In Situ AFM Imaging of Solid Electrolyte Interfaces on HOPG with

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In Situ AFM Imaging of Solid Electrolyte Interfaces on HOPG with Ethylene Carbonate and Fluoroethylene Carbonate-Based Electrolytes Cai Shen, Shuwei Wang, Yan Jin, and Wei-Qiang Han ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.5b08238 • Publication Date (Web): 26 Oct 2015 Downloaded from http://pubs.acs.org on November 1, 2015

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ACS Applied Materials & Interfaces

In Situ AFM Imaging of Solid Electrolyte Interfaces on HOPG with Ethylene Carbonate and Fluoroethylene Carbonate-Based Electrolytes Cai Shen*, Shuwei Wang, Yan Jin, Wei-Qiang Han* Ningbo Institute of Materials Technology & Engineering, Chinese Academy of Sciences. 1219 Zhongguan Road, Zhenhai District, Ningbo, Zhejiang, China. Fax: 86-574-87910728; Tel: 86-574-86682743; KEYWORDS: Lithium-ion battery; Atomic force microscopy; Solid electrolyte interfaces; Electrolyte; Electrochemistry; ABSTRACT: Chemical and morphological structure of solid electrolyte interphase (SEI) plays a vital role in lithium-ion battery (LIB), especially for its cycleability and safety. To date, research on SEI is quite limited due to the complexity of SEI and lack of effective in situ characterization techniques. Here, we present real-time views of SEI morphological evolution using electrochemical atomic force microscopy (EC-AFM). Complemented by an ex situ XPS analysis, fundamental differences of SEI formation from ethylene carbonate (EC) and fluoroethylene carbonate (FEC)-based electrolytes during first lithiation/delithiation cycle on HOPG electrode surface were revealed.

INTRODUCTION Solid electrolyte interface (SEI), a sacrificial layer reduced from electrolyte solution, enables commercial lithium-ion batteries (LIBs) to operate at a potential of above 3.0V when organic electrolyte is applied (vs. Standard Hydrogen Electrode, SHE).1-3 SEI is a good lithium ion (Li+) conductor and electric insulator. Physicochemical properties of SEI determine not only the reversibility of Li+ intercalation at the anode but also strongly affect the kinetics of Li+ transport across the electrode-electrolyte interface.4-6 SEI plays a vital role in operation, safety and cyclability of LIBs.7-14 Continuous growth of SEI which led to loss of available Li+ is well known as the primary reason for longterm degradation of large-scale LIBs.9,15 Thus, understanding of SEI formation on anode materials especially graphite is important for development of high-performance LIBs.16 To date, SEI formation on graphite anode has been clarified to a considerable extent using a variety of techniques.1,10,17-25 However, details on SEI formation (3D evolution), composition, stability, and its influence on the performance of LIBs are still controversial. More research efforts to improve SEI stability and to better understand the nature of SEI formation on graphite anodes are needed. Ideally, SEI layer should be compact, insoluble and irreversibly adhere to the active surface. Upon formation, SEI layer should be stable enough to stop further decomposition of the electrolyte solution. SEI formed from fluoroethylene carbonate (FEC)-based electrolyte on anode is

known to improve cyclability and shelflife of LIBs.26,27 This is mainly due to preferential reduction of FEC over other electrolyte species which led to formation of an electrochemically stable SEI layer on the anode.28-32 For example, uniform lithiation of silicon nanowire was observed in FEC-containing electrolyte using transmission electron microscopy (TEM). Meanwhile, a nonuniform lithiation was observed in a FEC-free system.28 To date, the exact mechanisms underlying the improvements are still controversial and poorly understood. Nakai et al. found that FEC-containing electrolytes formed very thin SEI layers as compared to those of ethylene carbonate (EC) electrolytes.26 In contrast, McArthur et al. found a thicker SEI layer on anodes when cycled with FEC-containing electrolyte.33 Scanning probe microscopy (SPM) include scanning tunneling microscopy (STM) and atomic force microscopy (AFM), are useful tools to measure electronic current and surface topography.34-43 Studies of SEI layer using STM were limited by the fact that SEI layer is an electronically insulating layer.7 Thus, only reactions happen at the early stage of the electrochemistry can be observed.7,44 In situ analysis by atomic force microscopy (AFM) with electrochemical control on the electrode allows direct study of surface reaction and topography evolution, while maintaining conditions that closely simulate real-life devices with minimal destructive impact.18,21,45-53 It provides the capability to directly monitor changes of SEI layers as a function of applied electrochemical potentials and/or

