Electrochimica Acta 334 (2020) 135619

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Facile, economical and environment-friendly synthesis process of

porous N-doped carbon/SiOx composite from rice husks as
high-property anode for Li-ion batteries
Jinlong Cui a, Haibang Zhang a, b, **, Yunying Liu a, Shaohui Li c, Wenxiu He a,
Jiangliang Hu d, Juncai Sun b, *
a
Inner Mongolia Engineering Research Center of Comprehensive Utilization of Bio-coal Chemical Industry, Inner Mongolia Key Laboratory of Coal Chemical
Engineering & Comprehensive Utilization, School of Chemistry and Chemical Engineering, Inner Mongolia University of Science & Technology, Baotou,
014010, China
b
Institute of Materials and Technology, Dalian Maritime University, Dalian, 116026, China
c
College of Materials Science and Engineering, Zhengzhou University, Zhengzhou, 450001, China
d
Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Taiyuan, 030024, China

a r t i c l e i n f o a b s t r a c t

Article history: To enhance electrochemical properties of C/SiOx composite for business application, N-doped carbon/
Received 25 November 2019 SiOx composite has been successfully fabricated using rice husks as the raw material of both C and Si
Received in revised form sources and urea as N source via an environmentally friendly and economically viable strategy. The
22 December 2019
obtained N@C/SiOx composite exhibits a porous irregular particle morphology with a high specific sur-
Accepted 2 January 2020
Available online 3 January 2020
face area. SiOx particles are uniformly dispersed in N-doped C skeleton. As an anode material for Li-ion
batteries, the porous structure, N doping and high reduction degree of SiO2 endow N@C/SiOx electrodes
with an outstanding reversible capacity up to 1018.5 mAh/g at 0.1 A/g and a remarkable initial coulombic
Keywords:
N@C/SiOx
efficiency of 72.2%, which is larger than that of carbonized rice husks (45.7%). Even if the current density
Rice husks rises to 1.0 A/g, the reversible specific capacity can maintain at 623.3 mAh/g with a capacity degradation
Li-ion batteries of merely 4.0% after 1000 cycles.
Anode material © 2020 Elsevier Ltd. All rights reserved.
High-performance

1. Introduction lithium intercalation potential and low-cost. In conventional view,

each C6 ring of graphite can only connect with one Liþ, resulting in a
Highly efficient electrochemical energy storage systems are in low theoretical capacity of 372 mAh/g [4]. Thence, many new high-
high demand with the ever-increasing development of electrical performance anode materials have been prepared to act as the new
vehicles (EVs) and mobile devices [1]. In recent years, the wide- generation anodes of LIBs [5e7]. Among these anode materials,
spread applications of plug-in hybrid EVs has extremely promoted silicon oxide materials (SiOx, 0 < x < 2) have drawn the special
the global research interests to exploit Li-ion batteries (LIBs) with interest of many researchers on account of their high specific ca-
an outstanding rate capability, reversible capacity, and cycling pacity [8], and relatively small volume expansion during the lith-
stability [2]. The performance of LIBs depends mainly on the iation/delithiation process [9]. Nonetheless, SiOx, which is
characteristics of active materials utilized in the electrodes. The semiconductor, possesses a poor electronic conductivity, directly
anode material plays a vital role in the aspects of the safety per- restricting its electrochemical performance [10]. In addition, while
formance and specific capacity of LIBs [3]. Graphite is the most the volume expansion of SiOx is much smaller than that of pure Si,
common commercial anode material for LIBs due to its lower SiOx particles still have approximately 200% volume expansion
during the charging/discharging process [11]. These two drawbacks
severely limit the commercial application of SiOx anode materials.
* Corresponding author. To surmount the aforementioned shortcomings, numerous
** Corresponding author. Institute of Materials and Technology, Dalian Maritime efficacious approaches have been employed to improve the elec-
University, Dalian, 116026, China.
tronic conductivity and relieve the volume changes of the SiOx
E-mail addresses: [email protected] (H. Zhang), [email protected]
(J. Sun).
anode materials. These strategies include the construction of

https://doi.org/10.1016/j.electacta.2020.135619
0013-4686/© 2020 Elsevier Ltd. All rights reserved.
 2 J. Cui et al. / Electrochimica Acta 334 (2020) 135619

Scheme 1. Green synthesis and structure of N@C/SiOx composite.

