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Research Papers

Freestanding Flexible Si Nanoparticles–Multiwalled Carbon Nanotubes Composite Anodes for Li-Ion Batteries and Their Prelithiation by Stabilized Li Metal PowderOPEN ACCESS

[+] Author and Article Information
K. Yao

Materials Science and Engineering,
Florida State University,
Tallahassee, FL 32310;
Aero-Propulsion, Mechatronics and Energy
Center (AME),
Florida State University,
Tallahassee, FL 32310;
High-Performance Materials Institute (HPMI),
Florida State University,
Tallahassee, FL 32310

R. Liang

High-Performance Materials Institute (HPMI),
Florida State University,
Tallahassee, FL 32310;
Department of Industrial and Manufacturing
Engineering,
Florida A&M University—Florida State
University College of Engineering,
Tallahassee, FL 32310

J. P. Zheng

Aero-Propulsion, Mechatronics and Energy
Center (AME),
Florida State University,
Tallahassee, FL 32310;
Department of Electrical and Computer
Engineering,
Florida A&M University—Florida State University
College of Engineering,
Tallahassee, FL 32310
e-mail: zheng@eng.fsu.edu

Manuscript received December 23, 2015; final manuscript received March 20, 2016; published online xxxx x, xxxx. Assoc. Editor: Partha Mukherjee.

J. Electrochem. En. Conv. Stor. 13(1), 011004 (Apr 19, 2016) (6 pages) Paper No: JEECS-15-1026; doi: 10.1115/1.4033180 History: Received December 23, 2015; Revised March 20, 2016

Abstract

Freestanding flexible Si nanoparticles–multiwalled carbon nanotubes (SiNPs–MWNTs) composite paper anodes for Li-ion batteries (LIBs) have been prepared using a combination of ultrasonication and pressure filtration. No conductive additive, binder, or metal current collector is used. The SiNPs–MWNTs composite electrode material achieves first cycle specific discharge and charge capacities of 2298 and 1492 mAh/g, respectively. To address the first cycle irreversibility, stabilized Li metal powder (SLMP) has been utilized to prelithiate the composite anodes. As a result, the first cycle irreversible capacity loss is reduced from 806 to 28 mAh/g and the first cycle coulombic efficiency is increased from 65% to 98%. The relationship between different SLMP loadings and cell performance has been established to understand the prelithiation process of SLMP and to optimize the construction of Si-based cells. A cell containing the prelithiated anode is able to deliver charge capacity over 800 mAh/g without undergoing the initial discharge process, which enables the exploration of novel cathode materials.

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Introduction

Si is emerging as a promising alternative anode material for the next-generation of high-energy LIBs due to its high theoretical gravimetric capacity of 4200 mAh/g (for Li4.4Si) and abundance. However, it is not viable for practical application because of the severe volume expansion upon lithiation of approximately 400%. Compared to bulk Si, the nanoscale materials are reported to achieve improved cycling performance by effectively managing the large stresses associated with the expansion and contraction of Si alloy electrodes during electrochemical cycling [1,2]. The nanostructured Si under study includes nanowires [37], nanotubes [8,9], and nanoparticles [1014]. Although improvements in both the specific capacity and the cyclability of cells using Si nanowire- or nanotube-based electrodes have been found, the drawbacks are obvious: delicate structural design, complicated low-throughput preparation process, and high cost, which are not favorable for industrialization. The SiNPs, on the other hand, are the most cost-effective and easily obtainable. They have been studied by means of high-energy mechanical milling [15], dielectric barrier discharge plasma assisted milling [16], chemical vapor deposition (CVD) [14,1719], pulsed laser deposition (PLD) [20], spin coating [21], and sonication and suction filtration [13].

Besides developing novel high-capacity anode materials, elimination of the mass of nonactive materials such as binder and metal current collector reduces the electrode weight and therefore benefits the battery energy density. Carbon nanotubes (CNTs), renowned for their exceptional electrical and mechanical properties, have been studied as a replacement of the conductive additives and current collectors in electrode construction. Forney et al. [18] investigated Si freestanding anodes obtained by low-pressure CVD and plasma-enhanced CVD onto single-walled carbon nanotube (SWNT) current collectors. Wang and Kumta [19] deposited nanoscale amorphous/nanocrystalline Si droplets directly on vertically aligned multiwall CNTs (VACNTs) using two-step liquid injection CVD process. Chou et al. [20] prepared flexible Si/SWNT composite paper by depositing Si onto SWNT paper through PLD. Park et al. [21] adopted CVD using acetylene gas and spin coating using commercial Si nanopowders. Smithyman et al. [22] developed binder-free composite electrodes using SWNT networks to host activated carbon microparticles.

