Thermal stability of solid electrolyte interphase of lithium-ion batteries

Thermal stability of solid electrolyte interphase of lithium-ion batteries

Applied Surface Science 454 (2018) 61–67 Contents lists available at ScienceDirect Applied Surface Science journal homepage:

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Applied Surface Science 454 (2018) 61–67

Contents lists available at ScienceDirect

Applied Surface Science journal homepage:

Full Length Article

Thermal stability of solid electrolyte interphase of lithium-ion batteries Shiqiang Huang a b c




, Ling-Zhi Cheong , Deyu Wang , Cai Shen



Ningbo Institute of Materials Technology & Engineering Chinese Academy of Sciences, 1219 Zhongguan Road, Zhenhai District, Ningbo, Zhejiang 315201, China University of Chinese Academy of Sciences 19 A Yuquan Rd, Shijingshan District, Beijing 100049, China School of Marine Science, Ningbo University, Ningbo 315211, China



Keywords: Solid electrolyte interphase Atomic force microscopy Lithium ion battery Thermal stability

Solid electrolyte interphase (SEI) is an electronically insulating and Li+-conducting layer formed on electrodes. It is still the most mysterious part of lithium ion batteries (LIBs). Understanding the nature of SEI is vital to suppress capacity loss, increase cycle life and improve safety of LIBs during cycling. Herein, we employ atomic force microscopy (AFM) technology, X-ray photoelectron spectroscopy (XPS) and Electrochemical Impedance Spectroscopy (EIS) to comprehensively study the evolution and thermal stability of SEI formed on highly oriented pyrolytic graphite (HOPG) surface in three type of electrolytes containing 1 M LiPF6 dissolved in a mixture of DMC/EC (1:1, V: V). Morphology, mechanical properties, chemical composition and resistance changes of SEI were systematic studied as a function of temperature. Our results show that both fluoroethylene carbonate (FEC) and lithium oxalyldifluoroborate (LiDFOB) additives can improve the thermal stability of SEI. This combined approach enables us to further understand the effects of temperature on SEI which will be helpful for designing of LIBs with enhanced performance.

1. Introduction Global warming is a worldwide problem partly caused by burning fossil fuels, thus, developing renewable energy sources has become urgent at present. Solar, waves and wind are green energy sources, however, they are affected by weather conditions [1]. Rechargeable batteries like lithium ion batteries (LIBs) are capable to transform chemical energy into electrical energy and deliver it with high conversion efficiency. At the same time, LIBs have the ability to store energy from other sources, which is unique and irreplaceable compared with other green energy sources [2,3]. To develop advanced LIBs, two challenges have to be overcome: (1) new kind of electrodes with high energy density must be developed; (2) the safety problem of LIBs must be solved [4–6]. For the former challenge, many new materials and novel structures have been designed [7–17]. Thermal runaway is the main reason for safety problem, which can be partly suppressed by the formation of robust SEI film [5,6]. Although significant improvements have been achieved for LIBs during the past two decades, SEI film is still the most mysterious part of LIBs. SEI film is an electronically insulating and Li+-conducting layer. The major role of this layer is to suppress continuous electrolyte reduction and capacity loss during cycling. Uniform and stable SEI film can increase cycle life and improve safety of LIBs [18,19]. In order to understand the nature of SEI film, different kinds of techniques have

Corresponding author. E-mail address: [email protected] (C. Shen). Received 24 October 2017; Received in revised form 2 May 2018; Accepted 18 May 2018 Available online 19 May 2018 0169-4332/ © 2018 Elsevier B.V. All rights reserved.