nanostructured and porous SiOx [12,13], and the synthesis of SiOx- expansion of the SiOx particles. In addition, the porous structure of
based composite materials [14]. Among them, the nanostructured the N@C/SiOx composite can efficaciously alleviate the mechanical
and porous structures of SiOx anode materials could obviously in- strain caused by the volume shrinkage and swelling of the SiOx
crease their specific surface area (SBET) and thus provide more particles during Liþ insertion/extraction process and facilitate the
available Liþ storage sites [12]. Moreover, these structures could diffusion of Liþ between the electrolyte and N@C/SiOx. Finally, the 改善

also shorten the transmission paths of Liþ and electrons and thus presence of N atoms can also increase the reversible specific ca-
effectively improve the electronic conductivity of the SiOx anode pacity and initial CE of the C/SiOx electrode. Therefore, the obtained
materials [15]. It is more important that these structures could N@C/SiOx anode materials displayed a larger specific capacity of
effectively mitigate the volume expansion of the SiOx particles 1018.5 mAh/g and an ameliorative initial CE of 72.2% at 0.1 A/g. The
during the charging/discharging process [16]. Another appealing raw material and activating agent all have no pollution to the
approach for improving the electrochemical performance of SiOx- environment or harm to the human health. Moreover, the entire
based anode materials is to manufacture core-shell composites by production process is a zero emissions and zero pollution process.
coating SiOx nanoparticles with a conductive layer of C or a C matrix This work could offer an economical and environment-friendly way
[9]. C coatings/matrixes are especially attractive since they could to convert RHs into commercial LIB electrode materials.
relieve the volume expansion of the SiOx electrode during cycling,
and therefore, could enhance the electronic conductivity of the 2. Experimental methods and materials
electrode and impede the agglomeration of the SiOx nanoparticles
[15]. Thus, C/SiOx composites with different morphologies and 2.1. Synthesis of N@C/SiOx composites 尿素
structures were synthesized by using chemical reagents [17,18], and 干燥
silicon-containing biomass [15,19]. Furthermore, heteroatoms 杂原子 RHs were obtained from a rice mill in Liuzhou City, China. The
(such as P, N and B) doped carbon can effectively improve the ingredients of RHs are enumerated in Table S1. Urea was purchased
electrochemical performance of the C-based anodes. That is from Aladdin and its analytical purity was not further purified. The
because the presence of heteroatoms at the C surface can improve RHs were washed with triple distilled water to eliminate any
伪，假
的
the electrical conductivity, and provide pseudo-capacitance and adhering dust and soil. After desiccated at 105  C in an electro-
extra Liþ storage sites [20]. In addition, these heteroatoms can also thermal blowing dry box for 24 h, the cleaned RHs were grinded
inhibit the decomposition of the electrolyte and the surface side into 70 mesh powder. The obtained RHs powder was soaked in urea
reactions between the C electrode and electrolyte to some extent solution for 20 h with a weight ratio of RHs powder to urea of 9:1,
and thus improve the initial Coulomb efficiency (CE) of the elec- 8:2 and 7:3 at room temperature. The immersed RHs were dried at
trode [21,22]. Of note, N atoms, which possess a comparable atomic 80  C over night and then heated from ambient temperature to
size and five valence electrons for bonding with C atoms, have been 550  C with a heating speed of 10  C/min under N2 atmosphere in a
extensively used for the doping of C-based materials [23]. tubular furnace. Being calcined at 550  C for 2 h and naturally
Rice husks (RHs) are mainly composed of organic cellulose, cooled to ambient temperature, the obtained products were
hemicellulose, lignin, and inorganic Si compound (Table S1). denoted as S9-1, S8-2 and S7-3, respectively. The carbonized rice
Therefore, RHs can be used to prepare low-cost electrode materials, husks (CRH) sample was achieved in a similar process without
such as carbonaceous and silicon-based anode materials. Several adding urea during the formation procedure.
studies have explored the synthesis of anode materials by using C
[24,25] and nanostructured Si [26,27] with RHs as raw materials. 2.2. Characterization
Moreover, silica, which naturally exists as nanoparticles, is assim-
ilated from soil in the form of silicic acid during the growth of rice. N2 adsorption/desorption isotherms were received using Bru-
Silica is uniformly deposited on the cell wall material as a polymer nauereEmmeteTeller (BET) analysis at 77 K via an Quantachrome
of hydrated and amorphous silica. Thus, silica is homogeneously Autosorb NOVA2200e analyzer. X-ray diffraction (XRD, Rigaku, D/
coated by the disordered C generated during the carbonization of max-A with Co-Ka radiation) was employed to identify the phase
RHs under an N2 atmosphere without any complex C coating structure. Raman spectra were obtained using a Digilab FTS3500
technology [15]. Here, we synthesized porous N-doped carbon/SiOx from Bio-Rad with a laser wavelength of 532 nm. The chemical
(N@C/SiOx) composite using RHs as the raw material of both C and state and electronic binding energy of CRH and N@C/SiOx samples
Si source and urea as N source via a facile, economical and were examined via X-ray photoelectron spectroscopy (XPS, Perki-
environment-friendly synthesis process(Scheme 1). In the obtained nElmer PHI 1600 ESCA). The morphology of resulting N@C/SiOx
N@C/SiOx composite, SiOx particles are uniformly dispersed in N- sample was observed by TEM (JEOL, 2100F) and field-emission SEM
doped C skeleton, which can effectively improve the electronic (SUPRA-55, CARL ZEISS) equipped with EDS (X-Max, OXFORD). The
conductivity of N@C/SiOx composite and alleviate the volume O and N contents of CRH and N@C/SiOx samples were measured via
 J. Cui et al. / Electrochimica Acta 334 (2020) 135619 3

