Accepted Manuscript

Tin nanoparticles embedded in porous N-doped graphene-like carbon network as

high-performance anode material for lithium-ion batteries

Dan Zhou, Wei-Li Song, Xiaogang Li, Li-Zhen Fan, Yonghong Deng

PII: S0925-8388(16)34355-9
DOI: 10.1016/j.jallcom.2016.12.426
Reference: JALCOM 40349

To appear in: Journal of Alloys and Compounds

Received Date: 22 September 2016

Revised Date: 28 December 2016
Accepted Date: 31 December 2016

Please cite this article as: D. Zhou, W.-L. Song, X. Li, L.-Z. Fan, Y. Deng, Tin nanoparticles embedded
in porous N-doped graphene-like carbon network as high-performance anode material for lithium-ion
batteries, Journal of Alloys and Compounds (2017), doi: 10.1016/j.jallcom.2016.12.426.

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 ACCEPTED MANUSCRIPT

Graphical abstract

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Tin nanoparticles embedded in porous N-doped graphene-like carbon network as

high-performance anode material for lithium-ion batteries

Dan Zhou , Wei-Li Song , Xiaogang Li , Li-Zhen Fan * and Yonghong Deng *
1 1 1 1 2

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Key Laboratory of New Energy Materials and Technologies, Institute of Advanced Materials and

Technology, University of Science and Technology Beijing, Beijing 100083, China

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Department of Materials Science and Engineering, South University of Science and Technology of China,
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Shenzhen 518055, China

*Corresponding author: E-mail: fanlizhen@ustb.edu.cn (Li-Zhen Fan), yhdeng08@163.com (yonghong

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Deng);Tel./fax: +86-10-62334311
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Abstract

Sn-based materials have received particular attention as high capacity anodes for rechargeable

lithium-ion batteries (LIBs). However, poor stability induced by a serve volume expansion during

repeated cycling still remains great challenges in practical application. In this paper, well-dispersed Sn

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nanoparticles embedded in the porous N-doped graphene-like carbon network (Sn@PNGC) were simply

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fabricated via a one-step thermal reaction. Owing to the advantages of the unique porous N-doped

graphene-like carbon network, the Sn@PNGC composite can not only avoid the direct contact between

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metallic Sn and electrolytes coupled with accommodating the aggregation and volume expansion of Sn

nanoparticles, but also provide sufficient active sites for Li+ insertion and favorable transport kinetics for

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electron transport. As a consequence, the as-prepared Sn@PNGC anode suggests remarkable
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electrochemical performance with enhanced capacity, improved stable ability and rate capability, thus

delivering an initial discharge capacity of 1129 mAh g−1 and a high reversible capacity of 595 mAh g−1
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after 100 cycles at 100 mA g−1, along with an enhanced rate capacity of 437 mAh g−1 after 300 cycles at
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500 mA g−1. The facile approach demonstrates great potential for the low-cost and scalable fabrication
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of advanced Sn-based anode materials for LIBs.

Keywords: Lithium-ion batteries; Anode; Sn; Electrochemical performance

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1. Introduction

Rechargeable lithium-ion batteries (LIBs) are considered as promising energy power sources in the

fields of consumer electronics, electric vehicles (EVs) and power grids due to the large energy/power

density and long lifespan [1−3]. However, the classical commercial graphite anode suffers low

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theoretical capacity of 372 mAh g−1 and therefore the LIBs deliver a limited energy output [4,5]. In

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developing high-performance LIB systems, the studies on advanced anode materials with high capacity

and excellent stability have been massively made. Among various available anode materials, metallic Sn

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that holds high theoretical capacity (Li4.4Sn: 993 mAh g−1 or 7262 mAh cm−3), high electrical

conductivity as well as moderate operating voltage [6−8], has been substantially investigated.

