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Systematic Investigation of Prelithiated SiO2 Particles for High-Performance Anodes in Lithium-Ion Battery

National Laboratory of Solid State Microstructures, College of Engineering and Applied Sciences and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China
Nanjing Foreign Language School, Nanjing 210008, China
Author to whom correspondence should be addressed.
Appl. Sci. 2018, 8(8), 1245;
Submission received: 22 June 2018 / Revised: 20 July 2018 / Accepted: 24 July 2018 / Published: 27 July 2018
(This article belongs to the Special Issue High Capacity Electrode Materials for Advanced Lithium Ion Batteries)


Prelithiation is an important strategy used to compensate for lithium loss during the formation of a solid electrolyte interface (SEI) layer and the other irreversible reactions at the first stage of electrochemical cycling. In this paper, we report a systematic study of thermal prelithiation of SiO2 particles with different sizes (6 nm, 20 nm, 300 nm and 3 μm). All four lithiated anodes (LixSi/Li2O composites) show improved performance over pristine SiO2. More interestingly, lithiated product from micron-sized SiO2 particle demonstrates optimum performance with a charge capacity of 1859 mAhg−1 initially and maintains above 1300 mAhg−1 for over 50 cycles.

1. Introduction

Next generation high-capacity electrode materials are needed to meet the demands of the explosion of electricity-fueled forms of transportation [1,2,3]. Graphite, the commercial anode material, cannot completely satisfy the requirements of electric vehicles due to its relatively low theoretical specific capacity. To overcome this problem, numerous researchers have focused on silicon-based anode materials because of its high theoretical specific capacity and relatively low charge/discharge voltage. Among them, silica (SiO2), the main institutions of sand and quartz, is generally considered to be a promising candidate [4,5,6,7]. Silica is easier to prepare and is much more economical than silicon, while also stores a large quantity of lithium and has a relatively low potential platform. However, bulk-SiO2 is generally conformed to be lithium inactive due to instinctive insulation [8,9,10,11]. Therefore, considerable efforts have been devoted to various nanostructures, such as hollow nano-spheres [12], nano-films [8,11], nano-cubes [13], nanotubes [14] and nano-belts [15].
There is no denying that nano-structures can facilitate the diffusion of electron and lithium ion effectively. However, nano-structuring also has its limitations. Its higher specific surface area consumes the more electrolyte to form solid electrolyte interface (SEI), which results in lower Coulombic efficiency (CE) and capacity fading [16]. In addition, nano-structured materials usually have a low tap density, leading to a low volumetric capacity and a thick electrode at high mass loading [16,17]. As a result, maintaining the electrical and ionic pathways during cycling is difficult. Furthermore, nano-structuring usually requires a multi-step and advanced preparation process, leading to a higher cost. More seriously, silica can form a great deal of irreversible lithium silicates and Li2O during the first lithiation cycle. This process consumes an excess amount of cathode materials [6,7,8,13,18,19], which significantly reduces the total energy density of full-cells, thereby preventing their practical applications. In order to tackle this issue, researchers have proposed prelithiation of the electrode material, which directly compensates for the irreversible loss of lithium during the first cycle [20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37]. For example, Tarascon’s group developed an electrochemical lithiation method to preload lithium in the Si and SiO2 materials, which required the fabrication of a temporary cell and an inert atmosphere [35]. Recently, Cui’s group developed thermal alloying silicon nanoparticles with molten lithium metal to obtain crystalline LixSi with good crystallinity and acceptable dry stability [31,32].
Here, we applied the thermal alloying method to the silica particles, achieved the prelithiated composites (LixSi/Li2O), and finally studied their electrochemical properties. Such composites have multiple advantages: (1) prelithiation effectively improves the electrical conductivity of silica, making it easier to function as an anode with high capacity and cycle stability; (2) LixSi/Li2O composites can address the low initial Coulombic efficiency (ICE) issue of Si-based anodes, which is a huge challenge for practical application; (3) LixSi/Li2O composites alloy can serve as a promising anode containing lithium to pair with high-capacity lithium-free cathodes such as S for next-generation lithium-ion batteries. We have chosen different SiO2 particles with different sizes (6 nm, 20 nm, 300 nm and 3 μm), and systematically studied their electrochemical performance. All prelithiated LixSi/Li2O composites exhibit better performance than that of pristine SiO2 particles. More interestingly, prelithiated composite from SiO2 microparticle shows the best cycling stability, achieving a delithiation initial capacity of 1859 mAhg−1 and keeping above 1300 mAhg−1 after 50 cycles.