O/N/H analyzer (LECO, ONH836), and their C content through C/S using CRH as anode and commercial LiCoO2 as cathode with the
analyzer (LECO, CS230). The contents of metallic element impu- before-mentioned method. The mass loading of CRH composite is
rities (e.g., Zn, Ca, Na, Mg, Fe, and K) of CRH and N@C/SiOx samples the same as N@C/SiOx anode slice in the N@C/SiOx/LiCoO2 battery.
were measured via inductively coupled plasma (ICP)-optical The capacity of LiCoO2 cathode slice was also 0.792 mAh, while that
emission spectrometer (Optima 2000DV). The amount of Si was of CRH anode slice is 0.239 mAh. Thence, the final full batteries are
calculated as a difference to 100%. all anode-limited and the specific capacities of these full batteries
are calculated according to the mass of active substance on the
anode slices. The electrochemical tests were performed between
2.3. Electrochemical measurement
2.2 and 3.7 V for complete anode-limited full batteries at a constant
current density of 1.0 A/g with respect to the anode mass on the
The electrochemical properties of the CRH and N@C/SiOx sam-
LAND-2100 battery test system.
ples were investigated by using them as anode materials in LIBs in
coin-type half-cells, which were laboratory-assembled by a CR2025
press in an argon-filled glove box. The working electrodes were 3. Results and discussion
fabricated using polyvinylidene fluoride (PVDF) as binder and N- 等温线 微孔 介孔
methylpyrrolidinone (NMP) as solvent. A mixture of active mate- N2 adsorption/desorption isotherms were performed to inves-
rials (80 wt%), PVDF (10 wt%), and C black (10 wt%) was prepared by tigate the porosity of the synthesized samples. The N@C/SiOx
grinding them for 60 min with the proper amount of NMP. The samples display combined type II isothermals with H3 hysteresis
resultant slurry was then homogeneously coated on a Cu foil cur- loops at the relative pressure (P/P0) of 0.5e1.0 (Fig. 1a), which in-
rent collector which was subsequently dried overnight in vacuum. dicates that they are microporous and mesoporous materials [28].
水平
The mass loading of the N@C/SiOx composite was in the range of Nevertheless, the isotherm curve of CRH is an approximately hor-
1.6e2.0 mg/cm2. A lithium foil was used as the counter electrode izontal line, demonstrating that CRH has few pores in it [29]. The
and reference electrodes, and Celgard 2300 was used as the sepa- S7-3 sample possesses the largest pore volume and biggest SBET in
rator. A 1 M LiPF6 solution in ethylene carbonate (EC), diethyl car- all analysed N@C/SiOx samples (Table S2). Moreover, the SBET and
bonate (DEC), and ethyl methyl carbonate (EMC) with a volume pore volume of the N@C/SiOx samples gradually increase with the
ratio of 1:1:1 was used as the electrolyte. The cells were galva- increase of doping urea content, which is probably due to the
nostatically charged and discharged in the voltage range from activation of higher urea content to produce more pores. Fig. 1b
0.005 V to 3.0 V (versus Li/Liþ) at different current densities at room exhibits the homologous pore size distribution curves of all N@C/
temperature on a LAND-2100 battery test system. Cyclic voltam- SiOx samples and their pore type is mainly mesoporous. This hi-
metry (CV) measurements were conducted using an electrochem- erarchical porous structure can promote the diffusion transfer of
istry workstation (CHI760E) over the potential range of 0.005e3.0 V the electrolyte, and then efficaciously accelerate the transmission
vs. Li/Liþ at the scan rate of 0.05 mV/s. Electrochemical impedance of Liþ [15]. Beyond that, these porous structures can also effectually
spectroscopy (EIS) data were also acquired using the same equip- alleviate the volume expansion of the SiOx nanoparticles during Liþ
ment at a frequency region from 0.01 to 100 kHz. insertion/extraction process [30]. In addition, the big SBET of the
A full battery was assembled by using the as-synthesized N@C/ N@C/SiOx samples can provide more available Liþ storage sites [31].
SiOx as anode and commercial LiCoO2 as cathode (Shanghai ND The XRD spectra of CRH and N@C/SiOx samples are shown in
Energy Technology Co. Ltd, China) in the coin-type CR2025 cell. An Fig. 2a. These samples exhibit similar diffraction features with a
organic solution of 1.05 M LiPF6 in a mixture of EC, DEC and EMC (v/ 无定形broad diffraction peak centered at approximately 27, which is
v/v ¼ 1:1:1) served as the electrolyte and a Celgard 2300 mem- corresponded to the overlapping peak of amorphous C and SiOx
brane was used as the separator. To make a full battery, copper and [32]. Furthermore, a weak diffraction peak around 51 is designated
aluminum foil as the current collectors were jointed to the side of to amorphous C [33]. More remarkably, the 27 diffraction peaks of
anode and cathode electrodes, respectively. Nickel foam was all N@C/SiOx samples have no significant fluctuations compared to
applied as a filler. The capacity of LiCoO2 cathode slice was 0.792 that of CRH, demonstrating that adding urea does not distinctly
mAh, which is much higher than that of N@C/SiOx anode slice change the lattice spacing of CRH. That may be because N atoms are
(0.407 mAh). For comparison, a full battery was also assembled by close to C atoms in size, and thus do not obviously change the lattice