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Unfortunately, identical to other high capacity anode materials such as Si (4200 mAh g−1) [9−11], Ge
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(1600 mAh g−1) [12,13] and SnOx (SnO: 875 mAh g−1, SnO2: 782 mAh g−1) [14−17], the metallic Sn

anode often suffers from intrinsically dramatic volume expansion (~300%) due to the Li+
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insertion/extraction, which results in serve pulverization, weak electrical contact between Sn and the
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current collector, and continuous formation of unstable solid electrolyte interphase (SEI) film on the
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surface of Sn, and thus rapid capacity decay and weak cyclability for the electrode during cycling

process [18,19].
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Enormous works have been done to address the drawbacks of Sn-based anodes in the practical

application. One feasible approach is to construct novel nanostructures of metallic Sn to avoid the
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pulverization of anodes and improve the kinetics for Li+ storage [20−22]. However, serious issues such
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as aggregation of Sn nanoparticles (NPs) arising in the cycling process, and continual formation of an

unstable SEI film on the surface of Sn NPs resulted from the direct exposure with the electrolyte,

leading to a large irreversible capacity and weak cyclability. To solve these obstacles, designing hybrid

anodes integrating nanosized Sn and various carbonaceous matrix reveal promising potential. In this

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regard, a variety of Sn-carbonaceous anodes involves nano-Sn filled into carbon nanotubes [23,24],

carbon coated Sn nanocomposite [25,26], and Sn NPs dispersed in porous carbon [27−29] have been

developed. Several merits reveal for the hybrid anodes design. For one hand, the nano-sized Sn particles

are conducive to reducing the absolute volume variation [30,31]. For another, Sn NPs are stabilized in

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the porous carbonaceous matrix with elastic feature to effectively relieve the strain associated with large

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volumetric expansion, further overcoming the aggregation and improving the electrical conductivity of

Sn, and thus a significant improvement for the cycling stability [32].

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Impressively, two-dimensional (2D) materials such as graphene-based nanosheets, which integrate the

intriguing properties of superior electrical conductivity, exceptionally high surface area (theoretically

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greater than 2600 m2 g−1) and good elasticity, may serve as excellent electrode materials for
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electrochemical reactions [33,34]. Specially, 2D materials with porous structures can act as matrix for

growing nanosized Sn particles, which seem to be a promising strategy for anode materials. However, it
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still remains a critical challenge to develop a simple and scalable process to produce Sn-based anode
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materials with a 2D layered structure for high-performance LIBs.

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In this work, we demonstrated a facile method for the fabrication of porous Sn-carbon hybrid anodes

with metallic Sn nanoparticles embedded in the porous N-doped graphene-like carbon network (named
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as Sn@PNGC) via one-step thermal reaction. With low-cost glucose, urea, and SnCl4·5H2O as raw

materials, this unique strategy is suitable for scalable fabrication. The as-synthesized Sn@PNGC
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composite can avoid Sn aggregation during the electrochemical process, and can further improve the
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electrical conductivity of metallic Sn with the presence of conductive carbon matrix. Additionally, the

porous carbon network could provide sufficient space for the expansion upon Li+ insertion. As a

consequence, the Sn@PNGC anode exhibits remarkable electrochemical performance with enhanced

capacity, improved stable ability and rate capability, delivering an initial discharge capacity of 1129

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mAh g−1 and a high reversible capacity of 595 mAh g−1 after 100 cycles at 100 mA g−1, along with an

enhanced rate capacity of 437 mAh g−1 after 300 cycles at 500 mA g−1.

2. Experimental section

2.1. Preparation of the Sn@PNGC composite

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The Sn@PNGC composite was prepared by a one-step thermal reaction process using low-cost

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glucose, urea and SnCl4·5H2O as raw materials. In a typical synthesis, 0.84 g of SnCl4·5H2O, 20 g of

urea, and 1 g of glucose were mixed and dissolved in 200 mL deionized water under vigorous stirring at

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80 oC. After the deionized water was evaporated, the resultant Sn@PNGC precursor was treated at 800
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C for 2 h in N2 atmosphere with a rising rate of 3 oC min−1, and thus Sn@PNGC powders were finally

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obtained. For the control sample, carbon embedded Sn (Sn@C) was synthesized by annealing the
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precursors without urea.