Furthermore, the availability of a special form of Li metal, SLMP, has stimulated research interest regarding their application in anodes, such as graphite [2326], hard carbon [25,2730], and CVD-based Si-CNT [31]. The SLMP provides an alternative Li source so the Li in the cathode is spared from being consumed during solid electrolyte interphase (SEI) formation. Although there have been previous attempts of adding extra Li to Li-ion cells to compensate for the first cycle irreversible capacity of anode materials, such as chemical or electrochemical prelithiation and the use of sacrificial Li electrode (typically Li foils) [23,24], the SLMP prelithiation method gains attention due to its unique advantages. First, unlike normal Li powder which can only be used safely in a glovebox, SLMP can be handled safely in a dry room atmosphere, which allows ease of operation. Second, the Li loading amount can be controlled and adjusted easily as needed. Third, Li powder can be distributed uniformly throughout the electrode.

Thus far, only CVD-derived Si thin film anode has been investigated with SLMP prelithiation [31], and there has been no systematic study regarding the influence of different amounts of SLMP loading on the performance of SiNP-based electrode materials. Also, most of the CNT studies focused on SWNTs. However, Chew et al. [32] revealed that films based on MWNTs are much better than single-walled and double-walled CNTs films in terms of electrochemical performance when used as flexible LIB electrodes alone. Although MWNT-embedded SiNP film electrode has been reported [21], the costly CVD process was used and the high irreversible capacity upon first cycling was not discussed. Herein, we would like to report the scalable preparation of a light-weight freestanding flexible SiNPs–MWNTs composite paper anode for LIBs by ultrasonication and pressure filtration. The composite showed specific capacities much higher than the commercial graphite anodes. We utilized the SLMP to prelithiate the anodes to see a reduction in the first cycle irreversible capacity as well as an increase in the first cycle coulombic efficiency. Simultaneously, the influence of the SLMP loading amount on the cell properties was studied, in the hope of establishing a guideline for building SLMP-prelithiated Si-based energy storage devices. The incorporation of SLMP allowed the cell to deliver charge (Li extraction) capacity over 800 mAh/g without undergoing the first discharge (Li insertion) process. This gives nonconventional materials a chance to be considered cathode candidates so as to boost the capacity and energy density of LIBs.

Experimental

Materials and Electrode Fabrication.

The SiNPs were purchased from Alfa Aesar (Ward Hill, MA), are crystalline, and have average particle size of ≤50 nm with a purity of 98%. MWNTs used to prepare the composite paper samples are SMW200 from SouthWest NanoTechnologies (Norman, OK), with median outer diameter of 10 nm, median inner diameter of 4.5 nm, length of ∼4 μm, and carbon content ≥98%. The SLMP, supplied by FMC Lithium (Charlotte, NC), is Li powder with a passivation layer at surface and the median particle size of the powder is 25–60 μm. All the materials were used as-received.

The SiNPs–MWNTs composite paper was prepared by dispersing a mixture of SiNPs and MWNTs at 1:1 mass ratio in de-ionized (DI) water through ultrasonication with the aid of surfactant Triton X-100 and then carrying out pressure filtration on the resultant dispersion by use of a 0.4 μm pore size polycarbonate (PC) membrane. During filtration, the MWNTs and SiNPs were deposited onto the membrane surface to generate a composite thin film of dark green color. Upon natural drying overnight, the thin film could be peeled off from the PC membrane, creating a freestanding SiNPs–MWNTs composite paper. To remove the residual surfactant, the composite paper was washed with DI water, isopropyl alcohol (IPA), and DI water sequentially, followed by heat treatment at 500 °C in nitrogen gas atmosphere for 1 hr. Figure 1(a) gives the optical image of the obtained composite paper demonstrating its freestanding capability and flexibility.

Microstructural Analysis.

The microstructural analysis was carried out using a JSM-7401F Field Emission Scanning Electron Microscope (FE-SEM) from JEOL. The cross-sectional surface was obtained by cutting the sample with a razor blade.

Cell Assembly and Characterization.