Fig. 1. (a) N2 adsorption/desorption isotherm curves and (b) Pore size distributions of CRH, S9-1, S8-2 and S7-3.
 4 J. Cui et al. / Electrochimica Acta 334 (2020) 135619

Fig. 2. (a) XRD patterns and (b) Raman scattering patterns of CRH, S9-1, S8-2 and S7-3.

积分
spacing of the C skeleton after N doping [34]. The Raman spectra of some defects into C skeleton of N@C/SiOx samples and thus
CRH and N@C/SiOx samples possess two typical Raman bands improve their Liþ storage capacity [42]. While, graphite N atoms
(Fig. 2b), which are designated to the known D-band (1327.5 cm1) could accelerate the transportation of electric charges and improve
and G-band (1564.1 cm1), respectively. The integral areas value the electric conductivity of anode material [43,44].
ratio of D-band to G-band (ID/IG) is usually used to evaluate the As far as Si 2p XPS patterns of CRH and S9-1, the wide peaks can
number of defects in C materials [35,36]. The ID/IG of all N@C/SiOx be divided into three independent peaks at BE ¼ 104.51, 103.62 and
samples is larger than that of CRH, implying that the defects can be 102.81 eV, which are allocated to Si4þ, Si3þ, and Si2þ, respectively
introduced into C skeleton of N@C/SiOx composites during the urea [17]. While, the Si 2p XPS patterns of S7-3 and S8-2 can be fitted to
doping process. The relatively increased intensity of the D band for four peaks, which are designated to Si4þ, Si3þ, Si2þ and Siþ (Fig. S2).
all N@C/SiOx samples demonstrates that the content of disordered These results demonstrate that there are different molecular
C increases after N doping process [37]. Disordered C structure can structures of Si in N@C/SiOx, which is attributed to the carbo-
effectively increase the storage sites of Liþ [38], and then enhance thermal reduction reaction between SiO2 and C during calcining
the specific capacity of these N@C/SiOx samples. process [45]. Moreover, as the doping urea content increased, the
Except a small amount of metal impurities, C, O, Si, and N ele- relative content (atom %) of Si atoms with lower oxidation states
ments were identified in the N@C/SiOx samples (Table S3), which (Si2þ and Siþ) gradually increases firstly and then decreases
demonstrates that N atoms have been successfully introduced into (Table S4), illustrating that the reduction degree of SiO2 by C pro-
the N@C/SiOx samples during the urea activation process. gressively strengthens firstly and then weakens [46]. When the
Conversely, only the presence of C, Si, and O was detected in CRH weight ratio of RHs powder to urea is 8:2, the relative content
(Table S3). These results were further proved by XPS tests (Fig. 3 (atom %) of Si atoms with lower oxidation states (Si2þ and Siþ)
and Fig. S1). The intensity of the N1s peaks in the XPS patterns of reaches the highest value. There may be two important reasons for
the N@C/SiOx samples decrease with the decrease of doping urea these phenomena. First, the porous structure of the N@C/SiOx