2.2. Characterizations
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The surface morphology and microstructure were observed by a field-emission scanning electron
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microscopy (FE-SEM, JEOL JSM-6330) and a transmission electron microscopy (TEM, JEM-2010F).
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The phase structure was characterized using X-ray diffraction (XRD) on a Rigaku D/max-Rb X-Ray

diffractometer with Cu Kα irradiation (λ=1.5406 Å). X-ray photoelectron spectroscopy (XPS) tests were
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performed on an EscaLab 250Xi electron spectrometer equipped with Al Kα irradiation to examine the

surface of the samples. Energy dispersive X-ray spectra (EDS) measurements were carried out using an
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Oxford Instrument energy dispersive spectrometer. The carbonized structure was recorded with a
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confocal Raman microscope (Raman, Horiba Jobin-Yvon HR800). The Sn content of the Sn@PNGC

composite was determined by thermogravimetric analysis (TGA) on a STA449F3 simultaneous

thermalanalyzer under air atmosphere at a rate of 10 oC min−1 from ambient temperature to 800 oC. The

N2 adsorption–desorption isotherm was obtained by a gas Quantachrome autosorb-IQ adsorption

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analyzer. The specific surface areas and the pore-size distribution were calculated using the multipoint

Brunauer–Emmett–Teller (BET) method and Barrett–Joyner–Halenda (BJH) model, respectively.

2.3. Electrochemical measurements

The electrochemical performances of the electrode materials were evaluated using 2032 coin-type

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half-cells. To prepare the working electrodes, active materials (Sn@PNGC or Sn@C) were mixed with

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conductive carbon black and polyvinylidene fluoride at a mass ratio of 8: 1: 1 in N-methylpyrrolidinone

to form slurry, which was then homogeneously coated on a fresh copper foil followed by drying at 80 oC

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overnight under vacuum. Lithium foil was employed as the counter and reference electrode, 1 M LiPF6

dissolved in a mixture of ethylene carbonate/diethyl carbonate/dimethyl carbonate (1: 1: 1 V/V) as the

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electrolyte, and Celgard 2400 film as the separator. All the half cells were assembled in an argon-filled
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glove box with moisture and oxygen content below 1ppm. The galvanostatic charge/discharge cycles

were recorded using a LAND CT2001A battery test system (Wuhan Jinnuo Co., China) at various
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current densities in the voltage range of 0.01–3.0 V (vs Li/Li+). Cyclic voltammetry (CV) curves were
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collected at a sweep rate of 0.2 mV s−1 within 0.01–3.0 V (vs Li/Li+) using a CHI 660C electrochemical
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work station (Shanghai Chenhua Co., China). Electrochemical impedence spectroscopy (EIS)

measurements were also conducted on the CHI 660C electrochemical work station by applying an
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amplitude of 5 mV over the frequency range of 0.01–100 kHz. Without special emphasis, all the specific

capacities are calculated based on the total mass of the composites.

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3. Results and discussion

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The typical preparation route of the Sn@PNGC composite is schematically illustrated in Fig. 1.