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Cyclic Voltammetry Curves of Li-HOPG Cell with EC/DMC Electrolyte. Cyclic voltammetry (CVs) coupled with AFM scanning were performed in argon filled glovebox to investigate formation of SEI. HOPG, composed of atomically flat, high crystallinity and low surface area carbon, is an ideal substrate for probing dynamic reactions. Figure 1 shows the first CV curve of freshly cleaved HOPG basal plane at a scanning rate of 5 mV/s between 3.0 and 0.0 V( scanning direction: 3.0 V-0.0 V-3.0 V) in the 1 mol/L LiPF6/EC/DMC. The current flow above 1.0 V (figure 1, insert) is assigned to the reduction of trace oxy-

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RESULTS AND DISCUSSION

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Characterization. Ex-situ XPS analysis was performed on Kratos Axis Ultra X-ray photoelectron spectrometer using 1253.6 eV Mg KαX-rays. Samples were removed from the Li-HOPG cells and rinsed with dimethylcarbonate (DMC) to remove residual salt and solvent in an argon-filled glovebox. All samples were first gently cleaned in DMC solution and then dried under vacuum. Samples were then transported to XPS facility in sealed bags to avoid contact with air. The analyzed area of SEI layer was 300×700 μm2. The binding energies were referenced to the hydrocarbon C1s photoelectron peak at 284.8eV.

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Electrochemical Performance and Image Scanning Using EC-AFM. In situ AFM (Bruker Icon) experiments were conducted in an argon-filled glovebox (MBRAUN, H2O ≤ 0.1 ppm, O2≤ 0.1 ppm) at room temperature. The Li-HOPG cell was composed of HOPG substrate as working electrode (WE) and Li wire as counter and reference electrodes (CE and RE). HOPG (Bruker Corporation, ZYB Grade, 12×12×2 mm) was cleaved with adhesive tape to obtain a flat basal plane. Electrolyte solution used was 1 M LiPF6 dissolved either in a mixture of ethylene carbonate or fluoroethylene carbonate/dimethyl carbonate (EC/DMC or FEC/DMC, volume ratio of 1:1) (Shanshan Corporation). In order to form SEI layer on HOPG, the LiHOPG cell was studied by cyclic voltammetry (CV) at a scanning rate of 5 mV﹒s−1or 0.5 mV﹒s−1 between 3.0 and 0 V. AFM topography was collected simultaneously in ScanAsyst mode using nitride coated silicon probes (tip model: SCANNASYST-FLUID with k=0.7 N/m, Bruker Corporation). Contact mode was applied to scratch the surface using the same probe.

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Here, we report the morphological and compositional differences of SEI layer formed from EC and FEC-based electrolytes on HOPG electrode. Application of AFM for morphological analysis is complemented with XPS for chemical characterization which brings new insight into effects of electrolytes on structure and composition of SEI.

gen and water as well as contaminations in the electrolyte.21 A sharp cathodic peak which starts around 0.8 V and disappeared in the following cycles (figure S1), is attributed to the irreversible reduction of electrolyte and the formation of SEI.20,21 Decreased in potential to below 0.3 V led to steady increased of the cathodic current to the turning point (0 V). In the oxidation state, one broad peak appears at around 1.2 V. Continuous increment of the cathodic current under 0.3 V and the anodic peak at around 1.2 V are the results of lithium intercalation and de-intercalation at the step edges of HOPG basal plane, respectively.