一致
content, which is in conformity with element composition of N@C/ samples is beneficial to the release of CO and thus accelerates the
SiOx samples (Table S3). To acquire further insights into the struc- carbothermal reduction reaction between SiO2 and C
ture of the N@C/SiOx samples, their N 1s XPS patterns are decon- (SiO2þC/SiOx þ CO[) [47]. Therefore, the reduction degree of SiO2
voluted (Fig. 3d and e). Since the XPS peak intensity of S9-1 in the strengthens with the SBET of N@C/SiOx samples increasing. Second,
N1s binding energy (BE) range is too weak, we do not make a some C atoms of RHs are consumed during the activation process of
detailed analysis of it in this paper. There are four N functional urea. Thus, the number of C atoms around SiO2 nanoparticles de-
groups in N-doped C skeleton of S7-3 and S8-2. These include 协同 creases with the porosity of N@C/SiOx samples increasing and thus
吡咯
pyridine N (BE ¼ 399.3 ± 0.3 eV), pyrrole N (BE ¼ 400.3 ± 0.3 eV) the reduction degree of SiO2 weakens [45]. To sum up, these two
[39], graphite N (BE ¼ 401.3 ± 0.3 eV), and NeO of pyridinic-N factors have a synergy on the reduction degree of SiO2 by C. As a
五边形的
(BE ¼ 402.2 ± 0.3 eV, pyridinice(NþeOe)) [40]. Among them, N result, the reduction degree of SiO2 for sample S8-2 is biggest in this
六价的 atoms in the pentagonal pyrrole ring are bonded to two C atoms three N@C/SiOx samples.
吡啶
and provide two p-electrons for the aromatic p system. N atoms in Fig. S3 displays the XPS pattern of the CRH and N@C/SiOx
the hexatomic pyridine rings connect with two C atoms, donate one samples in the C 1s BE range. The C atoms with BE ¼ 286.20 or
p-electron to the p bond and locate at the edge of graphite struc- 287.13 eV can be easily identified in the XPS patterns of the N@C/
ture and the defect of C skeleton [37]. In addition, graphite N atoms SiOx samples, demonstrating the presence of C]N and CeN
are introduced into the graphene sheet and substitute C atoms chemical states [40]. Except for these two peaks, there are other
within a graphene plane. N atoms in the pyridinice(NþeOe) are four individual component peaks at BE ¼ 284.38, 284.86, 285.39,
linked with one O atom and two C atoms [41]. The N molecular 288.81 eV in the XPS patterns of CRH and N@C/SiOx samples, which
segments of C skeleton in the N@C/SiOx samples described thus far are assigned to CeC sp2, CeH, CeC sp3 and HOeC]O bonds,
are shown in Fig. 3f. Except for graphite N, the presence of N atoms respectively [37]. However, no peaks are found below 284 eV in the
in the other three chemical states mentioned above can introduce XPS patterns of the CRH and N@C/SiOx samples, indicating that no
 J. Cui et al. / Electrochimica Acta 334 (2020) 135619 5

Fig. 3. Wide survey XPS patterns of (a) S7-3, (b) S8-2 and (c) S9-1; High-resolution XPS patterns of N 1s (d) S7-3 and (e) S8-2; (f) Illustration of N-doped C skeleton with different
doping sites.

