Facile preparation of one-dimensional hollow tin [email protected] nanocomposite for lithium-ion battery anode

Journal Pre-proof Facile preparation of one-dimensional hollow tin dioxide@carbon nanocomposite for lithium-ion battery anode

Yanbin Chen, Feng Zhang, Qinghua Tian, Wei Zhang PII:

S1572-6657(20)30126-0

DOI:

https://doi.org/10.1016/j.jelechem.2020.113943

Reference:

JEAC 113943

To appear in:

Journal of Electroanalytical Chemistry

Received date:

2 October 2019

Revised date:

11 December 2019

Accepted date:

10 February 2020

Please cite this article as: Y. Chen, F. Zhang, Q. Tian, et al., Facile preparation of onedimensional hollow tin dioxide@carbon nanocomposite for lithium-ion battery anode, Journal of Electroanalytical Chemistry(2018), https://doi.org/10.1016/ j.jelechem.2020.113943

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© 2018 Published by Elsevier.

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Facile preparation of one-dimensional hollow tin dioxide@carbon nanocomposite for lithium-ion battery anode Yanbin Chen, Feng Zhang, Qinghua Tian* and Wei Zhang* Department of Chemistry, School of Sciences, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China *Corresponding author e-mail address: [email protected] (Qinghua Tian),

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[email protected] (Wei Zhang)

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Abstract: To improve the lithium storage performance of SnO2 anode for lithium-ion batteries, a

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one-dimensional hollow nanostructured SnO2@C composite has been synthesized by a

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well-designed facile approach. The good conductive and flexible carbon component can not only

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enhance the conductivity of whole composite but also buffer the volume change of key SnO2 component. With thin shells, meanwhile, the hollow structure can not only provide free space for

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accommodating the SnO2 volume change, but also shorten the diffusion length for both

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lithiun-ions and electrons. As expectedly, the synergistic effect of carbon and hollow structure offers the as-prepared SnO2@C composite with good structural stability and electrochemical properties. Consequently, the as-prepared SnO2@C composite exhibits good cycling and superior rate performance as an anode for lithium-ion batteries, a high capacity of 797 mAh g-1 is obtained at 200 mA g-1 after 390 cycles as well as 972, 887, 836, 751, 668, and 606 mAh g-1 can be obtained at 100, 300, 500, 1000, 2000, and 3000 mA g-1, respectively. Thus good performance offers the as-prepared SnO2@C composite great promising for a high-performance anode for lithium-ion batteries. Keywords: Facile preparation; One-dimensional hollow nanostructure; Synergistic effect; High capacity; SnO2 anode; Lithium-ion batteries 1 / 21

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1. Introduction Currently, the development of efficient and rechargeable energy storage devices has attracted more and more attention due to the urgency of energy renewal for handling the global risks of environmental pollution and energy shortage [1]. Owing to possession of many merits such as high energy density, low self-discharge and low cost, lithium-ion batteries (LIBs)-an famous

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electrical energy storage device have been identified as the favorite power sources for various

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portable electronic equipments and even electric vehicles [2, 3]. Nevertheless, there are still challenges that affect the wide application of existing LIBs in stationary energy storage and

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electric vehicles such as low energy density and unfavorable safety [4]. With respect to anode

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materials, the currently commercial graphite anodes cannot content with the ever-increasing

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demand of LIBs for high energy density and safety due to their low theoretical capacity (372 mA h

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g-1) and low lithiation potential that towards formation of hazard lithium dendrite at higher current densities [5]. For that reason it has undoubtedly become inevitable to develop alternative anode

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materials with high theoretical capacity and improved safety. To date, many works indicate that the metal oxides with alloying and/or conversion reactions have great potential to be the most promising candidates due to their advantages of resource abundance, high theoretical specific capacities and safer lithiation potential than graphite anodes [6]. Among metal oxides, SnO2 stands out as one of the most promising LIB anode materials and hence has been extensively researched because of its possession of high theoretical capacity of 1494 mAh g-1, and safer operation potential than graphite anode (～0.5 V vs. Li/Li+) [7-9]. However, there are intrinsic shortcomings of SnO2 that severely affect its practical use in LIBs, such as the poor conductivity and especially huge volume change during lithiation/delithiation 2 / 21

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cycle process [10]. The poor conductivity will impair the rate capability whereas the huge volume change will cause the capacity of battery decay quickly. Imaginably, to promote the practical application of SnO2 anode in LIBs, it is crucial to effectively solve above shortcomings. In current, carbon-coated SnO2 and especially carbon-coated hollow nanostructural SnO2 composites have been widely prepared to improve the lithium storage performance of SnO2 anodes such as cycling

