High-Performance Lithiated SiOx Anode Obtained by a Controllable

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High-Performance Lithiated SiOX Anode Obtained by a Controllable and Efficient Prelithiation Strategy Qinghai Meng, Ge Li, Junpei Yue, Quan Xu, Ya-Xia Yin, and Yu-Guo Guo ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b12086 • Publication Date (Web): 08 Aug 2019 Downloaded from pubs.acs.org on August 8, 2019

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ACS Applied Materials & Interfaces

High-Performance Lithiated SiOX Anode Obtained by a Controllable and Efficient Prelithiation Strategy Qinghai Meng, †,

§

Ge Li,†, ‡,

§

Junpei Yue, † Quan Xu, † Ya-Xia Yin,†, ‡ and Yu-Guo

Guo†, ‡, *

†

CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, CAS

Research/Education Center for Excellence in Molecular Sciences, Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, P. R. China ‡

University of Chinese Academy of Sciences, Beijing 100049, P. R. China

KEYWORDS: Li-ion batteries, SiOx anode, Full cells, Prelithiation, Initial Coulombic efficiency

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ABSTRACT

Silicon-based electrodes are promising and appealing for futuristic Li-ion batteries because of its high theoretical specific capacity. However, massive volume change of silicon upon lithiation and delithiation, accompanied by continual formation and destruction of solid electrolyte interface (SEI) leads to low Coulombic efficiency. Prelithiation of Si-based anode is regarded as the effective way for compensating the loss of Li+ in the first discharging process. Here, a high-performance lithiated SiOx anode was prepared by using a controllable, efficient and novel prelithiation strategy. The lithiation of SiOx is homogeneous and efficient in bulk due to well-improved Li+ diffusion in SiOx. Moreover, the in-situ formed SEI during the process of prelithiation reduces the irreversible capacity loss in the first cycle, and thus improves the initial Coulombic efficiency (ICE). Half cells and full cells based on as-prepared lithiated SiOX anode prominently increase ICE from 79 to 89%, and 68 to 87%, respectively. It's worth mentioning that the homogeneously lithiated SiOx anode achieves stable 200 cycles in NCM622//SiOx coin full cells. These exciting results provide applicable prospects of lithiated SiOx anode in the next-generation high energy density Li-ion batteries.


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INTRODUCTION

As one of the main origins of carbon emissions, traditional fuel vehicle is considered the main pollution source of haze which takes place frequently in cities.1 An increasing number of countries have announced plans to phase out fossil fuel vehicles.2 In the past 5 years, the electric vehicles have a rapid development all over the world owing to their environmental and economic merits. However, there are still several obstacles for the further evolution of electric vehicles, such as inconsistent availability of charging station, long charging time, and short continuing voyage ability et al. The first two issues can be solved by building more charging station or establishing rentable battery changing stations. To be candid, the last issue is challenging and can be conquered by means of developing next-generation high energy batteries. 3-8

Si-based novel materials are regarded as the ideal and prospective anodes for futuristic Li-ion batteries (LIBs), due to the high specific capacity of 3580 mA h g-1 (Li15Si4), which is up to 10 times higher than that of graphite anodes in conventional lithium-ion batteries.9-11 Hence, replacing graphite partly or entirely with Si-based materials will effectively increase the energy density. However, the large volumetric change is up to 300% during charging and discharging process, which leads to the break and formation of unstable, thick solid electrolyte interphase (SEI) layer and the pulverization and electrical isolation of Si particles.12-14 The continuous formation of SEI layer incessantly on the fresh Si surface consumes Li+ and electrolytes, resulting 3 ACS Paragon Plus Environment


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in low Coulombic efficiency (especially ICE) and fast specific charging/discharging capacity decay.15-16 Introducing additional Li+ into Si-based anode in advance, named by prelithiation, is a reliable method to alleviate this issue.17-23 Several prelithiation methods have been explored in both academic and industrial fields, including electrochemical prelithiation,24-26 laminating lithium foil or spreading stabilized lithium metal powder (SLMP) on anode,21,

27-29

introducing Li-rich materials into

cathode,30-31 or short circuit prelithiation by direct contact of anode with Li foil in electrolyte.32 Although great progress has been made, some key factors still need to be conquered. Electrochemical prelithiation is controllable and easy to operate in lab, but still have a long way for practical application. The prelithiation by using Li foil or SLMP can be grafted and integrated to industrialized electrode processing, however, the high reactivity of lithium foil especially lithium powder needs excessive environment demands for processing. Besides, the excess of Li will affect the safety and cycling stability of battery due to the growth of Li dendrites on the surface of anode. By mixing in cathode, Li-rich materials can supply redundant Li+ at the first charging process and then lose efficacy. Nevertheless, the inert and irreversible materials will decrease the energy density of battery. Lithiation by direct contact of anode with Li foil in electrolyte has advantages of high operating efficiency, ease for practical application, and no need of additional complicated device. However, this method lacks of precise control on the rate and degree of lithiation.