Firstly, the raw materials, glucose, urea and SnCl4·5H2O, are homogeneously mixed with deionized

water. In this section, the precursor of SnO2 (Sn(OH)4) would be formed via the hydrolysis of Sn4+ in

aqueous solution. Subsequently, the resultant mixture is directly annealed at 800 oC under N2

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atmosphere. During the sintering process, g-C3N4 would be formed via the thermal decomposition-

polymerization of urea [35,36]. The resultant g-C3N4 possesses a layered structure with various pores,

and could be used as both the nitrogen source and template in the structural evolution for achieving the

graphene-like carbon sheets [35,36]. The Sn species of SnO2 obtained by the pyrolysis of Sn(OH)4 and

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the carbon intermediates from glucose could enter the interspace of g-C3N4, which is formed via the

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complete thermolysis at 800 oC [35]. Simultaneously, g-C3N4 is decomposed completely [34] and Sn

species (SnO2) are carbothermally reduced to Sn NPs under inert gas (N2 flow), and the resulting

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Sn@PNGC composite is obtained. It should be noted that the annealing temperature is the great concern

in the whole formation of Sn@PNGC composite. Remarkably, the approach is simple, low-cost and

versatile for the scalable fabrication.

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X-ray diffraction (XRD) patterns are collected to reveal the phase structures of as-synthesized

Sn@PNGC and Sn@C composites. As shown in Fig. 2a, all of the diffraction peaks of Sn@PNGC and
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Sn@C can well match the tetragonal β-Sn crystal structure (JCPDS card No. 86-2265). The result
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implies that the SnO2 phase originated from the hydrolysis of Sn4+ is fully converted into metallic Sn
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after the carbothermal reduction. Raman spectrum is analyzed to demonstrate the graphitization degree

of the Sn@PNGC composite (Fig. S1). Two main peaks are observed at about 1327 and 1543 cm−1,
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which correspond to the D peak for the disordered carbon and the G peak for the graphite carbon,

respectively. The high intensity ratio ID/IG of 1.25 indicates that the carbon species possesses relatively
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low graphitization degree with sufficient structural defects in Sn@PNGC [37]. In addition,
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thermogravimetric analysis (TGA) is used to determine the Sn loading in the Sn@PNGC composite (Fig.

2b). A continuous mass loss is found below 575 oC, which corresponds to the evaporation of free water

and adsorbed water, burning of converted carbon, and partial oxidation of Sn to form SnO2. Above 575
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C, a slight mass increase is also ascribed to the further oxidation of metallic Sn. Considering the full

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oxidation of Sn to SnO2 at 800 °C in air, the content of Sn in the Sn@PNGC is calculated to be about

31.9 wt% (On the basis of the mass of SnO2 (40.47 wt%)). Similarly, the content of Sn in the Sn@C

composite is determined to be about 53.2 wt% (Fig. S2). Note that the different Sn contents in both

composites are ascribed to the doped nitrogen in Sn@PNGC, with a slight ignored error.

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X-ray photoelectron spectroscopy (XPS) spectrum is conducted to further analyze the chemical

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compositions of the Sn@PNGC composite. As exhibited in Fig. 2c, the full spectra of Sn@PNGC

confirmed the presence of C, Sn, O and N elements, and the nitrogen content is found to as high as

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12.43 at%. Apparently, the C, Sn and N species origin from the precursors of glucose, SnCl4·5H2O and

urea, respectively. O would be introduced by the air-exposed Sn@PNGC, in which slight oxidation

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occurs on the surface of metallic Sn [31,38−40]. Four singe peaks located at 284.6 eV, 285.8 eV, 288.1
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eV and 292.6 eV are observed in the high-resolution C1s spectrum (Fig. 2d), corresponding to the

formation of C=O, C=N & C-O, C-N & C=O, and O-C=N, respectively, which implies the existence of
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doped heteroatoms in the composite [41]. The high-resolution N1s spectrum in Fig. 2e suggests the three
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deconvoluted peaks of nitrogen in Sn@PNGC, which could be assigned to pyridinic-N (398.2 eV),
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pyrrolic-N (400.0 eV), and graphitic-N (401.0), respectively [42]. Nitrogen-doping in carbon materials

can increase the electrical conductivity and thus promote the transport of Li+ and electrons. Also, the
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induced defect sites and vacancies are favorable for the insertion of Li+, leading to excellent cycling

stability of the electrode [31,37,43]. In addition, the high resolution Sn3d XPS spectra can be
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deconvoluted into two sharp peaks of Sn 3d3/2 and Sn 3d5/2 at the binding energy of 486.6 eV and 495.1
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eV, respectively (Fig. 2f). The 486.6 eV binding energy is lower than that of 487.3 eV for Sn4+ and