been used, including Nuclear Magnetic Resonance (NMR) [20], Neutron Reflectometry [21], thermogravimetry-differential thermal analysis (TG-DTA) [22], scanning tunneling microscopy (STM) [23,24], electrochemical impedance spectroscopy (EIS) [25,26] and atomic force microscopy (AFM) [19,27,28]. Among these methods, AFM seems to be one of the most powerful tools due to its non-harmful characterization to this delicate layer. Additives are always used to improve the electrochemical performance of the batteries because they can promote to form the more stable SEI film [29–31]. Xu and his co-workers using in-situ AFM found that electrolyte with different additives (VC, FEC and HFiPP) will form the SEI films with different topography [27]. VC contained electrolyte will also have an effect on the mechanical properties of the SEI film [32]. The electrolyte containing ES additives will form the SEI with particles in the range of 40–60 nm at a much higher potential and contain Li2SO3, organic sulfides and ROSO2Li due to the decomposition of the ES. Furthermore, such electrolyte system can lead to a stable coulombic efficiency (almost 100%) while PES-containing electrolyte showed a fluctuation at high rate (5C) [33]. Wan and his co-workers compared two anions additives ([FSI]− and [TFSI]−). They found that [FSI]− contained electrolyte will form the nano-particles at the edge of the HOPG and then combined with each other to form the uniform and compact SEI film, which showed excellent cyclability and Coulombic efficiency. On the other hand, the [TFSI]− contained electrolyte will

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Fig. S1a–c, SEI film seems to be stable before 80 °C and the morphology almost kept the same. A significant change appeared at 80 °C (Fig. 1c), small particles grew rapidly from 157 ± 47 nm to 283 ± 60 nm (Fig. 2a–b and Fig. S2a), which announced the accumulation of species at trigger temperature and these species likely corresponded to the decomposition product from unstable organic component of SEI film (Fig. S3 area II). The particles got further growth and reached their maximum size of 431 ± 76 nm at 110 °C (Fig. 2c and Fig. S2a), and bigger particles had covered the whole surface instead of the initial small particles (Fig. 1f). However, with further heating, the particle size decreased to 344 ± 67 nm at 130 °C (Fig. 2d and Fig. S2a) and at 140 °C, it became much smaller (305 ± 47 nm, Fig. S2a) with some gullies appeared on the surface (Fig. S1f), which might be caused by another decomposition of organic compounds (Fig. S3 area III). We also explored the effect of heating time to surface morphology, extending heating time at 140 °C to 30, 60 and 120 min, as shown in Fig. S4, the gullies disappeared when heated for 30 min and did not show up with time increasing. Particles started to grow again and achieved 402 ± 89 nm at 120 min (Fig. S2b). The implication of this phenomenon is that some organic components began to gather together or even accompanied with melting process, as a result, the gullies were filled and the surface of the particles became smoother [32]. Fig. S5 compared the roughness of SEI film at different stage, obvious change occurred at 80 °C, at which temperature, the roughness of the surface increased from ~14 to ~17 nm, which corresponding to first species accumulation and particle increasing. Little change appeared when we extended heating time for 30 min, the roughness of the surface increased from ~16 to ~17 nm, which corresponding to second species accumulation and particle increasing. Quantitative nanomechanics (QNM) is one of the extended applications of AFM technology, and it is always used to measure the Young’s modulus [35]. As shown in Fig. 3 and Fig. S6, Young’s modulus mapping was gained with temperature increasing in electrolyte R. The Young’s modulus of the SEI-R was 2.1 GPa at RT. As the temperature went up to 70 °C, the Young’s modulus increased to about 4.92 GPa, which might result from decomposition of the very unstable and thin layer on the surface (Fig. S3 area I) while the morphology showed almost no changes. Although morphology changed obviously at 80 °C (Fig. 2c), the Young’s modulus just increased slightly to 5.05 GPa. The remarkable change appeared when temperature rose to 90 and 100 °C, as shown in Fig. 3d and 3e, the Young’s modulus increased to 6.63 GPa at 90 °C and 9.27 GPa at 100 °C, which was attributed to the continuous decomposition of soft organic component and homogeneous distribution of harder products. However, with further heating, Young’s modulus just mildly increased from 10.2 (110 °C) to 11.1 GPa (140 °C, Fig. S6f). Statistical analysis was carried out to clarify the trend of the modulus distribution with temperature (Fig. 3 g). Before heating, 100% SEI demonstrated a Young’s modulus between 0 and 5 GPa, but an obvious decreasing trend was observed with temperature increasing, it demonstrated 76%, 50%, 20% and 18% at 80 °C, 90 °C, 100 °C and 140 °C, respectively. On the contrary, more and more SEI demonstrated a Young’s modulus between 5 and 30 GPa, which increased from 0% (RT) to 77% (140 °C). The result suggested that the decomposition products were much harder than primary organic component. Fig. S7a–c exhibited images of Young’s modulus mapping of SEI at 140 °C when it was heated for 30, 60 and 120 min in electrolyte R. The mean modulus decreased from 11.1 GPa to 9.64 GPa as heating time increased to 30 min, but it almost did not change when we extended heating time. Fig. S7d showed the statistical analysis of the modulus distribution; more SEI demonstrated a Young’s modulus between 0 and 5 GPa as heating time increased, which means more soft component appeared on the surface. Besides, increasing heating time almost did not change the mean modulus and it demonstrated the stability of such component at the same temperature. XPS was applied as a complementary tool to obtain the chemical information for AFM was not able to achieve it. Fig. 4 shows the C 1 s, O