In this study, a high-performance lithiated SiOx anode was prepared by a controllable, efficient and novel prelithiation method. We optimized the prelithiation strategy of 4 ACS Paragon Plus Environment

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direct contact of anode and Li foil by inserting a resistance buffer layer (RBL) between them to regulate the rate and degree of lithiation. The porous structure and high electric conductivity of RBL are beneficial to the transfer of Li+ and the delivery of electrons, and the soft feature of RBL enables highly close contact of Li foil and anode, resulting in the homogeneous prelithiation of SiOx anode in an efficient way. Besides, the as-prepared lithiated SiOx anode possessed freshly-formed SEI layer during the process of prelithiation, and exhibited high ICE and specific capacity in both half cells and full cells.

EXPERIMENTAL SECTION

2.1 Preparation of electrode SiOx (Theoretical capacity 750 mA h g-1) and LiNi0.6Co0.2Mn0.2O2 (NCM622) powders obtained from Beijing IAmetal New Energy Technology Co., LTD and Hubei Ronbay Lithium Material Co., LTD were used as anode and cathode, respectively, and were dried in the vacuum oven before use. The anode slurry was prepared by mixing 80 wt% SiOx, 10 wt% Super P, and 10 wt% fluorinated polyacrylate composite binder in water. The pristine SiOX electrode was made by coating the slurry onto Cu foil and dried at 60 oC in vacuum oven overnight. Similarly, the NCM622 slurry was made in same formula except using 1-Methyl-2-pyrrolinone (NMP) as solvent. The cathode electrode was made by coating the slurry onto Al foil and dried at 80 ℃ in vacuum oven overnight. 2.2 Prelithiation of pristine SiOx anode



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The resistance buffer layer (RBL) was prepared by coating Polyvinyl Butyral (PVB) on CNT film (Suzhou Jernano Technology Co., LTD). The areal resistance can be controlled by the coating times. The pristine SiOX electrode was soaked in electrolyte under vacuum environment before use. For the prelithiation process, lithium foil, RBL, and pristine SiOX were laminated together, followed by dropping 50 μl electrolyte and then the prelithiation was conducted in vacuum condition for desired time ranging from 0 to 20 minutes with the press of a 2 kg weight. The high-performance lithiated SiOx anode was obtained after washing in 1, 3-dioxlane (DOL) to remove residual electrolyte. For assembling cells, anodes were cut out in disc electrodes with the diameter of 10 mm, and laminated with separators and cathode or lithium foil together. For full cells, the capacity ratio of anode to cathode was set to 1.05:1. 2.3 Instrumentation The morphologies of the SiOx anode and CNT films were investigated by field emission Scanning Electron Microscopy (SEM, Hitachi S-4800, Japan). Elemental analysis and depth profiles of the SiOx anode were determined by ToF-SIMS (TOF.SIMS5 IONTOF GmbH). XPS was carried out on the ESCALab 250Xi (Thermo Scientific) using 200W monochromatized Al Kα radiation. The specific resistance was tested by RTS9 (Guangzhou 4 probes tech). The charge and discharge measurements of batteries were carried out in a voltage window of 0.005–2.0 V (for half cells) and 2.5-4.3 V (for full cells) by LAND CT2001A. Electrochemical impedance spectroscopy measurements were performed using an Autolab workstation in the frequency range from 100 kHz to 0.1 Hz.


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RESULTS AND DISCUSSIONS During the prelithiation process, the transfer of Li+ and electrons between Li foil and SiOx electrode are illustrated in Figure 1. As shown in Figure 1a, with respect to the rough texture of Li metal and SiOx electrode in direct contact prelithiation process, the electron transfer only occurs in the contact point and radiates around due to diffusion process, resulting in the uneven prelithiation of SiOx electrode from the view of the plane.

Figure 1． Illustration of Li-ion and electron transfer in (a) direct contact prelithiation process and (b) RBL regulated prelithiation process. Furthermore, the strong reduction property of metallic lithium induces a highly inhomogeneous prelithiation in the perpendicular direction of the plane as well. As shown in Figure S1a, the RBL was prepared by coating Polyvinyl Butyral (PVB) on Carbon Nanotube film in order to deal with the issue faced in traditional direct contact prelithiation. Carbon nanotube film (Figure S1b) has excellent conductivity and its resistance can be adjusted through the PVB layer, which can regulate the electron transformation in some extent. Moreover, the flexible feature of the RBL provides a favourable contact between lithium foil and SiOx electrode (Figure 1b), which could



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alleviate the non-uniform electron transfer and facilitate the homogeneous prelithiation.