改善的 杂化
电负性 归因于
SieC bands were formed during the urea activation process [48,49]. S8-2 electrode are much higher than those of the C/SiOx composites
Fig. 4a exhibits the cyclic performance of CRH, S7-3, S8-2, and prepared using chemical reagents as raw materials (Table S5). The
S9-1 as LIBs anodes at 0.1 A/g for 100 cycles. Noticeably, the ameliorative reversible specific capacity and initial CE of these
reversible specific capacity of the N@C/SiOx samples increases N@C/SiOx electrodes may be ascribed to the following factors. First,
remarkably after urea doping. The first discharged specific capacity the strong electronegativity of N and the hybridization of N lone
and initial CE of the S8-2 electrode can reach 2225.2 mAh/g and pair electrons with the p electrons in C skeleton make favorable
72.2%, respectively, which are higher than those of the CRH, S7-3 binding sites for Liþ storage [50]. Second, the introduction of N
and S9-1 electrodes (Fig. 4a and Fig. S4). Even after 100 cycles, atoms also creates more defects in the C skeleton, which subse-
the discharge specific capacity of the S8-2 electrode still remains quently generates more Liþ storage sites [42]. Third, the bigger the
1018.5 mAh/g. The initial CE and discharge specific capacity of the reduction degree of SiO2 in N@C/SiOx, the larger its reversible

Fig. 4. (a) Cyclic stability test at 0.1 A/g for 100 cycles and (b) Nyquist plots after 100 cycles of CRH and N@C/SiOx electrodes.
6 J. Cui et al. / Electrochimica Acta 334 (2020) 135619

specific capacity [15]. Fourth, the big SBET of the composites can ascribed to the charge transfer resistances and the solid electrolyte
provide more available Liþ storage sites [31]. Finally, graphite N interface (SEI) film resistance, and one tilted straight line at low
only has a smaller specific capacity, so N@C/SiOx, which contains frequency associated with the Warburg impedance during Liþ
more graphite N, has a smaller specific capacity [51]. While, sample diffusion process [53,54]. Therefore, the smaller the diameter of the
S7-3 has more graphite N than sample S8-2. To sum up, these five semicircle is, the better the electronic conductivity of the related
factors have a cooperative action on the specific capacity of the material. Obviously, the semicircle diameters of N@C/SiOx elec-
N@C/SiOx electrodes. Hence, S8-2 possesses the biggest reversible trodes are smaller than that of CRH electrode, implying that the
specific capacity of all composite samples. charge transfer resistances of the N@C/SiOx electrodes are relatively
The hierarchical porous N@C/SiOx composites, which have a thin low. In addition, the charge transfer resistances of the N@C/SiOx
pore wall, can form an interconnected porous network structure, electrodes decrease as the amount of urea used for doping with the 并入
avoid the generation of irreversible Liþ intercalation sites, and thus increased. These phenomena were attributed to several factors.
improve their initial CE to a certain extent [52]. Furthermore, N Firstly, the incorporation of N atoms can create defects in the C
atoms can restrain the decomposition of the electrolyte and the skeleton, which can increase the electronic conductivity of the
surface side reactions between the C electrode and electrolyte to N@C/SiOx composites [42]. Secondly, the S7-3 composite contains
some extent, and thus, the initial CE of the electrode could increase more graphitic N than the other composites, which can ameliorate
after N doping [22]. Finally, the O/Si atomic ratio of the C/SiOx its electronic conductivity [51]. Last but not least, the high SBET and
composites is also an important factor affecting the initial CE of C/ large pore volume of the N@C/SiOx composites can not only provide
SiOx electrodes. The smaller the O/Si ratio of a material is, the less more available Liþ storage sites [31], but can also supply more
Liþ are expended by the formation of Li4SiO4 and Li2O during the effective ionic transport pathways to promote the diffusion of Liþ
first discharge process, and thereby the bigger the initial CE of the [55], hence obviously increasing the specific capacities of the N@C/
material is [15,46]. Consequently, the bigger reduction degree of SiOx composites and improving their electric conductivity.
SiO2 in the N@C/SiOx composites could mitigate Liþ consumption in As displayed in Fig. 5a and b, S8-2 shows an irregular bulk
the irreversible reaction of SiOx and can ameliorate the initial CE of particle morphology with many pores on its surface, which is in
the N@C/SiOx electrode. The combination of these three factors led accordance with BET results (Fig. 1 and Table S2). The EDS mapping
to the S8-2 electrode presenting the highest initial CE of all N@C/ distinctly displays that C, Si, O and N atoms are uniformly distrib-
SiOx electrodes in this study (Fig. S4). In order to further study the uted in the S8-2 composite (Fig. 5c), which certificates that N atoms
electrochemical behavior, EIS characterization for CRH, S9-1, S8-2 are evenly doped in the N@C/SiOx sample. Fig. 5d distinctly reveals
and S7-3 electrodes were recorded (Fig. 4b). The Nyquist plots are that SiOx particles are uniformly dispersed in C skeleton of the
consisted of one depressed semicircle at high frequency, which was N@C/SiOx sample, and some pores are observed on the surface of