lead to a porous and rough SEI film resulting in a serious capacity loss and a poor Coulombic efficiency [34]. So the properties of SEI film (including topography, mechanical properties and chemical information) are significant for the cyclability and Coulombic efficiency of LIBs. However, there is little research about the properties changed of SEI films with temperature. In this work, we employed AFM, X-ray photoelectron spectroscopy (XPS) and Electrochemical Impedance Spectroscopy (EIS) to study the topography, mechanical properties and chemical composition change of SEI film with temperature. AFM was used to observe the morphology and mechanical properties while XPS was applied to analyze the chemical composition of SEI film (grown on HOPG). Furthermore, EIS technique was used to study the resistance of SEI film with temperature in Li/graphite cells. 2. Experimental section 2.1. Sample preparations The HOPG-Li cell was assembled using Li wire as both reference and counter electrodes in the glovebox with O2 and H2O ≤ 0.1 ppm (HOPG: Bruker Corporation, ZYB grade, 12 × 12 × 2 mm). Three different electrolytes were prepared named as electrolyte R (1 M LiPF6 dissolved in a mixture of dimethyl carbonate and ethylene carbonate DMC/EC, 1:1, V: V; Shanshan Corporation), electrolyte A (reference electrolyte with 10% FEC; FEC: Shanshan Corporation), electrolyte B (0.1 M LiDFOB with 0.9 M LiFP6 dissolved in DMC/EC, 1:1, V: V; LiDFOB: Sigma–Aldrich). Cyclic voltammetry (CV) was applied to grown a SEI film with a scanning rate of 0.5 mV/s between 3.0 and 0.01 V. The graphite anodes were prepared by mixing polyvinylidene fluoride (PVDF, 10%, Alfa Aesar), super P (20%, Alfa Aesar) and graphite (70%, Aladdin) in N-methyl-2-pyrrolidone (NMP; Aladdin) solvent. Slurry was formed on Cu current collectors and then dried in a vacuum oven at 100 °C for 12 h to obtain anodes. 2032-type coin was assembled containing graphite anode, metallic lithium counter electrode, Celgard 2400 polypropylene separator and 1 M LiPF6/DMC/EC electrolyte. 2.2. Sample characterizations AFM topography and Young’s modulus mapping of SEI film was collected at PeakForce QNM (Quantitative NanoMechanics) mode using TAP525A (Bruker) tip. In this method, the deflection sensitivity of the probe was first calibrated on a clean, hard sample (Sapphire), and then polystyrene with known modulus was used to calibrate the probe by adjusting proper force set point of the tip and tip radius. After calibration, the tip was brought to measure the sample on a 2.5 × 2.5 μm2 area. Topography and QNM was measured at the same time in a way of 256 × 256 pixels/scan, i.e. 65,536 points of the sample were probed and their force curves were acquired. Young’s modulus was derived from these force curves according Derjaguin, Muller Toropov (DMT) model. Thermogravimetric (TG) analysis was performed on Diamond TG/DTA (PerkinElmer); sample was heated to 300 °C at a rate of 5 °C/ min under helium atmosphere. In our experiments, all samples were first gently cleaned by DMC solution in an argon-filled glovebox and then dried under vacuum. Samples were then transported to XPS facility in sealed bags to avoid contact with air and XPS analysis was performed using 1486.6 eV Al KαX-rays (Kratos Axis Ultra X-ray photoelectron spectrometer). EIS measurement was conducted on a CHI 760E Electrochemical Workstation using AC signal of 5 mV in amplitude and the frequency was from 0.1 to 0.1 M Hz. 3. Results and discussion Fig. 1 and Fig. S1 showed the morphology change of SEI film formed in electrolyte R (SEI-R) as the temperature increased from room temperature (RT) to 140 °C (heating time was 10 min). From Fig. 1a–b and 62

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Fig. 1. 3D AFM images of SEI-R after heating at (a) RT, (b) 70 °C, (c) 80 °C, (d) 90 °C, (e) 100 °C, (f) 110 °C. The scan areas are 2.5 × 2.5 μm2.