Prior to cell assembly, the freestanding composite paper was cut into circular electrode sheets using half-inch punch and dried at 120 °C in vacuum overnight to be used as a working electrode directly without any additives. The electrodes for prelithiation study were applied with SLMP on the surface by plate-press in a dry room. The SiNPs–MWNTs composite paper anodes with and without SLMP are displayed in Figs. 1(b) and 1(c), respectively. After pressing, a shiny uniform thin layer of SLMP was formed on the electrode surface as shown in Fig. 1(c). The CR2032-type coin cell was adopted for battery performance test. A Li metal foil was used as the counter electrode, with a glass fiber separator (EL-CELL, Hamburg, Germany) between the electrodes. The electrolyte was 1 M LiPF6 in ethylene carbonate:dimethyl carbonate (EC:DMC) at a weight ratio of 1:1 purchased from BASF Corporation (Independence, OH). The construction of the cells was carried out in an argon gas glovebox environment. The galvanostatic charge–discharge cycling performance was tested using MTI Battery Analyzer systems. All the specific capacity values are based on the total weight of SiNPs and CNTs in the electrode.

Results and Discussion

SEM Characterization.

SEM was conducted to examine the composite microstructure and the interactions of CNT network with SiNPs. Representative cross-sectional and top-view SEM images of the SiNPs–MWNTs composite paper are shown in Figs. 2(a) and 2(b), respectively. It can be seen from the cross section that the freestanding paper contains dense network formed from CNTs and has a thickness of ∼40 μm. The SiNPs are not visible in the cross section (at low magnification) due to their small size. The high-magnification micromorphology image shows that the size of the Si particles is less than 100 nm, and the SiNPs are observed to be uniformly distributed and embedded in the CNT network as a host matrix. With the CNT bundles bridging the particles and holding them together within the network, good electrical contact can be expected. In addition, the SiNPs–MWNTs electrode has good chemical and mechanical stability, because the composite paper is held together by van der Waals forces without any chemical binder.

Charge–Discharge Properties.

To study the electrochemical properties of the SiNPs–MWNTs composite paper, the sample was assembled into CR2032-type coin cell and cycled in a voltage range of 1–0.005 V versus Li/Li+ under a constant current of 1 mA. The first and second cycle voltage profiles are shown in Fig. 3. A drawback in using nanostructured materials for Si-based anodes is that their high surface area increases SEI formation on the first cycle, which can cause high irreversible capacity resulting in low coulombic efficiency [18,31]. In the first cycle in Fig. 3, the large voltage plateau resulting from SEI formation during Li insertion is observed at ∼0.7–0.8 V versus Li/Li+, which is close to the previously published reports (∼0.8–0.9 V versus Li/Li+) on Si-CNT anodes [18,31]. Such slight difference is understandable since specific material and method were employed. The first discharge capacity is 2298 mAh/g based on the SiNPs–MWNTs (1:1) weight, while the first charge capacity is 1492 mAh/g, which yields the ratio between charge and discharge capacities (it is usually called coulombic efficiency if the Li comes from one source) during the first cycle of 65%. To imagine such anode in a full LIB cell, during the discharge, the Li will come from cathode. After the first charge, the cathode will only have approximately 65% of its original capacity, if the cell is designed as having a matched capacity for anode and cathode. Such high irreversible capacity loss is attributed mainly to the formation of SEI upon first cycle. It is an obstacle that must be overcome in order to realize commercial application of nanostructured electrodes, including the SiNPs–MWNTs composite presented here. This work is therefore focused on addressing the initial capacity loss. Cycle life study on the electrode material is underway and will be reported separately. Despite the low coulombic efficiency, it is clear that the SiNPs–MWNTs sample shows specific capacity much higher than graphite's theoretical 372 mAh/g.

In the second cycle in Fig. 3, the SEI plateau near 0.7–0.8 V disappears from the voltage profiles, significantly improving the second cycle coulombic efficiency. The second discharge capacity is 1636 mAh/g and the second charge capacity is 1534 mAh/g, resulting in the second cycle coulombic efficiency dramatically rising to 94% from the previous 65%. This result indicates that irreversible capacity loss occurred during the first cycle. We can also see a slight increase in the charge capacity from first to second cycle, such increasing capacity during initial cycling has been reported to be the outcome of the activation of crystalline Si as it becomes amorphous during cycling, because higher Li mobility in amorphous Si allows insertion of Li into larger portions of the electrode as cycling progresses [1].

