Energy Technology

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Accepted Article
Title: Core-Shell Structured SiOx-C Composite for Lithium Ion Battery Anodes

Authors: Junying Zhang, Peipei Ma, Xiaoming Zhang, Zhi Liu, Jun Zheng,
Yuhua Zuo, Chunlai Xue, Buwen Cheng, and Chuanbo Li

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Energy Technology 10.1002/ente.201800800

Core-Shell Structured SiOx-C Composite for Lithium Ion

Battery Anodes

Junying Zhang[b], ‡, Peipei Ma[c], [d], ‡, Xiaoming Zhang[a] *, Zhi Liu[c], Jun Zheng[c],

Yuhua Zuo[c], Chunlai Xue[c], Buwen Cheng[c] and Chuanbo Li [a]

Accepted Manuscript
[a]
School of Science, Minzu University of China, Beijing 100081, China

[b]
School of Science, Beijing University of Chemical Technology, Beijing 100029,

China

[c]
State Key Laboratory on Integrated Optoelectronics, Institute of Semiconductors,

Chinese Academy of Sciences, Beijing 100083, China

[d]
Center of Materials Science and Optoelectronics Engineering, University of Chinese

Academy of Sciences, Beijing 100049, China

[email protected];[email protected];[email protected];[email protected];

[email protected];[email protected];[email protected];[email protected];cbli@s

emi.ac.cn

* Corresponding author: [email protected]

‡
These authors contribute equally.

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Energy Technology 10.1002/ente.201800800

Abstract

A simple method to synthesis a uniform composite material consists of

wet-milled SiOx core and carbon shell is studied. This SiOx-C core-shell composite is

then used as anode materials for lithium ion batteries, with wet-milled SiOx and raw

SiOx anodes as comparison. It is found that the batteries fabricated with wet-milled

Accepted Manuscript
SiOx-C composite show the best cyclic performance and excellent rate capability

compared with wet-milled SiOx and raw SiOx. This is benefit for the reduced size of

wet-milled SiOx powders. The coating of carbon shell is effective in improving the

conductivity of SiOx and relieving the volume effect during lithiation/delithiation

processes. Moreover, Li2O and Li4SiO4 generated in the first cycle will further

suppress the volume effects. Under galvanostatic mode with charging and discharging

current density of 0.1 Ag-1, wet-milled SiOx-C composite electrode delivers an initial

reversible capacity of 1279 mAhg-1, with an especially high capacity retention of as

large as 97.3% (1244 mAhg-1) even after 170 cycles and coulombic efficiency as high

as 99.8%. The approach is simple and has great potential for large scale production of

high performance SiOx-based anode materials.

1. Introduction

The rapid development of portable electronics, electrical vehicles and electricity

storage systems are making large demand for high capacity secondary lithium ion

batteries. As the most commonly used anode, graphite is very stable but its theoretical

specific capacity (372 mAhg-1) is insufficient for large capacity batteries. Among the

next generation high capacity anode materials, crystal Si is very outstanding due to its

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Energy Technology 10.1002/ente.201800800

much higher theoretical specific capacity (4200 mAhg-1, about ten times higher than

graphite), low Li+ alloying/dealloying potential, long discharge plateau and abundance

[1,2]
. However, the low intrinsic conductivity [3] and huge volume expansion/shrinkage

of Si particles during alloying/dealloying with Li+ results in the pulverization of the

electrode structure and further great capacity decay [4]. The pulverization will result in

Accepted Manuscript
lack of electronic contacts between Si particles and continuous growth of solid

electrolyte interphase (SEI) film even makes capacity fading worse and also decrease

[5]
the coulombic efficiencies (CEs) . To solve the above problems, many efforts have

been made on the synthesis and optimization of the material structure and composites.

Constructing nanostructured Si anode materials [6-14] or forming composites with other

[15-22]
active/inactive phases are very effective routes. But there is still a long way to

reach the requirement of practical applications for Si anode materials, as Si anodes

still impose great challenges in meeting various electrochemical performance

standards in full cells.

As an alternative anode material, SiOx has attracted special attentions recently,

[23, 24]
due to its high specific capacity and improved cyclic performance and also

[25]
adopted as commercial lithium ion battery products . SiOx has a structure of

embedded Si nanodomains in amorphous SiOx matrix and it will reduce the volume

effect of Si greatly during lithiation/delithiation processes [26]. Moreover, Li2O and

Li4SiO4, generated by the reaction of Li+ with SiOx anode during the first lithiation

process, can act as buffer components and further accommodate the volume

[27-30]
expansion, which lead to a superior cyclic performance compared to Si anode .