Fig. 2. 2D AFM images of particles change after heating at (a1–a5) RT, (b1–b5) 80 °C, (c1–c5) 110 °C, (d1–d5) 130 °C with five different positions on SEI film. The scale areas are 1.1 × 1.1 μm2.

1 s, F 1 s, Li 1 s and P 2p spectra of HOPG surfaces cycled in electrolyte R. after heating by different temperatures (signed as sample-RT, sample-80, sample-90 and sample-110). The main peaks at around 284.8 and 286.8 eV for all samples were characterized by CeC bond and CeO bond, while a small shoulder at higher binding energy of 290.2 eV was only found at sample-RT, which arose from eCO3 bond but disappeared with temperature increasing [36,37]. It might be caused by some attack reaction from decomposition of LiPF6 [26]. O 1 s spectra only shows one dominant peak at approximately 532.8 eV, which arose from a mixture of CeO and C]O environments and always associated with ROCO2Li species [36]. Two characteristic peaks at 684.8 and 686.5 eV in F 1 s spectra were indicated by LiF and LixPFyOz

species, respectively [36,38]. Li 1 s spectra revealed the only presence LiF with a peak at ~56 eV [39]. Two major peaks observed at ~134 and 137 eV were assigned to LixPFyOz and LiPF6 in P 2p spectra [40,41]. Table S1 described the area percentages (%) of each bond in SEI-R as function of temperature, it can be found that organic species decreased with the C content decreased (RT: 59.75%; 110 °C: 44.67%) while inorganic species increased with the Li and F content increased in SEI. As shown in Li 1 s spectra, the content of LiF increased from 3.56% to 10.96% when the temperature increased from RT to 110 °C.And it can also be proved in F 1 s spectra. LiF was much stiffer than other SEI components, which explained why the modulus increased with temperature.


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Fig. 3. The AFM images of Young’s modulus mapping of SEI-R after heating at (a) RT, (b) 70 °C, (c) 80 °C, (d) 90 °C, (e) 100 °C, (f) 110 °C. (g) Distribution of Young’s modulus of SEI-R after heating at different temperatures. The scale bars are 500 nm.

itself and the resistance of SEI film [26]. Fig. S8 showed the results of the fitting EIS data of each temperature. Rsei was 76.23 Ω at RT and it kept decreasing when the temperature increased to 70 °C (64.18 Ω). However, there was an increase during 70~90 °C, the Rsei reached 69.28 Ω at 90 °C. Rsei decreased again to 24.79 Ω when the temperature increased to 110 °C. The oscillation during 70~100 °C may be caused

Li/graphite coin cells were precycled one time between 3 and 0.01 V using reference electrolyte at RT to grow a SEI film. And then the resistance change of SEI was measured from RT to 110 °C. Fig. 5a presents the typical electrochemical impedance plots of graphite anodes and Fig. 5b shows equivalent circuit. The depressed semicircle in high-frequency region represented both contact resistance of carbon particles

Fig. 4. C 1 s, O 1 s, F 1 s, Li 1 s and P 2p spectra of the SEI film after heating at different temperatures (RT, 80 °C, 90 °C, 110 °C). 64