Figure 2. ToF-SIMS elemental distribution images of (a) Li－, (b) C－ and (c) the overlay of Li－ (red) and C－ (green) species in the direct contact prelithiated SiOx electrode, and (d) Li－, (e) C－ and (f) the overlay of Li－ (red) and C－ (green) species in the RBL regulated prelithiation of SiOx electrode. The practical prelithiation results can be demonstrated by the Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis as shown in Figure 2. For the direct contact prelithiated SiOx electrode, the elemental distribution image of Li

－

is

punctate (Figure 2a and 2c) owing to the insufficient interfacial contact, which could be attributed to the uneven surface of Li foil and SiOx electrode (Figure 2b). On the contrary, the signal of Li－ in the SiOx electrode prelithiated with RBL is much more uniform than that in the SiOx electrode by direct contact prelithiation (Figure 2d and 2f), indicating the improved interfacial contact between Li foil and SiOx electrode by the flexible RBL. In addition, the Li－ ion intensity in the RBL regulated prelithiated 8 ACS Paragon Plus Environment

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SiOX electrode diminished gradually along with prolonged sputter time as shown in the depth profiles, unlike the rapidly reduction in the direct contact prelithiated SiOx electrode (Figure S2). The diverse distribution of Li－ ion confirmed that the flexible RBL can successfully solve the issues faced by direct contact prelithiation (Figure 2c and 2f) and achieve homogeneous prelithiation of SiOx electrode from width and depth under the condition of rough texture (Figure 2b and 2e).

Figure 3. SEM images of (a) SiOx electrode without prelithiation, (b) the cross section of SiOx electrode without prelithiation, (d) SiOx electrode with RBL regulated prelithiation and (e) the cross section of SiOx electrode with RBL regulated prelithiation. XPS spectra of Si2p in (c) SiOx electrode without prelithiation and (f) SiOX electrode with RBL regulated prelithiation. In order to clarify the effect of RBL regulated prelithiation on the morphology and chemical oxidation state and bonding information of SiOx electrodes, the scanning electron microscopy (SEM) images and X-ray photoelectron spectroscopy (XPS) analysis of pristine and prelithiated SiOx electrodes were performed as shown in Figure 3. For the pristine electrode, various particles on the electrode surface are well



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defined without any adhesion and have average particle size of 10 μm (Figure 3a), and the electrode thickness is about 54 μm as shown in Figure 3b. After 20 min of RBL regulated prelithiation, no cracks and pulverization of the particles on the surface of SiOX electrode are observed and the average particle size increases to about 15 μm (Figure 3d and S3) and the electrode thickness increased to 78 μm as well (Figure 3e) due to the volume expansion of SiOX composite materials during the lithiation process. The volume expansion degree (approx. 1.5 times of the pristine one) from the top view and cross section is identical, indicating the homogenous lithiation in all direction. Furthermore, the coverage of SEI on SiOX electrode after prelithiation can be confirmed by XPS measurements illustrated below. The in-situ formed SEI layer during prelithiation can reduce the loss of active Li-ions at the first cycle and increase the Coulombic efficiency as well.33-34 From the XPS survey, F1s peak were observed in pristine and lithiated samples (Figure S4e), which is originated from binders. Obviously, Li1s peak (Figure S4f) located at 55.8 eV occurs after prelithiation and can be assigned to lithiated SiOx (Li4SiO4) and SEI components (Li2CO3).35-36 The Si2p core level XPS peaks are shown in Figure 3c and the Si2p peaks located at 98.8 and 102.9 eV with orbit-spin splitting energy of 0.65 eV can be assigned to Si and SiOx/SiO according to the previous report.37 The peak located at 104.5 eV with a large splitting energy (1.1 eV) maybe derived from SiO2.19 Meanwhile, the deconvolution of Si2p peaks in the SiOx electrode prelithiated with RBL demonstrates the two states of Si (Figure 3f), Li4SiO4 at 102.2 eV and SiOx at 103.4 eV. The molar ratio of Si in Li4SiO4 and SiOx is more than 3, indicating a high lithiated level. In the O1s spectrum