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electrolyte compositions/additives.54 Therefore, electrochemical AFM was employed instead of STM to clarity the whole reactions happening during the SEI formation.20,55

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Figure 1. CV curves of the freshly cleaved HOPG in 1 mol/L LiPF6/EC/DMC. Scanning rate is 5 mV/s. The insert shows the current flow from 1.0 to 2.5 V. In Situ AFM imaging of SEI formation with EC/DMC Electrolyte. Peak Force Tapping mode was used to trace the morphological evolution of electrode surface under potential control. Peak Force Tapping mode performs a very fast force curve at every pixel in the image. The peak force of each curves was then used as the imaging feedback signal to provide direct force control. This allows it to operate at even lower forces than Tapping Mode, which protected the delicate samples. Furthermore, cantilever tuning is not required as Peak Force Tapping mode does not resonate. This is particularly advantageous in fluids. Figure 2 shows surface structural evolution of HOPG electrode during the first lithiation-delithiation cycle. Upon injection of electrolyte into the cell, there were some small particles (figure 2a) with the height of few nm formed on the surface of HOPG (in the stage of open circle potential, OCP), which might due to the decomposition of contaminations. Large amount of SEI began to grow after voltage swept down to ~0.8 V (figure 2c). Further reduction of the potential induced the breakout of precipitates which covered the whole surface of HOPG (figure 2d). Appearance of substance on the surface is consistent with the electrochemical result. The surface remained unchanged during the anodic sweeping (figure 2e,f). Line profile (figure S2) revealed that the heights of

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these precipitate are in the range of 10-30 nm and the sizes of them are in the range of ~100-200 nm.

Figure 3. (a) Exposed area of the lower layer of SEI after removal of the top layer by AFM scanning in the contact mode. (b) Line profile of the lower nodular layer. Figure S4a shows the surface structure of HOPG electrode cycled in a slow scanning rate of 0.5 mV/s. No dramatic change was found in comparison to those of the fast scan (figure 2). However, line profile (figure S4c) revealed that the heights of the precipitate are in the range of 50-100 nm, which is larger than the one deposited from the slow scan. In Situ AFM imaging for SEI formation with FEC/DMC Electrolyte. Figure4 shows the first CV curve of freshly cleaved HOPG basal plane at a scanning rate of 5 mV/s between 3.0 and 0.0 V (scanning direction: 3.0 V0.0 V-3.0 V) in the 1 mol/L LiPF6/FEC/DMC.

Figure 2. In situ AFM images of HOPG electrode cycled at a scanning rate of 5 mV/s between 3.0 and 0.0 V in the 1 mol/L LiPF6/EC/DMC(a-f). The arrow indicates the AFM scanning direction. The potential in image d starts from cathodic 0.3 V to o.o V, and then reverse to anodic 0.95 V. The scales bars are 1μm. Precipitates formed were easily scraped off with a force of about 70 nN by repeated AFM scanning (normally 1-2 scans is sufficient) in the contact mode. Figure 3 shows an AFM image and a height profile of the same area of figure 2. The lower layer consisted of nanometer-sized, nodular features that decorated both the basal planes and edge sites. In comparison to the precipitates of the upper layer, the lower nodular layer was very thin and only have a height of ~few nanometers as revealed by the height profile (figure 3b). It is also noted that the lower layer was very stable even under repeated AFM scanning by maximum force in the contact mode. The results of AFM observation revealed that the SEI composed of two layers, that is, a loosely packed precipitates on the top and a hard nodular layer underneath. It is found that the SEI remained unchanged in the following cyclic voltammetry (figure S3), which suggested that once the SEI was formed, it is stable and play a vital role in suppressing further reductive decomposition of solvent molecules and salts.

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Figure 4. CV curves of the freshly cleaved HOPG in 1 mol/L LiPF6/FEC/DMC. Scanning rate is 5 mV/s. The CV curve is similar to the one observed in the LiPF6/FEC/DMC electrolyte, however, a broader cathodic peak starts around 1.1 V. Unlike the CV curves obtained from LiPF6/EC/DMC electrolyte, where no obvious cathodic peak was observed after the first CV sweep, small cathodic peak was still observed after three scans in LiPF6/EC/DMC electrolyte (figure S5). It has been reported that the SEI film formation starts at a higher potential for FEC-based electrolytes.6,56 Introduction of a F group into an ester resulted in the drop of energy levels for both highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). The former has