2. Materials and Methods

2.1. Synthesis of LixSi/Li2O Composites

SiO2 powders (about 6 nm, 20 nm, 300 nm, and 3 μm) were first dried under vacuum for 24 h to remove trapped water. Typically, the variously sized SiO2 particles (200 mg) were mixed with Li metal (196 mg) in a tantalum crucible. Then, the mixtures were heated at 200 °C while they were mechanically stirred inside the tantalum crucible at 400 rpm for at least 6 h in a glove box (Ar atmosphere, O2 level < 1.2 ppm, and H2O level < 0.1 ppm, respectively). The powder turned to black during the reaction. The products were denoted as LixSi/Li2O-1, LixSi/Li2O-2, LixSi/Li2O-3 and LixSi/Li2O-4, corresponding to the different pristine SiO2 particle sizes (6 nm, 20 nm, 300 nm, and 3 μm).

2.2. Morphological and Structural Characterizations

The crystal structures of the products were identified by X-ray diffractometer (XRD, Ultima III, Rigaku, Tokyo, Japan) using Kα radiation (40 Kv, 40 mA). The structure and morphology details of the products were observed by field-emission scanning electron microscopy (FESEM, Ultra 55, Zeiss, Germany) and transmission electron microscopy (TEM, Tecnai G2 F20 X-TWIN, FEI). The particle size and size distributions were examined by Dynamic Light Scattering (DLS, Zetasizer Nano-ZS90, Malvern, UK).

2.3. Electrochemical Measurements

The electrochemical properties were carried out using LIR 2032-type coin cells. The active material was mixed with binder acetylene black and carboxymethyl cellulose (CMC) (weight ratio of 65:20:15) in tetrahydrofuran (THF) to form a slurry. Then, the slurry was uniformly spin-coated on copper foils. The mass loading of the slurry on each copper foil (12 mm) is about 0.3–3.5 mg. The electrodes were assembled in an Ar-filled glove box using lithium foil as the counter electrode and a Celgard 2300 film as the separator. An electrolyte solution consisting of 1 M LiPF6 dissolved in ethylene (EC)/dimethyl carbonate (DMC) (1:1 by volume) was used to assemble the coin cells. Galvanostatic charge-discharge measurements were tested between 0.01 and 1.0 V at a rate of 0.05 C on the cell tester (LAND CT2001A, Wuhan, China). Cyclic voltammetry (CV) was conducted on an electrochemical workstation (Bio-logic VMP3) at a scan rate of 0.1 mVs−1 in a potential range from 0.01 to 3.0 V. Electrochemical impedance spectroscopy (EIS) measurements were carried out on the same electrochemical workstation with frequencies ranging from 100 kHz to 10 MHz, with an alternating voltage of 5 mV. All electrochemical measurements were carried out at room temperature.