487.0 eV for Sn2+, but higher than 485.0 eV of Sn0, suggesting that the Sn NPs in Sn@PNGC contains a

tin suboxide, probably resulted by the slight oxidation on the metal surface under the ambient condition,

as is reported in the previous work [31,38−40].

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The surface morphologies and microstructures of the synthesized Sn@PNGC are further examined by

SEM and TEM. As shown in Fig. 3a, the resultant composite reveals a typical graphene-like structure,

which is assembled by the layered g-C3N4 template [35]. Typical TEM images show that the

graphene-like carbon sheets are decorated by a layer of uniform metallic Sn NPs with the size of 2–5 nm

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(Fig. 3b-3d and Fig. S3). Notably, the HRTEM images in Figure 3c–d show that the metallic Sn NPs

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(the region with obvious lattice fringe) are homogenously wrapped by the graphitic carbon sheets (the

surrounded region with no lattice fringe). Besides, the lattice spacing observed is about 0.29 nm (Figure

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3d), corresponding to the (200) plane of metallic Sn, which coincides with the result of XRD analysis. In

contrast, the Sn@C composite suggests non-uniform morphologies, with different particle size and

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different degree of carbon coating (Fig. S4). The difference in morphology of Sn@PNGC and Sn@C is
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probably associated with the different synthesis mechanisms. Due to the existence of g-C3N4, the growth

of Sn in Sn@PNGC was limited and a relatively uniform distribution in the carbon matrix. For Sn@C,
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the precursor of SnO2 was simply coated with glucose under stirring. Then, the glucose was carbonized
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and, meanwhile, SnO2 was reduced to Sn during the thermal process. Some non-uniform coated Sn
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particles would further grow and larger size was finally obtained. The EDS elemental mapping images

of a representative area (the selected area in Fig. 3b) of Sn@PNGC were investigated to confirm the
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elemental distribution of the composite (Fig. 3e–3g), which clearly demonstrates the presence and

distribution of C, N, and Sn elements in the Sn@PNGC. The observed nitrogen element should be
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derived from urea, and the image of Sn element further confirms the uniform distribution of Sn NPs in
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the graphene-like carbon sheets.

Moreover, N2 adsorption/desorption isotherms are measured to investigate the pore structure of the

Sn@PNGC (Fig. 4a). The specific surface area is determined to be about 102 m2 g−1 and the average

pore diameter centered at 1.9 nm with a pore volume of 0.28 cc g−1 (Fig. 4b). The present of pores in the

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Sn@PNGC is probably attributed to gas evolution during the annealing process, inducing from the

thermolysis of carbonitride. Noticeably, the conductive porous structure is responsible for enhanced

ionic and electronic transport as well as sufficient space to accommodate the volume expansion upon the

lithiation/delithiation process, leading to an improved electrochemical performance of LIBs [44].

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As the anode materials for Li+ storage, the electrochemical behaviors of the Sn@PNGC composite are

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evaluated in comparison with the control electrode of Sn@C. In the voltage range from 0.01–3.0 V, Fig.