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higher resistance against oxidation, while the latter has poorer resistance against reduction. Figure 5 shows the surface structural evolution of HOPG electrode cycled at a fast scanning rate of 5 mV/s between 3.0 and 0.0 V in the 1 mol/L LiPF6/FEC/DMC during the first lithiation-delithiation cycle. Similar to the observation in LiPF6/EC/DMC electrolyte, SEI started to grow after voltage swept down to ~1.0 V (figure 5c). However, precipitates are in a much smaller sizes in comparison to those of LiPF6/EC/DMC electrolyte. A dense and compact SEI was found to cover the whole surface after the potential was reduced to zero (figure 5d).The surface remained mostly unchanged during the anodic sweeping (figure 5e,f). Line profile shown in figure S6 revealed that the SEI was relatively flat with a surface variation of less than 100 nm. It was found that ridges were evolved from the step edges of HOPG.

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the lower nodular layer has a height of ~10-20nm (figure 6b). Upon a second lithiation-delithiation cycle, the scraped area was repaired by formation of an additional SEI (figure S7), which demonstrated the self-repairing nature of SEI. It also explains the capacity loss of batteries during charge/discharge, in which volume expansion induced crack of SEI.

Figure 6. (a) Exposed area of the lower layer of SEI after removal of the top layer by AFM scanning in the contact mode. (b) Line profile of the lower nodular layer.

Figure 5. In situ AFM images of HOPG electrode cycled at a scanning rate of 5 mV/s between 3.0 and 0.0 V in the 1 mol/L LiPF6/FEC/DMC(a-f). The arrow indicates the AFM scanning direction. The scales bars are 1μm. Precipitates formed in LiPF6/FEC/DMC under fast scanning rate can still be scraped off by repeated AFM scanning in the contact mode, however, a bigger force and more scans (>10) are needed. Figure 6 shows an AFM image of an exposed area of the lower layer of SEI after removal of the top layer by AFM scanning in the contact mode under a force of 175 nN. Height profile revealed that

Figure 7. In situ AFM images of HOPG electrode cycled at a scanning rate of 0.5 mV/s between 3.0 and 0.0 V in

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the 1 mol/L LiPF6/FEC/DMC(a-h). The arrow indicates the AFM scanning direction. The scales bars are 1μm. Under slow scanning rate, it was found that a thicker SEI was obtained. Figure 7 shows the surface structure of HOGP electrode cycled in a slow scanning rate of 0.5 mV/s in LiPF6/FEC/DMC electrolyte. As revealed by the height profile (figure S8), the surface shows a significant large height variation of 100-250 nm after the first lithiation-delithiation cycle. In comparison to SEI formed in LiPF6/EC/DMC electrolyte, SEI formed in LiPF6/FEC/DMC electrolyte under slow scanning rate (0.5 mV/s) is dense and compact. No damage was found even under maximum force scanned by AFM in contact mode. Based on the aforementioned findings, a schematic mode was described in figure 8 to show the differences in SEI layers formed from LiPF6/EC/DMC and LiPF6/FEC/DMC electrolytes.

Figure 8. A proposed model for the SEI layers formed from (a) LiPF6/EC/DMC electrolyte and (b) LiPF6/FEC/DMC electrolyte. As AFM is hard to precisely provide chemical information, XPS was employed as a complementary tool to gain chemical insight into the observed SEI structures. Figure 9 shows the C 1s and O 1s spectra of HOPG surfaces cycled in EC/DMC and FEC/DMC electrolytes. The C 1s signal exhibited a main component at 284.8 eV (C-C, C-H), which is attributed to contaminated hydrocarbon and carbon atoms of organic species bound to carbon or hydrogen only. The shoulder observed at 286.6 eV can be assigned to carbon atoms bound to one oxygen atom (CO), while the two small components at 288.1 eV and 289.9 eV found only in the SEI formed from FEC electrolyte correspond to carbon atoms characterized by a C=O bond and CO3 bond, respectively.1 The peak around 289.9 eV (characteristic of carbon bound to three oxygen atoms), is typical of carbonate-like species which could be Li2CO3 or alkyl carbonates ROCO2Li. In the O 1s core peak, for SEI formed from FEC electrolyte, oxygen atoms associated with ROCO2Li species represent the main contribution of the spectrum with the intense component located at 532 eV.