Fig. 5. (a) and (b) SEM morphologies, (c) EDS mappings of C, O, Si, and N, (d) TEM image, (e) HRTEM image and (f) selected area electron diffraction (SAED) patterns of S8-2.
 J. Cui et al. / Electrochimica Acta 334 (2020) 135619 7

Fig. 6. (a) CV curves for the first 5 cycles, (b) Charge/discharge curves at 0.1 A/g, (c) Nyquist plots before cycling and after 5th, 30th, 70th, 90th, 100th cycle in the discharged state,
and (d) Rate performance curves of S8-2 electrode.

N@C/SiOx sample, which are in line with the SEM morphology and increases, owing to the activation of the N@C/SiOx electrode. After
EDS mapping analysis results. These structures will be beneficial to 100 cycles, the resistance of the S8-2 electrode is stable at
ameliorate the electronic conductivity of the N@C/SiOx samples and approximately 70 U, and does not further increase, illustrating that
effectively alleviate the aggregation of SiOx particles during the Liþ the S8-2 electrode can perform a commendable electrochemical
insertion/extraction process [32]. We can find that there are no reaction in the charge/discharge process. The rate performance of
obvious lattice fringes in the HRTEM image of S8-2 (Fig. 5e). And the S8-2 electrode at various current densities from 0.1 A/g to 1.6 A/
thus, N@C/SiOx sample is amorphous, which is further proven by g was recorded to further estimate its electrochemical properties
SAED patterns of S8-2 (Fig. 5f). (Fig. 6d). The S8-2 electrode displays an excellent rate performance
Fig. 6a displays the CV curves for S8-2 electrode explored at the with discharge capacities of 946.6 mAh/g at 0.2 A/g, 835.8 mAh/g at
scan rate of 0.05 mV/s in the voltage window of 0.005e3.0 V for the 0.4 A/g, 719.8 mAh/g at 0.8 A/g, 612.4 mAh/g at 1.0 A/g, 549.3 mAh/g
first 5 cycles. Two reduction peaks at 1.0e1.3 V and 0.7 V appear in at 1.2 A/g and 447.3 mAh/g at 1.6 A/g, respectively. Additionally,
the first cycle, both of which disappear in the subsequent cycles. after the current density returns to 0.2 A/g and 0.4 A/g, the capacity
The peak at 1.0e1.3 V is associated with the irreversible reactions of S8-2 electrode can still maintain at 935.2 and 822.1 mAh/g,
between the electrolyte and electrode [32]. Meanwhile, the peak at respectively, indicating that the S8-2 electrode is not damaged
0.7 V is ascribed to the formation of the SEI film and decomposition during the high rate test. The specific capacity of the S8-2 electrode
of the electrolyte [56]. The sharp peak at about 0.8e1.2 V observed could still maintain at 623.3 mAh/g even at the high current density
during the anodic scan is attributed to the dealloying processes of of 1.0 A/g, and the capacity retention could stabilize at approxi-
LixSi and a part of Li2Si2O5 [30,57]. The cathodic peak at near 0 V mately 96% after 1000 cycles (Fig. 7). Figs. S5a and b display the
corresponds to the alloying process of SiOx [57,58]. The CV curves cycling performance of S8-2/LiCoO2 and CRH/LiCoO2 full batteries
nearly overlap from 2nd to 5th cycle, demonstrating extremely cycled between 2.2 and 3.7 V at 1.0 A g1, respectively. Obviously,
promising reversibility and stability of the S8-2 electrode. During the S8-2/LiCoO2 full battery shows an ameliorative cycling stability
the first cycle, the voltage drops rapidly and appears two plateau at compared with CRH/LiCoO2 full battery. The initial CE of S8-2/
about 0.7 and 1.2 V, which is identical with the initial CV curve LiCoO2 at 0.1 A/g is 75.60%, which is bigger than that of CRH/LiCoO2
(Fig. 6b). Moreover, the curves almost overlap from 5th to 100th (41.26%). The specific capacity of the S8-2/LiCoO2 full battery
cycle, attesting that the S8-2 electrode has the extraordinary maintains a nearly constant value of approximately 564.6 mAh/g
cycling stability. (Fig. S5a), which is a little smaller than S8-2 half-cell at 1.0 A/g.
To further understand the resistance change characteristics of For comprehensive acquaintance with the mechanical stability
the S8-2 electrode during the charge/discharge process, Nyquist of the N@C/SiOx electrodes, the SEM images of S8-2 electrode
plots were obtained before cycling and after the 5th, 30th, 70th, before and after cycling were carried out. Noticeably, a thin SEI film
90th and 100th cycle in the discharged state. From Fig. 6c, the was generated on the electrode surface after cycling (Fig. 8a and b).
charge transfer resistance decreases as the number of cycle Even after 100 cycles, the structure and morphology of N@C/SiOx
8 J. Cui et al. / Electrochimica Acta 334 (2020) 135619

