presents better rate capability of the composite electrode at various current densities of 0.1, 0.2, 0.5, 1, 2 and 5 A g-1 compared to 3D-NPC and SnNPs ones (Figure 3h). The capacity fade of Sn@3D-NPC electrode is relatively slow, varying from 844 to 749, 641, 562, 462, and 302 mAh g-1 at each discharge current. Even at the high current of 5 A g-1, the capacity can still be retained 300 mAh g-1. Once the discharge current goes back to 0.1 A g-1, a reversible capacity of 760 mAh g-1 can be reversed with the best capacity retention among the three type electrodes. In detail, the reversible capacities for 3D-NPC electrode are 581, 489, 373, 280, 203, 112 mAh g-1, and for SnNPs electrode are 535, 321, 138, 69, 25, 7 mAh g-1 at each discharge current. After 200 cycles, the Sn@3D-NPC structure is found sustained well under SEM and EDS (Figure S2, Supporting Information), further evidencing the promising stability for long cycle running. Obviously, the Sn@3D-NPC composite can sustain itself behaving better at various working current conditions due to its higher capacity and recovery capability. The electrochemical impedance spectroscopy (EIS) was performed to study the ion diffusion in the electrodes (Figure 3i). The data were collected after the 5 cycles (after the formation of


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SEI film). The spectra features with depressed semicircle located from medium to high frequency and linear trail at low frequency are consistent with the typical Sn electrode.[50] Apparently, Sn@3D-NPC electrode shows the smallest impedance in the three electrodes, indicating its lowest contact and charge migration resistance, which are also responsible for better electrode performance. In this study, Sn@3D-NPC composite was constructed by doping small Sn nanoparticles simultaneously into the unique 3D porous carbon network which was derived from ZIF-67. Such architecture shows desired structural features: a) The porous carbon frameworks provide sufficient void space, buffering the volume changes of Sn nanoparticles during the chargedischarge; b) The carbon networks prevent the aggregation of Sn nanoparticles during the prolonged cycling; c) The inside channels in the porous structure facilitate the transport of lithium ion in the Sn@3D-NPC based anode. As a result, Sn@3D-NPC shows high reversible capacity of 740 mAh g-1 after 200 cycles at a current density of 200 mA g-1 and excellent rate performance (300 mAh g-1 at 5 A g-1) when applied as anodes of LIBs. Sn@3D-NPC architecture was demonstrated to have the promising potential for the development of high performance lithium ion batteries. Experimental Procedures Synthesis of ZIF-67: All the chemicals were used after purchase without further purification. In a typical synthesis, 1.455 g of Co(NO3)2·6H2O and 1.642 g of 2-methylimidazole were dissolved in 40 ml methanol respectively. Then the 2-methylimidazole solution was added into the Co(NO3)2·6H2O solution under vigorous stirring for 1 min and aged at room temperature for 22 h. The resulting purple precipitate was collected by centrifugation and washed with ethanol 3 times, and finally vacuum dried.[51] Preparation of 3D-NPC: The as-prepared ZIF-67 was loaded into a quartz boat and placed in a furnace. The 3D-NPC was obtained by directly annealing ZIF-67 crystal under nitrogen atmosphere at 800 °C for 3 h at a rate of 2 °C min-1, followed by washing with 37% HCl to remove the cobalt component. Then the sample was washed with deionized water several times and vacuum dried at 60 °C.