3. Results and Discussion

To systematically study the effect of particle size, we selected different sizes of SiO2 particles. As shown in Figure 1, the morphology and size distributions of particles were characterized by TEM, SEM and DLS measurement. Figure 1a–d show the morphology of pristine SiO2 particles with different sizes from 6 nm to 3 μm. The TEM (Figure 1a,b) and SEM (Figure 1c,d) images clearly demonstrate all the silica particles have the spherical structures and uniform size. The size statistics by DLS further confirm that SiO2 particles have a quite narrow size distribution (Figure 1e,h).
The SiO2 particles with different sizes were alloyed with molten Li metal under Ar atmosphere to form LixSi/Li2O NPs, as schemed in Figure 2a. The powder color changes from white to black within ten minutes, indicating the formation of LixSi alloy. SEM and TEM images (Figure 2b–e) demonstrate the morphology of as-prepared LixSi/Li2O composites. After prelithiation, the surface of SiO2 particles becomes rougher due to the coverage of oxide layer and volume expansion. Moreover, the images show that they have similar morphology despite being derived from variously sized SiO2 particles. It is found that although the pristine SiO2 particles varied from 6 nm to 3 μm, the over-all sizes of as-lithiated samples are all around several micrometers, which can be clearly seen from the enlarged SEM images in the insets. This can be attributed to the smaller particles undergo more sever aggregation during SiO2 lithiation. As a result, Nanoparticles trend to aggregate into microparticles, while micro- or submicro-ones prefer to retain their size in the lithiation process. Figure 3a shows the XRD patterns of prelithiated SiO2 particles. A home-made sealed sample holder was used to avoid exposing the products to the air. The diffraction peaks of Li2O and Li21Si5 are shown in the Figure 3a, demonstrating the formation of Li2O (PDF# 04-001-893) and Li21Si5 (PDF# 00-018-747) phases. It has been reported that Li21Si5 is the most thermally stable phase among the crystalline lithium silicates [21]. The XRD patterns of the four LixSi/Li2O composites are similar, indicating that pristine particle size does not have a big effect on the formation of crystalline Li21Si5. As calculated by the Scherrer equation, the crystalline sizes of the four composites are 28.2, 29.3, 31.9 and 37.5 nm, indicating that the SiO2 microparticles produce relatively large Li21Si5 domains.
To invest the electrochemical behavior of the prelithiated products, half cells were fabricated with Li metal as a counter electrode. Figure 3b shows the charging/discharging profiles of LixSi/Li2O electrodes. The open-circuit voltage (OCV) of the half cells is around 0.35 V, which is significantly lower than ~2.0 V of the SiO2/Li cell (SI, Figure S1). This proves that most SiO2 particles were well lithiated. All of the lithiated SiO2 electrodes exhibit the similar potential plateaus around 0.45 V, indicating the same active materials (LixSi) of the electrodes and their high crystallinity, consistent with the XRD results. The prelithiation capacities of the SiO2 particles are 1972, 2267, 1776, and 1412 mAhg−1, which are listed in Table 1. Here, the prelithiation capacity is determined by subtracting the lithiation capacity from the delithiation capacity at the first cycle. The thermal lithiation can effectively compensate for the huge irreversible lithium loss during the first cycles via the formation of lithium silicates and Li2O. The cyclic voltammetry (CV) tests are conducted for both the pristine and prelithiated SiO2 half cells for 3 consecutive cycles between 3.0 V and 0.01 V at a scan rate of 0.05 mVs−1 (Figure 4). The pristine SiO2 electrode exhibits cathodic peaks above 1.0 V corresponding to the irreversible electrochemical reactions between the SiO2 and Li, which disappears in the subsequent cycles. The cathodic peak below 0.2 V can be ascribed to the lithiation process of silicon. The electrochemical equations can be expressed as followed:
SiO2 + 4Li+ + 4e → 2Li2O + Si
2SiO2 + 4Li+ + 4e → Li4SiO4 + Si
5SiO2 + 4Li+ + 4e ⇋ 2Li2Si2O5 + Si
For the LixSi/Li2O-4 anode, the corresponding peak of silicon lithiation is very pronounced. The cathodic peak at 0.5 V at the first cycle confirms the formation of highly crystalline LixSi. Two distinct anodic peaks at about 0.34 and 0.51 V during the second and third cycle agree with the characteristic peaks of delithiation process from amorphous LixSi to Si. The electrochemical equation can be expressed as followed:
Si + xLi+ + xe ⇋ LixSi
The corresponding Nyquist plots measured at the first cycle are illustrated in supplement information (SI, Figure S2). LixSi/Li2O-4 anode demonstrated a smaller semicircle than the corresponding SiO2 anode, indicating a lower charge transfer resistance (Rct). It is clear that the prelithiated sample provides a fast electron transport pathway between the LixSi domains in the microparticles.
The cycling performance of prelithiated SiO2 composites is shown in Figure 5a and listed in Table 1. The LixSi/Li2O composites deliver a first delithiation capacity of around 2000 mAhg−1 at C/20, with a corresponding Coulombic efficiency (CE) that is above 90% at initial cycles (Figure 5a and Figure S3). Very interestingly, the LixSi/Li2O-4 anode, prepared from micron-sized silica, has the best cycling stability among the four samples. It is able to maintain a stabilized reversible capacity of around 1300 mAhg−1 with acceptably small decay (~71% capacity retention) after prolonged 50 cycles. The longer cycling performance is shown in supporting information, remaining around 800 mAhg−1 after 500 cycles. (Figure S4). The rate performance of LixSi/Li2O-4 anode was shown in Figure 5b. It yields a reversible capacity of over 1500 mAhg−1 at 0.05 C, around 1200 mAhg−1 at 0.1 C and 800 mAhg−1 at 0.2 C. At a high rate of as high as 1 C, the capacity is as low as 100 mAhg−1. However, when the current rate reversed to 0.05 C, a high specific capacity have been recovered.
As schemed in Figure 6, LixSi nano-domains are homogeneously dispersed in robust Li2O matrix after the thermal prelithiation. For nano-sized SiO2 particles, the LixSi domain is small and each domain is covered by a Li2O layer. This Li2O layer, formed by trace air oxidization of surface LixSi, is electrical insulating, which hinders the electrical conductivity between the LixSi/Si nano-domains. After many electrochemical cycles, the electrical contact becomes even worse due to the SEI formation on these small domains. While for micron-sized particles, the LixSi domains are relatively large. In addition, oxidized Li2O surface layer is mainly wrapped out of the whole microparticle, leaving LixSi domains contacting with each other inside the particle. The Li2O outer layer can spatially limit the direct SEI formation on LixSi/Si cores during the cycling. As a result, the LixSi/Li2O from SiO2 microparticles can achieve enhanced cycling stability in half cells. Therefore, SiO2 microparticle should be a very promising anode material, considering its low cost and the high cycling stability.