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stability and rate capability, owing to their following structure advantages [11, 12]. One hand, by

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comparison with SnO2, the carbon has better conductivity and flexiblility, thereby can not only enhance the conductivity of whole electrode but also buffer the volume change of SnO2 during

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cycle. On the other hand, the nanosized thin shells can reduce the absolute volume change of SnO2

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and transfer distances of both ions and electrons as well the hollow cavity can offer adequate free

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space for mitigating the volume change of SnO2 component, thus further improve the

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electrochemical kinetics and structure stability. For example, currently reported textile-based ultra-flexible SnO2/C electrode revealed a capacity as high as 968.6 mAh g-1 after 100 cycles at 85

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mA g-1 [13]; Thin two-dimensional hollow SnO2/C nanocomposite displayed improved capacities of 707.8 and 483.2 mAh g-1 after 100 cycles at 200 and 1000 mA g-1 [14]; 3D graphene network encapsulating SnO2 hollow spheres delivered a high capacity of 1107 mAh g-1 after 100 cycles at a current density of 100 mA g-1 [15]; Mesoporous C@SnO2@C hollow nanospheres exhibited improved cycling stability, revealing a capacity of 712.6 mAh g-1 after 300 cycles at 200 mA g-1 [16]; and hollow SnO2/C nanotubes presented a capacity of 596 mAh g-1 after 200 cycles at 500 mA g-1 [17]. It is thus indicated that carbon-coated hollow nanostructural SnO2 composites have great promising for effectively improving the electrochemical performance of SnO2 anode for LIBs. 3 / 21

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To this end, we utilize the one-dimensional SnC2O4 nanowires (NWs) that can be facile prepared to be a template for facile fabrication of SnO2/C nanotubes, as seen in preparation schematic (Fig. 1). Due to the SnC2O4 that can be etched by ammonia, the intermediate SiO2 nanotubes (NTs) were obtained through SiO2 depositing on the surface of SnC2O4 NWs by hydrolysis of tetraethyl orthosilicate in ammonia solution. The as-prepared intermediate SiO2 NTs

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were dispersed into a solution including ammonium fluoride, stannous chloride and glucose

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chemicals and then treated by a hydrothermal process. During hydrothermal process SnO2 and polysaccharide (Ps) were successively coated on the surface of SiO2 NTs while the SiO2 NTs were

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gradually etched by ammonium fluoride solution, and hence form the SnO2@Pa NTs. After further

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carbonization the SnO2@Pa NTs transformed into SnO2@C NTs (namely tubular SnO2@C

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nanocomposites) successfully. As mentioned above, the as-prepared SnO2@C NTs showed

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improved lithium storage performance as an anode for LIBs due to the synergistic effect of carbon coating and one-dimensional hollow nanostructure, disclosing a high capacity of 797 mAh g-1

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after even 390 cycles.

Fig. 1 Preparation schematic of SnO2@C NTs 2. Experimental section 2.1 Materials preparation According to a previous work [18], the SnC2O4 NWs were synthesized firstly. The SnC2O4 NWs (0.1) were dispersed into a mixture of deionized water (70 ml) and anhydrous ethanol (70 ml) 4 / 21

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by ultrasound for 30. Next, cetyl trimethyl ammonium bromide (CTAB, 0.4 g) and 25-28 wt.% ammonia solution (1.5 ml) were successively added to thus suspension and then continuously stirred for 1 h. The tetraethyl orthosilicate (TEOS, 0.3 ml) was added to the suspension by dropwise and then continuously stirred for another 6 h. After that, the SiO2 NTs were prepared and collected through centrifugation, rinsed by deionized water (three times firstly) and ethanol (one

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last time), and dried at 70 oC overnight. The as-prepared SiO2 NTs (0.1 g) were well dispersed into

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60 ml deionized water by ultrasound for 30 min and then successively added by 1.2 g glucose, 0.2 g tin dichloride dehydrate and 0.044 g ammonium fluoride under continuous stirring. After stirring

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for 30 min thus suspension was transferred into a Teflon-lined stainless steel autoclave and then

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placed in an oven for 24 h at 180 oC. When set hydrothermal time was up, the autoclave was

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cooled down naturally. After that, the as-obtained SnO2@Pa NTs intermediate was gathered via

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centrifugation, rinsed by deionized water (three times firstly) and ethanol (one last time), and dried at 70 oC overnight. After final carbonization of SnO2@Pa NTs at 500 oC for 3 h under an Ar