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(Figure S4h), the peak at 531.98 eV is assigned to Li2CO3.35, 38 Similarly, two newly appeared peaks located at 283.2 and 290.1 eV in C1s core level XPS spectra (Figure S4d and S4h) after prelithiation can be assigned to LixC and Li2CO3, which can be attributed to the lithiation of carbon materials in SiOx electrode and the formation of SEI, respectively.7, 19, 39 Furthermore, the peak located at 685.1 eV in F1s can be attributed to LiF,40 and in combination with Li2CO3 confirmed the inorganic components in SEI, which are similar with normal SEI formed during electrochemical cycles (Figure S4j). In combination of the data from ToF-SIMS, SEM images and XPS measurements, the homogenous lithiation of SiOx electrode from the view of all direction can be achieved through the specially-designed RBL regulated prelithiation method. Different degrees of lithiation can be achieved with tunable prelithiation parameters in the RBL regulated prelithiation method. As shown in Figure 4a, the areal resistance of RBL, which can regulate the current efficiently during the prelithiation process, raise evidently with the increase of coating times of PVB (Figure S5a). Obviously, a high resistance results in a low current, meaning a slow lithiation rate and a low prelithiation degree at given time, corresponding to a low ICE of SiOx electrode and high open circuit potential, and vice versa. Furthermore, the prelithiation time is an essential parameter to tune the lithiation degree. As shown in Figure 4b, a long prelithiation time can reduce the open circuit potential of a half-cell and promote the ICE, representing a deeper lithiation. The facile tunable parameters enable the accessibility of different lithiation degree and large-scaled production.



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Figure 4. (a) Specific resistance of CNT-PVB film and ICE of SiOx electrode with corresponding RBL regulated prelithiation in dependency of the PVB coating time. (b) Open circuit potential and ICE in dependency of the prelithiation time. (c) Initial charge and discharge profiles, (d) cyclic voltammetry profiles, (e) electrochemical impedance plots, and (f) cycling performance and Coulombic efficiency of SiOx electrode with and without prelithiation. To evaluate the merit of prelithiation by using the RBL, initial charge-discharge curves of SiOX electrodes with various prelithiation times were measured in the SiOx-Li half-cell (Figure S5b). Taking the curve of 5 min prelithiation as an example, the ICE is promoted to 89.2% (specific discharge capacity, 833 mA h g-1) from 79.4% (SiOx electrode without prelithiation, specific discharge capacity, 944 mA h g-1).The capacity loss, which mainly results from the irreversible capacity caused by the formation of Li2O and SEI, has been reduced to 90 mA h g-1 (capacity loss 2) from 194 mA h g-1 (capacity loss 1) as shown in Figure 4c.12 Specifically speaking, the 12 ACS Paragon Plus Environment

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capacity loss at the first cycle can be compensated via as-formed SEI and adding active Li+ source. As shown in Figure 4c, SEI is electrochemically formed at the potential range of 1.0 and 0.3 V vs Li+/Li, and contributes 60 and 5 mA h g-1 of the overall irreversible capacity for pristine and prelithiated SiOx electrodes, respectively. This significant reduction of irreversible capacity also confirms the formation of a partial SEI during the prelithiation process. The pre-built SEI, which is crucial in promoting the cycle stability and ICE, is also verified by the absence of cathodic peak at ~0.8 V in the cyclic voltammetry (CV) profiles (Figure 4d).35, 41-42 Figure 4e and S5c show the results of electrochemical impedance spectroscopy (EIS) plots. For SiOx without prelithiation, one semicircle at high frequency (corresponding to charge-transfer resistance) and a straight sloping line at low frequency (associated with diffusion resistance through the bulk of the active material) can be seen clearly.43 However, two semicircles of SiOx electrode with RBL regulated prelithiation were observed. The related equivalent circuit was shown in Figure S6, and the solid lines in Figure 4e and S5c are the fitted results and agree well with the actual Nyquist plot.27 Obviously, SiOx electrode with RBL regulated prelithiation exhibits the semicircles of Rsei which cannot be found in Nyquist plot of SiOx without prelithiation, indicating the formation of SEI and results in higher ICE. Besides, the Rct of SiOx electrode with RBL regulated prelithiation is lower than that of SiOx without prelithiation due to the well wetting of electrolyte during the process of prelithiation in vacuum condition and the improvement of electronic conductivities of electrode after lithiation. Furthermore, the cycle stability of the prelithiated electrode



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with high ICE (89.2%) is maintained, which demonstrates 75.4% capacity retention after 300 cycles and is comparable with that of electrode without prelithiation (77.2% capacity retention) as shown in Figure 4f.