4. Conclusions

In conclusion, this study explores the potential of using prelithiated SiO2 particles as anode materials for high-capacity batteries. We systematically invested SiO2 particles with different sizes varying from 6 nm to 3 μm. All prelithiated composites exhibit better performance than that of untreated SiO2. The nano-particle, which is often thought to be more competitive in battery performance, however, lost its superiority after prelithiation. Contrary to our expectations, the micron-sized SiO2 particle demonstrates more stable cycling performance, delivering a prelithiation capacity of 1412 mAhg−1 and a reversible specific capacity over 1300 mAhg−1 after 50 cycles. Considering the encouraging battery performance displayed, together with its abundance and low-cost, SiO2 microparticle demonstrates a promising future as a novel anode material with high capacity in lithium-ion batteries.

Supplementary Materials

The following are available online at, Figure S1: Galvanostatic charge/discharge profiles SiO2 electrodes (2 nm, 10 nm, 300 nm, and 3 μm) before and after lithiation; Figure S2: Electrochemical impedance spectroscopy of SiO2-4 electrodes before and after prelithiation at the first cycle. Figure S3. The Coulombic efficiency of four LixSi/Li2O composites. Figure S4. Cycling performance of LixSi/Li2O-4 composite.

Author Contributions

Y.H., X.L. and Z.L. did the experiment and wrote this work together.


National Natural Science Foundation of China (Grant No. 21601083), Natural Science Foundation of Jiangsu Province (Grant No. BK20160614), the Fundamental Research Funds for the Central Universities, and Jiangsu Innovative and Entrepreneurial Talent Award.