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Sn@3D-NPC composite: Dried 3D-NPC powder (20 mg) was immersed in a solution of SnCl4·5H2O (140 mg) in methanol (20 ml) and the mixture was sonicated for 3 h. Then a solution of NaBH4 (100 mg) in methanol (1 ml) was added quickly to the mixture under strong stirring at room temperature for 30 min. The product was collected by centrifugation, washed with methanol several times, and vacuum dried at 60 °C. Characterizations: The crystal phase was investigated by X-ray powder diffractometer (Bruker D8 Advance) using Cu Kα radiation (λ=1.5406 Å). Scanning electron microscope (SEM) images and elemental analysis were taken by a JEOL JSM-7600 field-emission SEM with an accelerating voltage of 5 kV with energy dispersive X-ray spectroscope. Transmission electron microscope (TEM) characterizations were taken by a JEOL JEM 2100F at an accelerating voltage of 200 kV and the elemental mapping was obtained using the energy-dispersive X-ray spectroscopy attached to the JSM 2100F. Thermogravimetric analysis was performed on a Q500 TGA (TA Instruments). Nitrogen sorption analysis was carried out on a Micromeritics Tristar Ⅱ 3020 at 77 K. Electrochemical Measurements: The working electrode was prepared by mixing the active materials, super-P carbon black and polyvinylidene fluoride (PVDF) at a weight ratio of 80:10:10 in N-methyl-2 pyrrolidinone (NMP) solvent. The resulting slurry was pasted onto Cu foil and dried at 60 °C for 12 h under vacuum. The electrochemical tests were carried out using CR 2032 coin-type cells. Lithium metal acted as the counter electrode and Celgard 2400 membrane was used as the separator. The electrolyte was 1 M LiPF6 dissolved in ethylene carbonate (EC) and diethyl carbonate (DEC) (50:50 in weight ratio). The coin cells were assembled in an argon filled glove box with oxygen and moisture less than 1 ppm. The cyclic voltammetry (CV) were performed on an electrochemical workstation (CHI 660C) in a potential range of 0.001-3.0 V at the scan rate of 0.1 mV s-1. Charge-discharge tests were carried out using a NEWARE battery tester within a voltage range of 0.001-3.0 V. Acknowledgements This work was financially supported by the National Natural Science Foundation (21574065, 21604038), the National Science Foundation for Distinguished Young Scholars (21625401), the Jiangsu Provincial Founds for Distinguished Young Scholars (BK20140044), the Jiangsu


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Specially-Appointed Professor, the Program for Outstanding Young Scholars from the Organization Department of the CPC Central Committee, the National Key Basic Research Program of China (2015CB932200), Singapore MOE AcRF Tier 1 grants 2016-T1-002-065, RG113/15 and Singapore A*STAR Pharos program SERC 1527200022. This work was also supported by the U.S. Department of Energy (DOE) under Contract DE-AC0206CH11357 with the support provided by the Vehicle Technologies Office, DOE, Office of Energy Efficiency and Renewable Energy (EERE). Additional information Competing financial interests: The authors declare no competing financial interests. Corresponding

authors:

[email protected]

(J.L.);

[email protected]

(F.H.);

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Scheme 1. Schematic diagram for the preparation process of the Sn@3D-NPC composite.


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Figure 1. SEM images of (a) ZIF-67, (b) 3D-NPC and (c) Sn@3D-NPC. TEM images of (d) ZIF-67, (e) 3D-NPC and (f) Sn@3D-NPC. (g) High-resolution TEM image of Sn@3D-NPC. (h) Elemental mapping images.



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Figure 2. (a) XRD pattern, (b) Raman spectra of Sn@3D-NPC. (c) TGA analysis in air with a heating rate of 5 °C min-1 of 3D-NPC and Sn@3D-NPC. Nitrogen adsorption˗desorption isotherms and the pore size distribution curves (inset) of (d) 3D-NPC and (e) Sn@3D-NPC.


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Figure 3. The initial five CVs of a) Sn@3D-NPC, b) 3D-NPC and c) SnNPs. The first three discharge-charge profiles of d) Sn@3D-NPC, e) 3D-NPC and f) SnNPs. g) The cycling performances of Sn@3D-NPC, 3D-NPC and SnNPs at a current density of 200 mA g-1, 0.005˗3 V. h) Rate capabilities of Sn@3D-NPC, 3D-NPC and SnNPs. i) Nyquist plots of the three Sn@3D-NPC, SnNPs and 3D-NPC electrodes after 5 cycles.



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Sn Nanoparticles Encapsulated in 3D Nanoporous Carbon Derived

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