Figure 5. (a) Initial charge and discharge profiles of NCM622-Li half-cell. (b) Initial charge and discharge profiles, (c) electrochemical impedance plots and (d) cycling performance and Coulombic efficiency of NCM622-SiOx full-cell with and without prelithiation. It is worth noting that a high ICE would increase the stability and life time of a full battery rather than a half-cell with metallic lithium as a counter electrode. Hence the NCM622-SiOx full cells were assembled to examine the practicability of the RBL regulated prelithiation (Figure 5), which is assembled with LiNi0.6Co0.2Mn0.2O2 cathode and SiOx anode. As shown in Figure 5b, the discharge capacity of prelithiated NCM622-SiOx full cell achieved 173 mA h g-1 with ICE of 87.3%, which is consistent with that of NCM622-Li half cell (Figure 5a) and much higher than that of 14 ACS Paragon Plus Environment

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NCM622-SiOX full cell without prelithiation with 134 mA h g-1 discharge capacity and 68.9% ICE. In addition, the average potential of prelithiated NCM622-SiOX full cell is improved apparently by the prelithiation process, which can enhance the cell energy density directly. The cathode-limited ICE and improved average potential indicate the brilliant electrochemical performance of prelithiated SiOX electrode, which emphasize the merit of prelithiation process. Two semicircles (Figure 5c) in the high-frequency range and identical slope (Figure S6c) in the low-frequency range in the electrochemical impedance spectra also proved the evidences of prelithiation in NCM622-SiOX full cell. After 200 cycles, the reversible capacity of prelithiated NCM622-SiOX full cell maintains at 128 mA h g-1 with 74% capacity retention, which is much superior than that of NCM622-SiOX full cell without prelithiation with only 66 mA h g-1 as shown in Figure 5d. Moreover, the rate capability of prelithiated NCM622-SiOX full cell is also improved and approaches to that of NCM622-Li half cell (Figure S6a and S6b, supporting information), which indicates the promising prospect of the prelithiation method.

CONCLUSIONS In summary, a high-performance lithiated SiOX anode was obtained by a controllable and efficient prelithiation strategy. The use of RBL highly improves the homogeneous of lithiation through regulating the Li-ion and electron dispersing interface between Li and SiOX anode. SEI was pre-built and Li-ion was compensated in advance during the process of prelithiation. Thus, the capacity loss resulting from



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the irreversible capacity and the formation of SEI was alleviated during the RBL regulated prelithiation. The lithiated SiOX anode based half cells present tunable ICE ranging from 78% to 137% and full cells simultaneously exhibit 173 mA h g-1 of initial specific discharge capacity and 87% of ICE at current density of 0.1 C. Moreover, 77% capacity retention was obtained after 200 cycles of charging and discharging at current density of 0.5 C. The initial Coulombic efficiency, specific capacity and cycling stability of lithiated SiOX based half and full cells were improved significantly, indicating great prospects for the commercial application of Si based anode materials. ASSOCIATED CONTENT Supporting Information The preparation of resistance buffer layer and the process for prelithiation, SEM images, ToF-SIMS depth profiles and XPS survey of SiOx with and without prelithiation, the electrochemical performances of SiOx with various prelithiation time and the equivalent circuit of electrochemical impedance plots were summarized. AUTHOR INFORMATION Corresponding Author *

E-mail: [email protected].

Author Contributions §

Q. H. Meng and G. Li contributed equally to this work.


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Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT Prof. Y.-G. Guo proposed the idea and supervised the work. Q. H. Meng and G. Li conducted the experiment and wrote the paper. Thanks for J. Yue’s discussion on results and revision of paper. This work was supported by the Basic Science Center Project of National Natural Science Foundation of China under grant No. 51788104, the National Natural Science Foundation of China (Grant Nos. 21773264 and 51772301), the National Key R&D Program of China (Grant No. 2016YFA0202500), the "Transformational Technologies for Clean Energy and Demonstration", Strategic Priority Research Program of the Chinese Academy of Sciences, Grant No. XDA21070300, CPSF-CAS Joint Foundation for Excellent Postdoctoral Fellows (Grant No. 2017LH028), and China Postdoctoral Science Foundation (Grant No. 2017M620913). REFERENCES (1) Chu, S.; Majumdar, A. Opportunities and Challenges for a Sustainable Energy Future. Nature 2012, 488, 294-303. (2) Eberle, U.; Müller, B.; Von Helmolt, R. Fuel Cell Electric Vehicles and Hydrogen Infrastructure: Status 2012. Energ. Environ. Sci. 2012, 5, 8780-8798. (3) Li, H.; Wang, Z.; Chen, L.; Huang, X. Research on Advanced Materials for Li‐



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High-Performance Lithiated SiOx Anode Obtained by a Controllable

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