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Energy Technology 10.1002/ente.201800800

However, at present inevitable volume effect and poor electrical conductivity are still

the main issues limiting the performance of SiOx-based anode materials [31].

Here, we present a novel and simple method to synthesize a uniform and small

sized SiOx anode materials by high energy ball milling method with ethanol added in

the mixture during the milling process (labelled as wet-milling method). Combining

Accepted Manuscript
with carbon coating, eventually, a composite material with a structure of SiOx as core

and carbon as shell was obtained as core-shell structured SiOx-C composite. It was

then used as anode materials for lithium ion batteries and their electrochemical

performance was observed. It was found that the wet-milling method by introducing

of ethanol will effectively reduce the size of SiOx powder and it will greatly reduce

volume effect of Si during lithiation/delithiation processes. Moreover, the carbon

coating on the surface of SiOx powders helps to improve their conductivity. As a

result, the core-shell structured SiOx-C composite as anode for lithium ion battery

exhibits extremely stable cyclic performance and excellent rate performance.

2. Results and discussion

In Fig. 1(a), the SEM image shows that irregularly shaped wet-milled SiOx

particles were obtained with small size of all less than 5μm. As comparison in Fig.

1(b), pristine SiOx has larger size distribution with largest size of nearly 50μm and

smallest size of about 5μm, which indicates that after wet-milling, the sizes of SiOx

particles were effectively reduced and the sizes distribution were much more uniform.

The size distribution of wet-milled SiOx particles was also observed and showed in

Fig. S1 to further prove the result. The single peak at about 1.7μm indicates the

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Energy Technology 10.1002/ente.201800800

particle size is effectively reduced after the wet-milling process and the range of size

distribution is decreased largely, which is corresponding to the SEM results in Fig. 1.

Accepted Manuscript
Fig. 1 SEM images of (a) wet-milled SiOx particles and (b) pristine SiOx particles

Fig. 2 shows the TEM images of core-shell structured SiOx-C composite. On the

surface of the composite as shown in Fig. 2(a), a uniform amorphous carbon shell can

be found with thickness of about 10 nm. In the SiOx core, the obvious lattice planes

marked with red ellipses are related to the Si nanocrystals as shown in Fig. 2(b). The

nanocrystals also retained after the carbon coating process as shown in Fig. 2(a).

However, because of the large contrast between SiOx core and carbon shell, the Si

nanocrystals are not so obvious compared to the ones in Fig. 2(b). It clearly shows

that the Si nanocrystals are embedded in amorphous SiOx matrix and it will reduce the

volume effect of Si greatly. That is because the surrounding amorphous SiOx has

smaller volume effect compared with Si, which is benefit for the electrode stability

and good cyclic performance.

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Energy Technology 10.1002/ente.201800800

Accepted Manuscript
Fig. 2 TEM images of (a) wet-milled SiOx-C composite and (b) wet-milled SiOx (red

circles in (b) are related to Si nanocrystals)

Crystal structures were analyzed for wet-milled SiOx-C composite and raw SiOx

by observing the XRD patterns as shown in Fig. 3(a). The broad peaks at about 10°

[32-34]
and 23° are assigned to amorphous SiO2 . The peaks appearing at 2θ= 28.04°，

47.05° and 56.03° are assigned to SiO [35]. All the peaks match well with the Bragg

peaks of SiO. Crystal structure of wet-milled SiOx-C composite keeps the same as raw

SiOx power, which indicates the ball-milling and carbon coating processes does not

affect the crystallization of the SiOx powder.

As shown in Fig. 3(b), the Raman spectra of the wet-milled SiOx-C composite and

wet-milled SiOx were both measured and compared to confirm the presence of carbon.

The peak at 460 cm-1 for SiOx sample corresponds to the crystalline SiOx. In the

SiOx-C composite, the peak at 460 cm-1 has a slight decrease. This is because the

uniformly coated carbon layer on the SiOx surface blocks the SiOx signal to some

degree. The two peaks at approximately 1350 cm-1 and 1600 cm-1 correspond to the D

[36]
and G bands of carbon, respectively . The result confirms the existence of carbon

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Energy Technology 10.1002/ente.201800800

layer in the wet-milled SiOx-C composite.