The SLMP coating for prelithiation was implemented by directly pressing the SLMP onto the electrode surface in a dry room where the SLMP can be handled safely. Dry pressing is employed here to avoid the use of toxic solvents such as xylene [25] and toluene [31]. Pressure activation of SLMP by breaking the protection layer covering the SLMP surface has been shown to be essential to utilize the Li powder properly, where the contact area between SLMP and Si surface is maximized by pressing the SLMP spheres onto the electrode surface [25,31]. Upon adding electrolyte to the cell, the SLMP will release Li ions into the electrolyte, then finally Li ions reach the anode surface to produce SEI layer and lithiated Si.

The SLMP-prelithiated anode was tested in the CR2032-type coin cell configuration against Li metal electrode in a voltage range of 1–0.005 V versus Li/Li+ under a constant current of 1 mA. The first cycle voltage profiles of the electrode with SLMP (SLMP/anode mass ratio = 0.26) are plotted in Fig. 4. It can be seen that the SLMP-prelithiated cell has a much lower open circuit potential (OCP) (∼0.14 V) than that of the SLMP-free cell (∼2.8 V) discussed earlier, which suggests Si inside the cell is already partially lithiated, as a result of insertion of the Li ions released by SLMP at anode side when they come into contact with electrolyte. The first discharge and charge capacities of the regular half-cell without SLMP reach 2298 and 1492 mAh/g, respectively. The first discharge capacity of the SLMP-containing cell is 1235 mAh/g, substantially lower than the 2298 mAh/g capacity achieved in the regular cell, confirming the partial lithiation behavior [26]. Moreover, the voltage plateau at ∼0.7–0.8 V during the first discharge of the regular cell (see Fig. 3 for comparison), which has been ascribed to the decomposition of electrolyte and the formation of SEI on anode surface, cannot be seen in the voltage profile for the SLMP cell, suggesting absence of SEI formation process during its first discharge. The first cycle irreversible capacity loss of the regular cell is 806 mAh/g, which is equivalent to a coulombic efficiency of 65%. The first charge capacity of the SLMP cell is 1207 mAh/g and hence yields a capacity loss of 28 mAh/g and a coulombic efficiency of 98%. Compared to the cell without SLMP, we see a large decrease of first cycle irreversible capacity loss by 97% and a significant improvement of first cycle coulombic efficiency by 51% in the SLMP-prelithiated cell.

The SiNPs–MWNTs composite paper anodes were applied with different amounts of SLMP, assembled into CR2032-type coin cells with Li metal counter electrode and tested in a voltage range of 1–0.005 V versus Li/Li+ under a constant current of 1 mA. After assembly, the OCP of each cell was recorded. The OCP of the fresh cells and the ratio between charge and discharge capacities after first discharge–charge cycle as a function of applied SLMP to SiNPs–MWNTs anode mass ratio are plotted in Figs. 5(a) and 5(b), respectively. In general, the more the SLMP applied, the lower the OCP and the higher the ratio between charge and discharge capacities during the first cycle. As the SLMP/anode mass ratio increases from 0 to 0.21, the OCP decreases from 2.8 V to 160 mV. It is also observed that the ratio between charge and discharge capacities during the first cycle increases from 65% to 90%. When the SLMP/anode mass ratio equals 0.26, the OCP is 140 mV and the ratio between charge and discharge capacities during the first cycle is 98%, which is the case described in Fig. 4. The inset of Fig. 5(b) gives a clearer image of the increasing trend of the first cycle charge/discharge capacity ratio for SLMP/anode mass ratio within 0.40. When the SLMP/anode mass ratio exceeds 0.50, the OCP drops to close to 0 V indicating a near full lithiation state where the first cycle discharge capacity could be very low. Therefore, an LIB can be designed using such fully prelithiated anode and non-Li providing cathode with a matched capacity for anode and cathode. It should be pointed that the ratio between charge and discharge capacities could be greater than 100%, because during the first discharge the measured discharge capacity corresponds to the amount of Li ions coming only from Li metal counter electrode; however, during the following charge the measured charge capacity corresponds to Li ions coming from two different sources, SLMP and Li metal counter electrode.