Fig. 7. Long-term cycling stability at 1.0 A/g for 1000 cycles of S8-2 electrode.

Fig. 8. SEM images of S8-2 electrode (a) and (c) before cycle and (b) and (d) after 100 cycles. (c) and (d) are SEM images of transverse section of this electrode.

裂纹 脱皮

hold stable without any fissures and desquamation, and SEI film the volume expansion of the SiOx particles. In addition, the pres-
still remains firmly attached to the electrode (Fig. 8b). Meanwhile, ence of the N atoms in the composites could also increase the
much lower volume expansion of the N@C/SiOx electrode occurs specific capacity and initial CE of the C/SiOx electrode. The initial CE
after lithiation (Fig. 8c and d). These results indicate that the hier- of the N@C/SiOx electrode was 72.2%, and its specific capacity rea-
archical porous structure and N doped C skeleton of the N@C/SiOx ches up to 1018.5 mAh/g at 0.1 A/g. The N@C/SiOx electrode also
composite could efficiently hinder the agglutination of SiOx parti- displayed an outstanding cycling stability, with a remained specific
cles and relieve the volume expansion of materials [59]. capacity of 623.3 mAh/g at a higher current density of 1.0 A/g and a
凝集 coulombic efficiency of 99.8% after 1000 cycles. The entire pro-
4. Conclusion duction process was a zero emissions and zero pollution process.
Therefore, this facile, economical and environment-friendly syn-
Porous N@C/SiOx composites were synthesized via a facile, thesis approach for preparing N-doped C/SiOx composite could be
economical and environment-friendly synthesis process. The SiOx easily industrialized.
particles were evenly dispersed in the N-doped C skeleton of
porous the N@C/SiOx composites. Structure defects were intro-
duced into the C skeleton of the N@C/SiOx composites during N Notes
doping. The N-doped C skeleton could effectively improve the
electronic conductivity of the N@C/SiOx composites and alleviate The authors declare no competing financial interest.
 J. Cui et al. / Electrochimica Acta 334 (2020) 135619 9

CRediT authorship contribution statement composite from rice husks as an anode material for lithium-ion batteries,
Electrochim. Acta 191 (2016) 411e416.
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bang Zhang: Data curation, Resources. Yunying Liu: Funding high-performance supercapacitors, Nano Energy 25 (2016) 193e202.
acquisition, Visualization. Shaohui Li: Writing - review & editing. [21] Z.S. Wu, W. Ren, L. Xu, F. Li, H.M. Cheng, Doped graphene sheets as anode
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Wenxiu He: Formal analysis. Jiangliang Hu: Software, Validation. Nano 5 (7) (2011) 5463e5471.
Juncai Sun: Conceptualization, Methodology. [22] Y. Mao, H. Duan, B. Xu, L. Zhang, Y. Hu, C. Zhao, Z. Wang, L. Chen, Y. Yang,
Lithium storage in nitrogen-rich mesoporous carbon materials, Energy Envi-
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