Accepted Manuscript
Fig. 3 (a) XRD patterns of raw SiOx and wet-milled SiOx-C composite and (b) Raman

spectra of wet-milled SiOx and wet-milled SiOx-C composite

To evaluate the electrochemical properties of the materials after the wet-milling

and the carbon coating processes. The cyclic performance of the batteries with

different charging and discharging current densities and rate performance of SiOx,

wet-milled SiOx and wet-milled SiOx-C composite electrodes were conducted and

compared as shown in Fig. 4. The wet-milled SiOx-C composite electrode exhibited a

remarkably improved electrochemical performance. As shown in Fig. 4(a), with the

charging and discharging current density of 0.1 Ag-1, the wet-milled SiOx-C

composite electrode has an initial reversible capacity of 1279 mAhg-1, with initial

coulombic efficiency (ICE) of 66.4% and an especially high capacity retention of

even 97.3% (1244 mAg-1) even after 170 cycles, with CE as high as 99.8%, which is

[37-39]
much better than previous reports . As comparison, the wet-milled SiOx and the

raw SiOx electrode have initial reversible capacities of 1384.3mAhg-1 and

1187.2mAhg-1, with ICE of 65.7% and 62.3%, respectively and the capacity

retentions are 94.0% and 84.9% after 170 cycles. Obviously, the wet-milled SiOx-C

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Energy Technology 10.1002/ente.201800800

composite electrode shows an outstanding performance with higher reversible

capacity, higher capacity retention and higher CEs. When it comes to larger current

densities, like charging and discharging current density of 0.3 Ag-1 and 0.5 Ag-1, the

differences of cyclic performance between the SiOx, wet-milled SiOx and wet-milled

SiOx-C composite electrodes are even more remarkable, which can be seen in Fig.

Accepted Manuscript
4(b) and 4(c). For the wet-milled SiOx-C composite electrode, at the condition of

charging and discharging current density of 0.3 Ag-1, it has an initial reversible

capacity of 1286.9 mAhg-1 with ICE of 66.3%. It has a high capacity retention of

85.2% (1096.5 mAhg-1) even after 170 cycles, with CE as high as 99.8%. When the

charging and discharging current density raises up to 0.5 Ag-1, the cyclic performance

is still very good with an initial reversible capacity of 1343.7 mAhg-1 and a high

capacity retention of 71.6% (961.5 mAhg-1) even after 170 cycles, with CE of 99.9%.

After the wet-milling process, the size of the SiOx particles becomes smaller and the

volume effects can be effectively relieved. This will contribute to the excellent long

cyclic performance. Moreover, the wet-milled SiOx-C composite has core-shell

structure with a uniform carbon layer on the surface. It can largely improve the

conductivity of SiOx and help to form stable SEI layer. In the experiments, we found

that the batteries made of SiOx materials exhibit relatively low ICEs due to the

consumption of Li+ in the process of the formation of Li2O and Li4SiO4 in the first

cycle. However, this issue can be solved effectively by prelithiation to prevent the

[40,41]
capacity lose in full cells . Although the formation of Li2O and Li4SiO4 reduces

the ICEs. They could act as buffers to suppress the volume effects of the material

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Energy Technology 10.1002/ente.201800800

during the lithiation/delithiation processes and contribute to the cyclic performance [42,

43]
.

The rate performance of the batteries made of wet-milled SiOx-C composite were

then performed at different current rates of 0.1 Ag-1, 0.3 Ag-1, 0.5 Ag-1, 0.8 Ag-1, 1

Ag-1 and then 0.1 Ag-1 as shown in Fig. 4(d). The reversible capacity of wet-milled

Accepted Manuscript
SiOx-C composite electrode exhibited a high reversible capacity of over 1359.3

mAhg-1 at 0.1 Ag-1. It maintains as high as 1051.4 mAhg-1 even at a high current rate

of 1 Ag-1, which retains 77.3% of the initial reversible capacity. When the current

density goes back to 0.1 Ag-1, the reversible capacity raises to a high value of 1374.1

mAhg-1, which is even higher than the initial reversible capacity. Clearly the rate

performance of wet-milled SiOx-C composite electrode is greatly improved compared

to both the raw SiOx electrode and the wet-milled SiOx electrode as shown in Fig. 4(d).