To understand more details, the impact of prelithiation on the cell discharge and charge capacities is depicted in Fig. 5(c). As expected, the higher the SLMP loading, the higher the prelithiation extent, and therefore the lower the first cycle discharge capacity. It is worth noting that the discharge capacity decreases almost linearly with increasing SLMP loading. Since the decrease in discharge capacity is a reflection of the contribution from effective insertion of SLMP, this near-linear relationship is indicative of uniform prelithiation of Si as more SLMP is applied. It can also be seen from Fig. 5(c) that the first charge capacity in general decreases with increasing the loading of SLMP, from ∼1500 mAh/g at no SLMP to ∼800 mAh/g at 0.5 SLMP/anode ratio. This result can be explained as follows: when the electrolyte is filled into the cell with SLMP-prelithiated anode, electrochemical reactions would be immediately started at a high rate, since the SLMP and anode are electrically connected with a short circuit. More SLMP loading would result in more intensive reactions, which could cause more SEI layer growth and SiNPs crystal structure damage that cause the low capacity of SiNPs.

Since the cells are already prelithiated, we believe they would be able to be charged without first discharge which is normally required to allow external Li source to intercalate into the anodes. To confirm this, a different batch of coin cells with varying SLMP loading were assembled and then directly charged to 1 V versus Li/Li+ under a constant current of 1 mA without first discharge process to measure the amount of Li that could be extracted from anode after prelithiation processes. Their first specific charge capacities are plotted against the SLMP/anode mass ratio in Fig. 6 (triangles). The SLMP utilization is defined as the ratio of the charge capacity measured experimentally to the capacity that the added mass of SLMP can provide theoretically and its relationship with the SLMP/anode mass ratio is also illustrated in Fig. 6 (circles). The theoretical capacity of added SLMP (CSLMP) is calculated using the following equation:

Display Formula

(1)$CSLMP=F×mSLMPMLi$

where F is the Faraday constant (96,485 C/mol), mSLMP is the weight of SLMP added, and MLi is the atomic weight of Li (6.94 g/mol).

It can be seen that both specific capacity and SLMP utilization increase with increasing the loading of SLMP. It can be understood as follows: when a tiny amount of SLMP (SLMP/anode mass ratio = 0.05) is applied, almost all the SLMP contributes to SEI formation by reaction with electrolyte, and therefore, the SLMP utilization is close to zero and so is the specific capacity. As SLMP/anode mass ratio goes up, Si-alloying SLMP comes into play and competes with SEI-forming SLMP. It should be pointed that the SLMP loaded on the surface of anode may not be totally consumed to form the prelithiated anode or SEI layer, some of SLMP could remain unreacted at the surface of SiNPs–MWNTs anode due to a poor electrical contact. Metallic Li was detected by NMR study which will be published separately. A schematic of the three possible outcomes of SLMP toward Si particles is illustrated in Fig. 7. The SLMP utilization agrees with OCP (Fig. 5(a)). At SLMP/anode mass ratio less than 0.2, most of SLMP contributes to the SEI growth, since the SEI growth rate is strongly dependent on the potential of the electrode; as SLMP/anode mass ratio becomes greater than 0.2, the potential of anode and SEI growth rate become stable, causing more SLMP to contribute to the insertion into the anode.

The percentage of SLMP utilized increases with increasing SLMP loading but remains relatively low (less than 40% even when the SLMP/anode mass ratio exceeds 0.5). However, the prelithiated anode is capable of providing specific capacity of 420 mAh/g for SLMP/anode mass ratio of 0.4 and specific capacity as high as 600–830 mAh/g when SLMP/anode mass ratio is around 0.5. These data thus affirm the idea that the prelithiated anodes can be paired with non-Li-providing cathode materials practically, which opens up the opportunity for improvement in Li-ion cell capacity and energy density.

Morphological Change After Prelithiation.

Figure 8 shows SEM image of a SiNPs–MWNTs anode containing SLMP at SLMP/anode mass ratio of 0.3 after prelithiation reaction. Compared with pristine anode as shown in Fig. 2(b), the Si nanoparticle size obviously increases, and the SEM image becomes blurred which is believed to be due to SEI layer growth at CNT and Si surfaces.