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atmosphere, the SnO2@C NTs were got. 2.2 Materials characterizations

Observation of morphology and microstructure was achieved by field emission scanning electron microscopy (FE-SEM, JEOL JSM-7401F) and transmission electron microscopy (TEM, JEOL JEM-2010). Elemental mapping was recorded via EDX which was attached to SEM. X-ray diffraction (XRD, Rigaku, D/max-Rbusing Cu Kα X-ray radiation) and Raman spectroscopy (Bruker, Senterra R200-L dispersive Raman microscope) were used to study the crystal structure and composition of SnO2@C NTs composite. The BET specific surface area and carbon content of SnO2@C NTs composite were measured by a Micromeritics ASAP 2010 BET nitrogen 5 / 21

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adsorption-desorption instrument and thermogravimetric analysis (TGA, SDT Q600 V8.2 Build 100), respectively. 2.3 Electrochemical characterization The electrochemical performance of SnO2@C NTs was tested by 2016-type coin cells that were assembled in an argon-filled glove box (German, M. Braun Co., [O2] < 1 ppm, [H2O] < 1 ppm).

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Working electrode was composed of SnO2@C NTs active material, acetylene black (AB,

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conductive agent), sodium carboxymethyl cellulose (CMC, binder) and Cu foil current collector. The SnO2@C NTs, AB and CMC with a weight ratio of 7:2:1 were well blended in deionized

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water to form slurry which was then pasted onto the Cu foil by a notch bar and vacuum dried at

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110 oC overnight. Then, Li metal and glass fiber (GF/A, Whatman) were used to be the anode and

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separator, respectively. And the electrolyte selected 1 M LiPF6 solution in a mixture of ethylene

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carbonate (EC) and dimethyl carbonate (DMC) (1:1 in volume). CHI660D electrochemical workstation was used to record the cyclic voltammograms (CVs) at a scanning rate of 0.3 mV s-1

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between 0.01 and 3.0 V under room temperature. LAND CT2001a cell test systems (LAND Electronic Co.) were used to test the galvanostatic discharge/charge cycling performance of as-assembled cells at different current densities between 0.01 and 3.0 V under room temperature. 3. Results and discussion Fig. 2 discloses the SEM images of SnC2O4 NWs, SiO2 NTs and SnO2@C NTs. It is thus clear that both the SiO2 NTs (Fig. 2b) and SnO2@C NTs (Fig. 2c) well retain the one-dimensional morphology of SnC2O4 NWs (Fig. 2c), determining the feasibility of preparation approach proposed here. Nevertheless, the surface of SnO2@C NTs is rougher than both SnC2O4 NWs and SiO2 NTs, which may be mainly attributed to the simultaneous occurrence of multiple reactions 6 / 21

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during hydrothermal process such as SnO2 deposition, Pa coating and SiO2 etching. Fig. S1 and Fig. 2d further disclose the EDX spectrum and elemental mappings of SnO2@C NTs, respectively, so as to reveal the elements and elemental distribution of as-prepared SnO2@C NTs composite intuitively. Therefore, we can find that the SnO2@C NTs consist of Sn, O and C elements all which have well distribution profiles in SnO2@C NTs. No observation of Si element that suggests

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almost complete removal of the amorphous SiO2 NTs during hydrothermal process.

Fig. 2 SEM images of (a) SnC2O4 NWs, (b) SiO2 NTs and (c) SnO2@C NTs; (d) Mapping image of elements of SnO2@C NTs.

Furthermore, to study the crystal structure of SnO2@C NTs, XRD patterns were recorded, as displayed in Fig. 3a. By comparison with the standard diffraction peaks that are marked by red font, all the diffraction peaks of as-obtained XRD patterns can be well indexed into the rutile phase SnO2 (JCPDS card No. 45-1445) [19]. The diffraction peaks for carbon, however, are not observed, which may be ascribed to overlap with the strong SnO2 peaks and the dominant amorphous structure of carbon in SnO2@C NTs caused by a low carbonization temperature. To 7 / 21

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support existence and crystal structure of carbon component, Raman spectrum was gained, as shown in Fig. 3b. Obviously, two peaks that corresponding to the characteristic peaks (D-band and G-band) of carbon materials are observed at 1356 and 1587 cm-1, and hence testify the presence of carbon in SnO2@C NTs. The ratio value of ID to IG is calculated to be 0.9, confirming the low crystalline of carbon [20]. It is in good agreement with the XRD results. And the analysis results

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of XRD and Raman are also consistent with mapping observation. Fig. 3c shows the TGA curve

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for measuring the carbon content of SnO2@C NTs. In view of that, the mass content of carbon is

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estimated to be 52.4%.