5a presents the cyclic voltammetry (CV) curves of the Sn@PNGC anode in the first three cycles at a

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constant scanning rate of 0.2 mV s−1. During the first cathodic scan process, two well-defined reduction

peaks are observed at around 1.5 V and 0.75 V. The former is assigned to the decomposition of the

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electrolyte on metallic Sn NPs, and the latter is attributed to the formation of a solid electrolyte interface
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(SEI) film [40,45,46]. The reduction peak located at about 0.2 V represents the reversible alloying

reaction, in which Li+ move into Sn lattice to form LixSn alloys (Sn + xLi+ + xe– →LixSn (0≤ x≤4.4)). In
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addition, the reduction peak close to 0 V is related to the intercalation of Li+ into the graphene-like
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carbon sheets. In the first anodic scan, two oxidation peaks around 0.65 V and 1.25 V correspond to the
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extraction of Li+ from the graphene-like carbon sheets, namely the dealloying of LixSn. For the

subsequent cathode scans, the peaks shifts to 0.26 V, suggesting the improved reaction kinetics due to
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the microstructure evolution via the initial lithiation. In the second scan of the CV curves, the reduction

and oxidation peaks deliver an identical profile to the third one, suggesting an excellent reversible
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performance [40,46]. In the control electrode of Sn@C, similar CV profiles could be observed in Fig. S5
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except for slight changes in the position and intensity of oxidation and reduction peaks, which is

probably assigned to the differences in the structure and composition between Sn@PNGC and Sn@C.

Fig. 5b depicts the representative galvanostatic charge-discharge curves for the 1st, 2nd, 5th, 10th and

20th cycles at a current density of 100 mA g-1. The charge and discharge capacities are 795 and 1129

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mAh g−1 in the first cycle, resulting in a Coulombic efficiency of about 70.4%. The irreversible capacity

loss of Sn@PNGC during the initial cycle is probably related to the formation of the SEI film and

decomposition of the electrolyte [40,46], corresponding to the results of the CV analysis. The initial

discharge curve exhibits a rapid potential drop and large sloping plateau above 0.5 V followed by a long

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slope with a short voltage plateau until the cut-off voltage, which can be assigned to formation of the

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SEI film and alloying of lithium with tin, respectively. In addition, the discharge curves of the electrode

tend to overlap and the related coulombic efficiency rapidly increases from the 2nd to 20th cycles,

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indicating the high reversibility and enhanced stability of the Sn@PNGC electrode upon cycling process

[47,48]. The cycling performance of the Sn@PNGC electrode was tested to evaluate the applicability,

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with Sn@C as control sample for comparison. As shown in Fig. 5c, both of the electrodes suffer a
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serious capacity loss during the initial stage, which is resulted from the formation of the SEI film and

decomposition of the electrolyte [48,49]. Impressively, the Sn@PNGC electrode shows the better
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cycling performance stability than the other one, delivering a retained discharge capacity of 595 mAh
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g−1 after 100th cycles, which is ascribed to the graphene-like carbon protection and the accommodation
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of the volume variation from the porous structure. Typical nyquist plots of the Sn@PNGC anode were

investigated to further understand the relationship between the structural evolution and electrochemical
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performance. Fig. 5d shows the impedance spectra of the Sn@PNGC anode before charge/discharge

process and after 100th cycles at the current density of 100 mA g−1. The impedance spectra possess an
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identical profile of a depressed semicircle from medium to high frequency region along with a linear tail
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in the low frequency area before charge/discharge process and after 50th and 100th cycles. Impressively,

the charge transfer resistance (Rct) shows slight increase from 97.9 Ω (initial status) to 104.5Ω (50th

cycle) and 106.3 Ω (100th cycle) along with the cycling process, suggesting the high structural integrity

of the Sn@PNGC. To further reveal the diffusion kinetics of Li+ in the electrode, the trend of the Li+

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diffusion coefficient determined is given based on EIS at different cycling status. As shown in Fig. S6,

the slope of the lines between Z’ and ω−1/2 suggests a slight increase with the cycling. Because σ2 (σ

represents the Warburg factor) is in inverse ratio to the diffusion coefficient of Li+ (DLi) [50], DLi in the

electrode exhibits a slight decrease during the cycling process. In overall, the variation of DLi is

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relatively stable. Besides, the Sn@PNGC electrode suggests better rate capability than Sn@C at all the