Conclusions

In summary, light-weight flexible freestanding SiNPs–MWNTs composite paper has been successfully synthesized by dispersing SiNPs and MWNTs in water-based system through ultrasonication followed by pressure filtration of resultant suspension. The composite paper is used as working electrode directly without any conductive additive or binder. The first specific discharge and charge capacities of the composite electrode material reach 2298 and 1492 mAh/g, respectively, which are much higher than the capacity of commercial graphite anode. However, there is a large capacity loss of 806 mAh/g and low coulombic efficiency associated with electrolyte decomposition and SEI formation during the first cycling process. The SLMP prelithiation approach is employed to improve the first cycle coulombic efficiency, and the SLMP loading is varied for the optimization of this battery chemistry. It has been shown that the SLMP amount has a significant impact on the cell OCP, first cycle coulombic efficiency, and specific discharge and charge capacities. At an SLMP/anode mass ratio of 0.26, we are able to compensate for the first cycle irreversible capacity loss leading to a rise of the first cycle coulombic efficiency from 65% to 98%.

It is well demonstrated that the SLMP provides an effective prelithiation approach for addressing the first cycle irreversibility, which renders the SiNPs–MWNTs composite paper as a promising candidate for the construction of new Si-based LIBs suitable for future high-energy applications due to its light-weight and high-capacity features. The incorporated SLMP also acts as a different form of Li source other than conventional Li-providing cathode materials and allows the cell to deliver charge capacity over 800 mAh/g without the first discharge process. This makes it possible for higher-capacity cathode materials to be used in the LIB chemistry. Future work will include studying the cycle performance and implementing the prelithiated Si anodes in full-cell assembly to explore the optimal anode–cathode combination.

Acknowledgements

This work was supported by DOE BATT Program through PNNL under Contract No. 212964. The authors gratefully acknowledge Dr. Qiang Wu and Dr. Wanjun Cao for their assistance and helpful discussions.

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Cao, W. , Li, Y. , Fitch, B. , Shih, J. , Doung, T. , and Zheng, J. , 2014, “ Strategies to Optimize Lithium-Ion Supercapacitors Achieving High-Performance: Cathode Configurations, Lithium Loadings on Anode, and Types of Separator,” J. Power Sources, 268, pp. 841–847.
Forney, M. W. , Ganter, M. J. , Staub, J. W. , Ridgley, R. D. , and Landi, B. J. , 2013, “ Prelithiation of Silicon-Carbon Nanotube Anodes for Lithium Ion Batteries by Stabilized Lithium Metal Powder (SLMP),” Nano Lett., 13(9), pp. 4158–4163. [PubMed]
Chew, S. Y. , Ng, S. H. , Wang, J. Z. , Novak, P. , Krumeich, F. , Chou, S. L. , Chen, J. , and Liu, H. K. , 2009, “ Flexible Free-Standing Carbon Nanotube Films for Model Lithium-Ion Batteries,” Carbon, 47(13), pp. 2976–2983.
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Cao, W. J. , Shih, J. , Zheng, J. P. , and Doung, T. , 2014, “ Development and Characterization of Li-Ion Capacitor Pouch Cells,” J. Power Sources, 257, pp. 388–393.
Cao, W. , Li, Y. , Fitch, B. , Shih, J. , Doung, T. , and Zheng, J. , 2014, “ Strategies to Optimize Lithium-Ion Supercapacitors Achieving High-Performance: Cathode Configurations, Lithium Loadings on Anode, and Types of Separator,” J. Power Sources, 268, pp. 841–847.
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Figures

Fig. 1

(a) A freestanding SiNPs–MWCNTs composite paper demonstrating its flexibility, (b) half-inch composite paper electrode, and (c) the electrode in (b) with SLMP pressed onto the surface

Fig. 2

(a) Cross-sectional and (b) top-view SEM images of SiNPs–MWCNTs composite paper

Fig. 3

Voltage profiles from first and second cycles of SiNPs–MWCNTs anode

Fig. 4

Representative first cycle voltage profile of SLMP-prelithiated composite paper anode

Fig. 5

(a) Open circuit potential, (b) first cycle charge/discharge capacity ratio, and (c) first cycle discharge (triangles) and charge (circles) capacities of SLMP-prelithiated cells as a function of SLMP to anode mass ratio. Inset in (b) shows the relationship for SLMP/anode mass ratio in the range of 0–0.4.

Fig. 6

First cycle specific charge capacity (without first discharge) of SLMP-prelithiated cells and SLMP utilization versus SLMP/anode mass ratio

Fig. 7

Schematic of three possible outcomes of SLMP toward Si particles. Note that the sizes of SLMP and Si particles are not true to scale.

Fig. 8

SEM image of SiNPs–MWCNTs composite anode after prelithiation by SLMP

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