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electrolyte A and electrolyte B. It can be seen that both FEC and LiDFOB can stabilize the SEI film. The morphology of SEI film formed in electrolyte A (SEI-A) and electrolyte B (SEI-B) kept stable even when temperature increased to 140 °C. Mean Young’s modulus change of SEI-A and SEI-B were presented in Fig. 8. The Young’s modulus of SEI-A film was 7.43 GPa at RT and kept stable until 100–120 °C (around 12 GPa); The Young’s modulus of the SEI-B film showed a slight and steady increase form 14.4 GPa to 17.9 GPa during the whole heating process. Fig. S9 and S10 provided the XPS data of SEI-A and SEI-B; it can be found that the main component of SEI-A and SEI-B was almost the same as that of SEI-R, which included eCO3,CeC,CeO,C ] O,LiF and LixPFyOz. However, as shown in Table S2 and S3, the atomic concentrations had changed a lot in SEI-A and SEI-B. More inorganic component appeared in the primary formed SEI-A and SEI-B: calculated from Li 1 s spectra, the content of LiF was 8.78% and 14.28% of SEI-A and SEI-B, respectively. In addition, there was more eCO3 contained species in SEI-B, both LiF and eCO3 contained species are stiffer than other organic species, which explained why the primary Young's modulus of SEI-A and SEI-B are higher than that of SEI-R. The atomic concentration change of SEI-A was similar to that of SEI-R, inorganic component LiF increased from 8.78% (RT) to 13.54% (110 °C) while organic component showed a decrease (RT: 53.38%; 110 °C:35.26%) with temperature increasing, which caused the increased Young's modulus. As for SEI-B, the inorganic component showed a subtly increase while organic component decreased a little, such small change did not make marked change but also lead to slight increase of Young's modulus.

Fig. 5. (a) Electrochemical impedance plots of graphite anodes, (b) Equivalent circuit.

by decomposition of LiPF6 (LiPF6 → PF5 + LiF) and further reaction with SEI components, which may had an effect on the SEI surface structure. [26,42] Firstly, the strong Lewis acid PF5 will attack species of SEI contained CeO and C2H5e groups [26]. Besides, PF5 can react with H2O (PF5 + H2O → 2HF + POF3) and the new formed POF3 will attack EC by two possible reactions: POF3 + EC → CH2FCH2OCOOPF2O; POF3 + EC + PF6−→CH2FCH2OCOOPF3O−+PF5.On the other hand, both PF5 and HF will react with CO32− and produce LiF (PF5 + 2Li++CO32− → 2LiF + POF3 + CO2; HF + 2Li++CO32− → 2LiF + CO2 + H2O), [42] that is also the reason why eCO3 group disappeared at C 1 s spectra at 80 °C and the SEI film became harder. Fig. 6 and Fig. 7 showed the morphology change of SEI film as the temperature increased from RT to 140 °C (heating time was 10 min) in

4. Conclusion In summary, we applied AFM,XPS and EIS methods to study the thermal properties of SEI films. Three stages of the heating process were identified in electrolyte R. At the first stage (from RT to 70 °C), the morphology of SEI film did not change and the particle size was 157 ± 47 nm. The Young’s modulus increased slightly from 2.1 GPa to 4.92 GPa while impedance gradually decreased, which can be ascribed to the decomposition of the unstable substances on the top surface. At the second stage (from 80 °C to 110 °C), particles started to grow and reached maximum size of 431 ± 76 nm at 110 °C. Decomposition of

Fig. 6. 3D AFM images of SEI-A after heating at (a) RT, (b) 70 °C, (c) 80 °C, (d) 90 °C, (e) 110 °C, (f) 140 °C. The scan areas are 2.5 × 2.5 μm2. 65

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Modulus (GPa)

Fig. 7. 3D AFM images of SEI-B after heating at (a) RT, (b) 70 °C, (c) 80 °C, (d) 90 °C, (e) 110 °C, (f) 140 °C. The scan areas are 2.5 × 2.5 μm2.




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12 8 electrolyte-R electrolyte-A electrolyte-B

4 0


60 80 100 120 140 Temperature (°C)

Fig. 8. Mean modulus change at different temperature in electrolyte-R, electrolyte-A and electrolyte-B.

both LiPF6 and unstable organic components will result in more inorganic component, which will accumulate to form bigger particles. The Young’s modulus continued to increase from 4.92 GPa to 10.2 GPa while impedance showed an oscillation. At the last stage (from 120 °C to 140 °C), with more decomposition of organic species, the Young’s modulus got slightly increase and particle size decreased to 305 ± 47 nm. In general, SEI films are stable before 70 °C and become harder as the temperature increase. Additionally, both FEC and LiDFOB additives can promote to form a thermal stable SEI.

Acknowledgements We thank the National key research and development program (Grant No. 2016YFB0100106) and the Youth Innovation Promotion Association, CAS for financial supports. Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at 66

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