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tested current densities from 100 mA g−1 to 3000 mA g−1 (Fig. 5e and Fig. S7). The reversible capacities

of the electrode are 629 mAh g−1, 547 mAh g−1, 469 mAh g−1, 351 mAh g−1, and 254 mAh g−1. More

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importantly, the reversible capacity can return to 676 mAh g−1 when the current density decreases to 100

mA g−1, demonstrating the unique structural advantage of the Sn@PNGC anode. Moreover, the

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electrode can still deliver a high reversible capacity of 437 mAh g−1 after 300 cycles at 500 mA g−1,
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which further demonstrates the cycling stability of the Sn@PNGC electrode.

Additionally, the long-term cycling performance of the Sn@PNGC electrode at a higher current
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density of 1000 mA g−1 is also investigated, and the result is shown in Fig. 6. Impressively, after the
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initial capacity decay for several cycles, the discharge capacity of the Sn@PNGC electrode could
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remain at about 223 mAh g−1 even after 400 cycles, demonstrating the excellent electrochemical

performance of Sn@PNGC in LIBs. Moreover, surface SEM images of the cycled electrode was
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examined to make sure that the Sn@PNGC electrode basically keeps stable after repeated Li+

insertion/extraction. As shown in Fig. S8, the cycled electrode basically keeps stable without obvious
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structural damage and the active materials are still mixed well with conductive carbon black and
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polyvinylidene fluoride, indicating that the aggregation and volume expansion of Sn NPs are effectively

alleviated during repeated cycling.

In comparison with other reported Sn-based anode materials in LIBs, the Sn@PNGC electrode

presents promising Li+ storage performance with high specific capacity, excellent cycling stability and

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enhanced rate capability (Table 1), which results from the unique porous N-doped graphene-like

network structure, with well-dispersed metallic Sn embedded in the conductive carbon matrix. The

relevant mechanism of the Sn@PNGC and Sn@C electrodes upon the cycling process is depicted in Fig.

7. Firstly, the graphene-like network of Sn@PNGC can further provide the metallic Sn superior

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electrical conductivity, leading to enhanced Li+/electron transport kinetics upon the electrochemical

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reaction process. Secondly, the small dimensions of metallic Sn NPs can reduce the strain associated

with large volumetric expansion and bring improved electrochemical activity of Sn. Thirdly,

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nitrogen-doping in Sn@PNGC can increase electrical conductivity and induce defect sites/vacancies,

which is conducive to the lithium storage. Besides, the unique porous architecture is responsible for the

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enhanced active sites, and reduced Li+ migration distance as well as sufficient space to accommodate the
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volume expansion upon the cycling process, leading to an improved electrochemical performance of

LIBs.
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4. Conclusions
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In summary, a novel porous Sn-carbon composite with metallic Sn NPs embedded in the porous
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N-doped graphene-like carbon network was prepared via one-step thermal reaction. Taking the merits

from the unique porous N-doped graphene-like network with well-dispersed metallic Sn embedded in
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the conductive carbon matrix, the Sn@PNGC composite suggests improved Li+ accessibility and

electrical conductivity, along with sufficient space for the accommodation of volume variation during
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the lithiation/delithiation process. The as-assembled electrode demonstrated promising Li+ storage
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performance, including high specific capacity, excellent cycling stability and enhanced rate capability.

Moreover, this one-step synthesis approach of porous Sn@PNGC composite provides a promising

potential in the scalable fabrication of advanced Sn-based anode materials for LIBs.

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Acknowledgements

Financial supports from NSF of China (51532002, 51372022, 51575030), 973 Project

(2015CB932500), and State Key Laboratory of New Ceramic and Fine Processing Tsinghua University

are gratefully acknowledged.

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Figure captions:

Fig. 1. Schematic illustration of the fabrication process for the Sn@PNGC composite.