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Fig. 3 (a) XRD patterns, (b) Raman spectrum and (c) TGA curve of SnO2@C NTs.

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To get a better observation of microstructure of SnO2@C NTs, TEM images were obtained, as seen in Fig. 4a and b. It is thus clear that the SnO2@C NTs have a typical one-dimensional hollow structure with diameters ranging from 150 to 350 nm and thicknesses from 30 to 50 nm. The magnified TEM image in Fig. 4b discloses that a thin layer of bright carbon exists on the surface of nanotube. The SAED patterns in inset of Fig. 4b shows clear diffraction rings, indicating good crystallization. Fig. 4c exhibits the HRTEM image for deeply detecting the distribution states of SnO2 and carbon components in shells of SnO2@C NTs. Many lattice fringes with a interplanar spacing of 0.33 nm are viewed on inner dark regions, which corresponding to the (110) plane of SnO2. Meanwhile, a layer of bright amourphous carbon with thicknesses ranging from 2 to 7 nm is observed on the outmost surface of shell. Therefore, the shells of SnO2@C NTs are composed of 8 / 21

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inner SnO2 and outer carbon coating, being in line with the expected results of the experiment. Additionally, the SnO2@C NTs have a larger BET specific surface area of 62 m2 g-1, determined by N2 adsorption/desorption isotherms as shown in Fig. S2. It is suggested that thus large specific surface area should be benefited from the one-dimensional hollow nanostructure of SnO2@C NTs

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composite.

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Fig. 4 (a, b) TEM and (c) HRTEM images of SnO2@C NTs; The inset in (b) shows the SAED patterns.

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Considering that hollow nanostructures of metal oxides have a promising application in anode

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materials for LIBs [21], the electrochemical properties of SnO2@C NTs have been studied by an electrochemical workstation and cell test systems. Fig. 5a discloses the initial three cycles of CV curves that are recorded by an electrochemical workstation at a scanning rate of 0.3 mV s-1 under voltage window ranging from 0.01 to 3.0 V. In first cycle a weak cathodic peak and a sharp cathodic peak are observed at 0.8 and between 0.54 and 0.01 V, respectively. The former peak is attributed to the irreversible formation of a solid electrolyte interphase (SEI) film and partially reversible reduction of SnO2 into Sn, whereas the latter peak is assigned to the reversible alloying reactions between Sn and lithium [22-24]. Then, there are two anodic peaks that corresponding to the dealloying reactions of Li-Sn alloys and oxidation reaction of Sn into oxide are observed at 0.63 and 1.22 V, respectively [25, 26]. In addition, it is thus obvious that the following two cycles 9 / 21

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present a overlapping trend, indicating good reversibility. Fig. 5b depicts the initial five cycles of galvanostatic discharge/charge curves at 200 mA g-1 between 0.01 and 3.0 V. We can find that two sloped plateau potentials are viewed in both discharge (1.0 and 0.3 V) and charge (1.2 and 0.5 V) branches, which are ascribed to the SnO2-to-Sn conversion (SnO2 + 4Li+ + 4e- ↔ Sn + Li2O) and Sn-Li alloying/dealloying reactions (Sn + 4.4Li+ + 4.4e- ↔ Li4.4Sn), respectively [27], being in

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good agreement with the CV observation. Fig. S3 gives the XRD patterns of SnO2@C NTs

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electrode after 1 cycle. It is thus clear that the peaks of metal Sn are observed but the obvious peaks of SnO2 are not observed, which indicate that the alloying reactions between Sn and lithium

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is reversible but the reduction of SnO2 into Sn is partially reversible (causing the content of SnO2

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is too little to be detected). It is in good agreement with the CV results. In first cycle the discharge

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and charge capacities are 1786 and 1061 mAh g-1, respectively, and hence lead to a coulombic

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efficiency of 59.4 %. But, the coulombic efficiency increases up to above 93% after first cycle. Therefore, the large initial capacity loss is suggested to correlate with the irreversible formation of