We acknowledge the support from National Laboratory of Solid State Microstructures, Collaborative Innovation Center of Advanced Microstructures, National Natural Science Foundation of China, Natural Science Foundation of Jiangsu Province, the Fundamental Research Funds for the Central Universities, and Jiangsu Innovative and Entrepreneurial Talent Award.

Conflicts of Interest

The authors declare no conflicts of interest.


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Figure 1. (a,b) TEM images of SiO2-1 (6 nm) and SiO2-2 (20 nm); (c,d) SEM images of SiO2-3 (300 nm) and SiO2-4 (3 μm); (eh) The corresponding DLS analysis of the samples.
Figure 1. (a,b) TEM images of SiO2-1 (6 nm) and SiO2-2 (20 nm); (c,d) SEM images of SiO2-3 (300 nm) and SiO2-4 (3 μm); (eh) The corresponding DLS analysis of the samples.
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Figure 2. (a) Schematic of the thermal-alloying process of the SiO2 with lithium metal; (be) SEM images of LixSi/Li2O-1, LixSi/Li2O-2, LixSi/Li2O-3, and LixSi/Li2O-4, respectively.
Figure 2. (a) Schematic of the thermal-alloying process of the SiO2 with lithium metal; (be) SEM images of LixSi/Li2O-1, LixSi/Li2O-2, LixSi/Li2O-3, and LixSi/Li2O-4, respectively.
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Figure 3. (a) XRD patterns of the four prelithiated composites; (b) The corresponding galvanostatic charge/discharge profiles of the LixSi/Li2O samples at the first cycle.
Figure 3. (a) XRD patterns of the four prelithiated composites; (b) The corresponding galvanostatic charge/discharge profiles of the LixSi/Li2O samples at the first cycle.
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Figure 4. Cycling voltammetry measurement of SiO2 electrodes before (a) and after (b) prelithiation.
Figure 4. Cycling voltammetry measurement of SiO2 electrodes before (a) and after (b) prelithiation.
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Figure 5. (a) Cycling performance of four LixSi/Li2O samples at C/20 (1C = 1.96 A g−1 LixSi, the capacity is based on the total mass of LixSi in the electrode). The green line is the Coulombic efficiency of LixSi/Li2O-4 composite; (b) Rate stability of LixSi/Li2O-4 composite.
Figure 5. (a) Cycling performance of four LixSi/Li2O samples at C/20 (1C = 1.96 A g−1 LixSi, the capacity is based on the total mass of LixSi in the electrode). The green line is the Coulombic efficiency of LixSi/Li2O-4 composite; (b) Rate stability of LixSi/Li2O-4 composite.
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Figure 6. Schematic Illustration of the thermal prelithiation and electrochemical cycling of nano- and micron-sized SiO2 particles.
Figure 6. Schematic Illustration of the thermal prelithiation and electrochemical cycling of nano- and micron-sized SiO2 particles.
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Table 1. Cycling performance for LixSi/Li2O electrodes.
Table 1. Cycling performance for LixSi/Li2O electrodes.
Electrode1st Delithiation Capacity/mAhg−1Prelithiated Capacity/mAhg−125th Delithiation Capacity/mAhg−150th Delithiation Capacity/mAhg−1

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Han, Y.; Liu, X.; Lu, Z. Systematic Investigation of Prelithiated SiO2 Particles for High-Performance Anodes in Lithium-Ion Battery. Appl. Sci. 2018, 8, 1245.

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Han Y, Liu X, Lu Z. Systematic Investigation of Prelithiated SiO2 Particles for High-Performance Anodes in Lithium-Ion Battery. Applied Sciences. 2018; 8(8):1245.

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Han, Yuyao, Xinyi Liu, and Zhenda Lu. 2018. "Systematic Investigation of Prelithiated SiO2 Particles for High-Performance Anodes in Lithium-Ion Battery" Applied Sciences 8, no. 8: 1245.

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