Fig. 2. (a) XRD patterns of as-synthesized Sn@PNGC and Sn@C composites, (b) TGA curve of the

Sn@PNGC composite, (c) XPS spectra of the Sn@PNGC composite, (d) High-resolution C1s XPS

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spectra of the Sn@PNGC composite, (e) High-resolution N1s XPS spectra of the Sn@PNGC composite,

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(f) High-resolution Sn3d XPS spectra of the Sn@PNGC composite.

Fig. 3. (a) FE-SEM images, (b–c) TEM images, (d) HRTEM image, and (e–g) EDS mapping of the

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Sn@PNGC composite.

Fig. 4. (a) N2 adsorption and desorption isotherms of the Sn@PNGC composite at 77 K, (b) Pore size

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distribution of the Sn@PNGC composite measured by BJH adsorption.
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Fig. 5. (a) CV curves of a LIB cell with Sn@PNGC electrode in the former three cycles at a constant

scanning rate of 0.2 mV s−1 in the voltage range from 0.01–3.0 V (vs. Li/Li+), (b) Charge-discharge
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curves of a LIB cell with Sn@PNGC electrode tested at a current density of 100 mA g−1, (c) Cycling
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performance of LIBs with Sn@PNGC and Sn@C electrodes at 100 mA g-1, (d) Electrochemical
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impedance spectra of Sn@PNGC electrode before charge/discharge process and after 100th cycles, (e)

Rate capability of LIBs with Sn@PNGC electrode at various current densities.

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Fig. 6. Long-term cycling performance of the Sn@PNGC electrode at 1000 mA g−1.

Table 1. Comparison of electrochemical performance of Sn@PNGC in this work with that of other
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reported Sn-based anode materials for LIBs.

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Fig. 7. Schemes of the relevant volume variation of the Sn@PNGC and Sn@C electrodes upon the

cycling process. (a) Volume expansion of metallic Sn in the Sn@C composite during lithiation can lead

to the dissolution Sn particles. Seriously, the fracture of carbon shell and aggregation of Sn NPs. (b) the

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unique porous architecture of Sn@PNGC can provide metallic Sn NPs sufficient space to accommodate

the volume expansion upon the cycling process, ensuring the integrity of structure.

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Fig. 1.

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Table 1

Sample Current density Cycles Capacity Ref.

Sn-MS-C 100 mA g−1 50 520 mAh g−1 [21]

Sn-CNT NCs 100 mA g−1 10 536 mAh g−1 [23]

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Sn/SnO2@C 100 mA g−1 100 591 mAh g−1 [51]

3D sphere-caged Sn/C 0.5C 200 885 mAh g−1 [52]

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Sn/C nanocapsules 100 mA g−1 100 585 mAh g−1 [53]

Sn@C 50 mA g−1 100 520 mAh g−1 [54]

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Sn@C–GNs 75 mA g−1 100 566 mAh g−1 [55]

Sn HNS 100 mA g−1 50 516.1 mAh g−1 [56]

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Sn/Cu foam 100 mA g−1 50 476.4 mAh g−1 [57]
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3D Sn@G-PGNWs 200 mA g−1 100 1089 mAh g−1 [58]

Sn-filled CNTs 100 mA g−1 100 437.5 mAh g−1 [59]

100 mA g−1 481 mAh g−1

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Sn@N-RGO 100 [60]

G/Sn/G 50 mA g−1 60 590 mAh g−1 [61]

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Sn@PNGC 100 mA g−1 100 595 mAh g−1 This work

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Research highlights

1. A novel porous Sn-carbon composite was prepared via one-step thermal reaction.

2. Sn NPs can be embedded in the porous N-doped graphene-like carbon network.

3. The strategy for the composite is suitable for scalable fabrication.

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4. The composite electrode delivers a high capacity of 1129 mA h g−1 at 100 mA g−1.

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5. The composite electrode exhibits improved stable ability and rate capability.

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