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a SEI film and partially reversible reduction of SnO2 into Sn in first cycle [28]. After that, Fig. 5c shows the cycling performance and corresponding coulombic efficiency at 200 mA g-1. After experiencing 390 cycles, a high capacity of 797 mAh g-1 can be retained as well as the coulombic efficiencies are stabilized at above 98% in whole cycle but exception of initial four cycles, indicating the good cycling performance of SnO2@C NTs electrode. Even compared to the other reported SnO2/C composites with different nanostructures, the lithium storage of as-prepared SnO2@C NTs is higher, as seen in Table S1. The superior lithium storage should be related to the structural properties of SnO2@C NTs. One hand, the good conductive and flexible carbon coating can not only enhance the conductivity of whole composite but also buffer the volume change of 10 / 21

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key SnO2 component; On the other hand, with thin shells, meanwhile, the one-dimensional hollow nanostructure can not only provide free space for accommodating the SnO2 volume change, but also shorten the diffusion length for both lithiun-ions and electrons, and thus guarantee good structural stability and electrochemical kinetics. The phenomenon that the capacity starts to decrease after 50 cycles and then increases after 150 cycles is commonly observed in metal

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oxide-based anodes and should be attributed to the structural adjustment of electrodes, deep

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penetration of electrolytes and further activation of active materials during long-term cycling process [6, 16, 29-33]. Fig. S4 further discloses a TEM image of SnO2@C NTs electrode after 100

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cycles at 200 mA g-1. The integrity of one-dimensional hollow nanostructure is kept but the

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thickness of shell increases and hollow space decreases, which indicates the appropriate structural

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adjustment for SnO2 volume change and hence confirms good structural stability of SnO2@C NTs

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electrode. Certainly, the good structural stability of SnO2@C NTs electrode is attributed to the synergistic effect of carbon (buffering the SnO2 volume change) and hollow structure

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(accommodating the SnO2 volume change, namely providing the free space for the SnO2 to expand inward). When the cycles increase up to 450 cycles, however, the fast decay of capacity of SnO2@C NTs electrode is observed, which is ascribed to the severely structural destroy (the one-dimensional tubular structure is almost completely damaged) of SnO2@C NTs electrode after long-term cycling process, as shown in Fig. S5. Fig. 5d gives the rate capability of SnO2@C NTs electrode at current densities ranging from 100 to 3000 mA g-1. The result is that 972, 887, 836, 751, 668, and 606 mAh g-1 are remained in 10th cycle at 100, 300, 500, 1000, 2000, and 3000 mA g-1, respectively, as well as a high capacity of 922 mAh g-1 can be restored after 10 cycles at 100 mA g-1, thus exhibiting superior rate performance. 11 / 21

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Fig. 5 Electrochemical performances of SnO2@C NTs: (a) Cyclic voltammograms (CVs), (b)

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galvanostatic discharge/charge curves, (c) cycling performances, and (d) rate capability. 4. Conclusions

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In summary, a one-dimensional hollow nanostructured SnO2@C NTs has been prepared by a

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facile approach. As expectedly, the well-designed synergistic effect of carbon and hollow structure provides the SnO2@C NTs with good structural stability and electrochemical kinetics when used as an anode for LIBs. As a result, the SnO2@C NTs exhibits good cycling and superior rate performance, a high capacity of 797 mAh g-1 is obtained at 200 mA g-1 after 390 cycles as well as 972, 887, 836, 751, 668, and 606 mAh g-1 can be obtained at 100, 300, 500, 1000, 2000, and 3000 mA g-1, respectively. Thus good performance offers the SnO2@C NTs great promising for a high-performance anode of LIBs. Acknowledgments We are grateful for financial support from Natural Science Foundation of Zhejiang Province (No. LQ18B030008), Scientific Research Start-up Foundation of Zhejiang Sci-Tech University 12 / 21

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[33] Z. Cai, L. Xu, M. Yan, C. Han, L. He, K. M. Hercule, C. Niu, Z. Yuan, W. Xu, L. Qu, K.

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batteries, Nano Lett. 15 (2015) 738-744.

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Zhao, L. Mai, Manganese oxide/carbon yolk-shell nanorod anodes for high capacity lithium

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Declaration of competing interests

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There are no interests to declare.

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Author Contribution Statement Yanbin Chen: Resources, Project administration, Investigation Feng Zhang: Resources, Formal analysis Qinghua Tian: Funding acquisition, Methodology, Writing- Original Draft, Supervision

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Wei Zhang: Writing- Reviewing and Editing, Supervision

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Graphical Abstract

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Highlights 1. The SnO2@C nanotubes were prepared by a well-designed method. 2. This composite had improved structural stability. 3. This composite anode exhibited superior electrochemical performance.

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4. It delivered a high capacity of 797 mAh g-1 at 200 mA g-1 after even 390 cycles.

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