These excellent rate performance results confirm the effect of wet-milling process on

the reduction of particle size and further the coating of uniform carbon layer, which

contribute to the improvement of conductivity and the formation of stable SEI layer.

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Energy Technology 10.1002/ente.201800800

Accepted Manuscript
Fig. 4 Coulombic efficiency and charge capacity of raw SiOx, wet-milled SiOx and

wet-milled SiOx-C composite electrodes with current density of (a) 0.1 Ag-1 (b)

0.3Ag-1 (c) 0.5Ag-1 and (d) rate performance of the three electrodes

In order to reveal the react processes of the materials in the lithiation/delithiation

processes, CV curves were obtained for the raw SiOx, wet-milled SiOx and wet-milled

SiOx-C composite electrodes and showed in Fig. 5(a), 5(b) and 5(c), respectively. It

can be found that the plateau at about 0.7 V, which is ascribed to the decomposition of

electrolyte and the formation of SEI, is disappeared for the wet-milled SiOx-C

[44-47]
composite electrode . This is because in the core-shell structured SiOx-C

composite material, the surface carbon layer can protect the particles form reacting

with the electrolyte and the SEI formation process is not obvious anymore. That is

why the core-shell structured SiOx-C composite with carbon on the surface exhibits

higher CEs. The peak at lower than 0.1 V is ascribed to the formation of Li-Si alloys

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Energy Technology 10.1002/ente.201800800

and can be seen in all the three electrodes. In the reverse process, the redox peaks at

about 0.2 V and 0.6 V originate from the extraction of Li+ from the Li-Si alloys [44]
.

This result demonstrates the benefit of carbon coating on the particles for higher CEs,

higher reversible capacities and excellent cyclic stability.

The conductivity improvement of the composite electrode due to the involvement

Accepted Manuscript
of surface carbon layer was demonstrated by investigating the impedance

spectroscopies for the raw SiOx, wet-milled SiOx and wet-milled SiOx-C composite

electrodes and the results are showed in Fig. 5(d). The intercept of the curve in high

frequency with the axis corresponds to electrolyte resistance. The diameter of

semicircle is related to the charge transfer resistance (Rct). Moreover, the straight line

[48]
in low frequency reflects the effect of ions diffusion . The wet-milled SiOx

electrode has a same value of electrolyte resistance of about 15 Ω as that of raw SiOx

electrode, but its Rct is about 50 Ω, which is larger than that of raw SiOx electrode

with about 37 Ω. That is because, the particles with smaller size after the ball-milling

process will involve more resistance. Fortunately, for wet-milled SiOx-C composite

electrode with carbon coating, both the electrolyte resistance and Rct are reduced

largely to 7 Ω and 25 Ω, respectively. This is benefit for the high conductivity of the

carbon layer coated on the SiOx particles. To further evaluate the effect of carbon shell

on the structure stability and electrical contact during long cycling, we also observed

the surface SEM images of wet-milled SiOx-C composite electrode and wet-milled

SiOx electrode of uncycled and after cycling as shown in Fig. S2. The wet-milled

SiOx-C composite electrode retains its integrated shape and only has some small

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Energy Technology 10.1002/ente.201800800

cracks compared to wet-milled SiOx electrode after cycling. This results reveal that

the carbon shell could mitigate the volume effect of SiOx and thus facilitates electrode

stability and good electrical contact during long cycling. The electrodes after cycling

have smooth surface compared to the as prepared electrodes before cycling, which

corresponds to the SEI layer in the interface of electrode and electrolyte.

Accepted Manuscript
Fig. 5 CV curves of (a) raw SiOx, (b) wet-milled SiOx, (c) wet-milled SiOx-C

composite electrodes and (d) EIS spectrum of SiOx, wet-milled SiOx, wet-milled

SiOx-C composite electrodes

3. Conclusions

Wet-milled SiOx-C composite anode material with SiOx core and carbon shell

was obtained by simple combining of wet-milling and carbon coating process through

pyrolysis of carbon source. The morphology and structure property of the wet-milled

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Energy Technology 10.1002/ente.201800800

SiOx-C composite were characterized. After the wet-milling process, SiOx particles

have reduced size, which is helpful for the relief of volume effects during

lithiation/delithiation processes. The carbon shell on the surface of wet-milled SiOx-C

composite material could effectively improve conductivity and help forming stable

SEI layer. Moreover, Li2O and Li4SiO4 generated in the first cycle could act as buffers

Accepted Manuscript
to further suppress the volume effects as discussed in our previous work. The

wet-milled SiOx-C composite electrode delivers a high reversible capacity with high

CEs and superior capacity retention after long cycles. The synthesis approaches used

in the experiments are simple and could be adopted for large scale production of high

performance SiOx anode materials. By introducing prelithiation method, the ICE

could be improved effectively to avoid capacity loss in full cells.