Figure 9. C1s and O1s core peaks of the SEI on HOPG electrode cycled at a scan of 0.5 mV/s between 3.0 and 0.0 V in the EC/DMC and FEC/DMC electrolytes. Figure 10 shows the F1s and Li1s spectra of HOPG surfaces cycled in EC/DMC and FEC/DMC electrolytes. LixPFy, characterized at 687 eV, was found to be another major component for SEI formed from EC electrolyte.57 For SEI formed from FEC electrolyte, it revealed the presence of LiF as a main component at 684.9 eV.54 The result is also confirmed by the P2P core peak analysis (figure S9).

Figure 10. F 1s and Li 1s core peaks of the SEI on HOPG electrode cycled at a scanning rate of 0.5 mV/s between 3.0 and 0.0 V in the EC/DMC and FEC/DMC electrolytes. Table 1 summarized the atomic concentrations of the C, O, F, Li, and P species. In general, LiF is the main component for SEI formed from FEC/DMC electrolyte in comparison to the EC/DMC electrolyte. LiF was found to be stiffer than other SEI components,57 which might explains why the SEI formed in FEC/DMC electrolyte was stable against the scratch by AFM tip. No Li2CO3 component was detected in EC/DMC-based electrolyte, while only trace found in the FEC/DMC-based electrolyte.

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Table 1. Atomic concentrations of C, O, Li, F, and P obtained from XPS. Atomic concentrations (%)

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ASSOCIATED CONTENT Supporting Information. Additional cyclic voltammetry, AFM images and XPS data. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

FEC/DMC

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Corresponding Author

EC/DMC

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*[email protected]; [email protected]

ACKNOWLEDGMENT Analysis of ex situ XPS should be carefully performed as some SEI layers formed from certain electrolytes are not stable and could be affected by solvent washing treatment.54 In our case, we did not observe any differences in SEI structure due to solvent washing.

We thank the National Natural Science Foundation of China (Grant No. 21303236and 51371186) and Zhejiang Province Key Science and Technology Innovation Team (2013TD16). Cai thanks the financial support from Ningbo “3315 plan”, the Youth Innovation Promotion Association, CAS, and SRF for ROCS, SEM.

CONCLUSION

REFERENCES

In situ AFM techniques were used in combination with ex situ XPS to study SEI layer on HOPG. Cyclic voltammetry and AFM observations show that interphasial species started to accumulate at ~0.8 V. Both SEI layers formed from EC/DMC and FEC/DMC electrolytes composed of a bottom layer and a top layer. The precipitate of the top layer of SEI layer formed from EC electrolyte was thin and scattered. It can be easily be removed by AFM tip under contact mode. In comparison to the SEI layer formed from EC/DMC based electrolyte, the SEI layer formed by FEC/DMC based electrolyte was thick and dense. Complementary ex situ XPS analysis of the two different SEI layers show that SEI layer formed by reductive decomposition of the EC/DMC electrolyte was principally composed of alkyl carbonates ROCO2Li, while the SEI layer formed by FEC/DMC electrolyte was mainly composed of LiF. Only trace of Li2CO3was found in the SEI layer formed from FEC/DMC electrolyte. The dense and hard nature of SEI formed by FEC/DMC electrolyte can protect the graphite against dendrite formation and could be the reason for better cyclability of FEC/DMC electrode as compared to those of EC/DMC based electrolyte. However, the thick nature of SEI also meant large amount of lithium are consumed. This may not be a problem in the half-cell where unlimited amount of lithium is present. Nevertheless, it will cause loss of lithium in the full-cell where commercial cathode such as LiFePO4 is used. Moreover, thick SEI layer will inevitably increase the impedance of the cell due to the insulating nature of SEI. A careful balance of the thickness, compactness and stiffness of the SEI with LIB’s performance should be optimized. Conventional method to evaluate electrolytes are usually complex and tedious procedures. Thus, combination of in situ electrochemical AFM and ex situ XPS could potentially serve as a fast diagnostic tool to evaluate the properties and quality of SEI formed on different electrodes from diverse electrolytes and additives.

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