4. Experimental

4.1. Materials and experimental procedures

Commercial SiOx powder (99.9%, 300 mesh, Beijing Huanqiu Jin Xin

international technology) was used as starting material. The powder was introduced

along with zirconia balls (12 mm, 10 mm, 8 mm and 5 mm) into a zirconia vial (100

mL) with a ball-to-powder mass ratio of 10:1. What is more, 10 mL ethanol was also

added to the mixture for 10 g powder. The wet-milling process was conducted with a

rotating speed of 350 rpm at room temperature for 10 h to obtain smaller particle size.

The as obtained SiOx (labelled as wet-milled SiOx) was mixed with citric acid mixed

with molar ratio of 1:1. After that, the mixture was stirred for 2 h in anhydrous alcohol

under water bath at 70 °C to form homogeneous sol. Then, SiOx and citric acid

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Energy Technology 10.1002/ente.201800800

mixture was heated to evaporate the ethanol in vacuum oven overnight and the gel

was obtained. At last, annealing process was conducted under N2 atmosphere at

600 °C for 4 h at a heating rate of 5 °C min-1 to carbonize the citric acid and SiOx-C

core-shell composite (labelled as wet-milled SiOx-C composite) was prepared [49].

Morphology and structure of the SiOx-C core-shell composite were characterized

Accepted Manuscript
then mixed with conductive agents (Sigma-Aldrich) with same amount of graphite,

Super P and vapor grown carbon fibers. At last, mixed with polyacrylic acid

[50]
(Sigma-Aldrich 10 wt%) and stirred for 6 h to be evenly mixed . The slurry was

then coated on a copper foil, followed by heating at 110 °C in a vacuum oven

overnight with a thickness of 100 μm before drying. To develop electrodes for cell

assembly, 15 mm disks were cut with an average mass loading of 1.4 mgcm-2.

4.2. Characterizations

The morphology characterizations of SiOx powder were performed by

transmission electron microscope (TEM) using a Tecnai G2F20S-TWIN TEM

operated at 200 kV.

The structure of materials was characterized by X-ray diffraction (XRD) analyses

which was carried out with a Brucker D8 diffractometer to find the crystallinity and

the radial data (2θ) were integrated over 3-90°. Raman spectroscopy was performed

on a Renishaw inVia system with a 633 nm laser to confirm the presence of Si, O and

C in the composite.

4.3. Electrochemical measurements

Coin-type half cells (2025R type) with lithium foils as counter electrodes were

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Energy Technology 10.1002/ente.201800800

assembled in a glove box (Mikrouna Super 1220/750) under an argon atmosphere.

The electrolyte was LiPF6 (1 M) in ethylene carbonate-methyl ethyl carbonate (30:70

vol %), with vinylene carbonate (5wt %) as additive. Glass fiber was employed to

stabilize the coin system. The coin-type half cells were cycled at galvanostatic mode

between 0.01 V and 1.2 V versus Li/Li+ with current density of 0.1 Ag-1, 0.3 Ag-1 and

Accepted Manuscript
0.5 Ag-1 on land battery test system. All the specific capacities of the samples were

calculated based on the weight of SiOx. Cyclic voltammetry (CV) curves bwtween

0.02-2.6 V (0.2 mV s-1) were measured using an electrochemical workstation

(PGSTAT302N, Autolab, Metrohm). Electrochemical impedance spectroscopy

measurement was then performed on the same workstation from 100 kHz to 0.01 Hz

(magnitude of 0.01 V).

Acknowledgements

This work was supported in part by the National Natural Science Foundation of

China [Grant number 61675195], the National Thousand Talents Program of China

and the Scientific Research Foundation for the Returned Overseas Chinese Scholars,

State Education Ministry.

Keywords: Silicon Suboxide; Carbon Coating; Anode; Lithium Ion Batteries

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