Non-flammable Fluorinated Carbonate Electrolyte with High Salt-to

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Non-flammable Fluorinated Carbonate Electrolyte with High Salt-to-solvent Ratios Enables Stable Siliconbased Anode for Next Generation Lithium-ion Batteries Guifang Zeng, Yongling An, Shenglin Xiong, and Jinkui Feng ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b05570 • Publication Date (Web): 05 Jun 2019 Downloaded from http://pubs.acs.org on June 7, 2019

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ACS Applied Materials & Interfaces

Non-flammable Fluorinated Carbonate Electrolyte with High Salt-to-solvent Ratios Enables Stable Silicon based Anode for Next Generation Lithium-ion Batteries Guifang Zeng,a Yongling An,a Shenglin Xiong,b Jinkui Fenga*

a.

SDU & Rice Joint Center for Carbon Nanomaterials, Key Laboratory for

Liquid Solid Structural, Evolution & Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jinan 250061, P. R. China b.

School of Chemistry and Chemical Engineering, Shandong University, Jinan

250100, P. R. China

*Address correspondence: [email protected]

Keywords: concentrated electrolyte, fluoroethylene carbonate (FEC), safe lithium batteries, di-2,2,2-trifluoroethyl carbonate (TFEC), non-flammable, silicon.

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Abstract: High energy density and safety are two key factors for the development of next-generation lithium-ion batteries (LIBs). Recently, silicon (Si) has attracted tremendous interest owing to its high theoretical capacity. However, the fast capacity decay triggered by huge volume change restricts its practical application. Moreover, higher energy density brings about more serious safety issues. To solve these problems, here we propose a safer high salt-to-solvent electrolyte consisted of non-flammable mixture solvents of di-2,2,2-trifluoroethyl carbonate (TFEC) and fluoroethylene carbonate (FEC). It is revealed that this electrolyte could not only enhance cycling stability toward silicon nanoparticles (SiNPs) anode but also solve the safety hazards. A high initial reversible capacity of 2644 mAh g-1 and a low capacity fading rate (only 0.064% per cycle) after 300 cycles are delivered. The performance enhancement mechanism is further explored by electrochemical impedance spectroscopy (EIS), Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). This study may shed an inspiring light on the development of next-generation high-energy density batteries.


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1. INTRODUCTION LIBs have been widely used in our daily life and may dominate the electric vehicles.1-4 Nevertheless, the energy density of current LIBs is insufficient to fulfill the expectation of electric vehicles.3-6 Moreover, the state-of-art electrolytes for LIBs make use of flammable carbonates as the main solvents, which may bring about serious safety problems.5, 7 Both the energy density and safety issues have been the key hindrances for the further application of LIBs.1-11 To enhance the high-energy density, one practical approach is to utilize cathode or anode materials with higher capacity.12 Recently, Si is considered as a promising anode candidate due to its high theoretical capacity (~ 3700 mAh g-1), abundant resource and low working platform.13-18 Unfortunately, its electrochemical performance is inhibited by several key factors.14-15, 19-20 The main challenge is the huge volume change (about 300%) during the alloying and de-alloying process, which may cause cracking and crumbing of active material, leading to partial and/or full disconnection with current collectors and exposing new surfaces to cost extra SEI layer, which results in active material loss, low coulombic efficiency (CE) and fast capacity decay.14, 20-22 To settle these issues, many strategies have been proposed such as nanostructures designing, carbon coating, binder optimizing, SEI additives et al.14, 23 However, the reports on developing new electrolyte system for silicon based anode are rare.14 Fluorinated carbonates have been proved to possess excellent physicochemical and electrochemical properties compared with their hydrogenated counterparts such as lower melting point, more stable SEI film and higher oxidation stability.5,


24-25


Moreover, recently it is found that certain fluorinated organic carbonates are nonflammable.26-28 Thus, utilizing fluorinated carbonates as electrolyte solvents may be a new strategy to enhance the safety of lithium batteries.26-27 In another aspect, concentrated electrolyte recently has attracted much attention due to their unique high salt-to-solvent characters, which could enhance the compatibility of electrolytes to electrodes.10, 29-37 Different from common dilute electrolyte, the highly concentrated solvents contain less free solvent molecules, which are more reactive.32 Benefiting from the special electrolyte, a robust passivation film can be formed on the surface of electrodes, which may alleviate the degradation of electrodes and electrolytes.30, 32-34, 38 It can be expected that the combination of non-flammable fluorinated carbonates with high concentrated salts may provide an attractive multifunctional electrolyte system for silicon-based anode. Here, we demonstrate an electrolyte composited of mixed fluorinated carbonate solvent of FEC and TFEC with 3.5 M lithium bis(fluorosulfonyl)imide (LiFSI) as the salt. It is found that this electrolyte system is nonflammable, moreover, Si based anode shows a significantly more stable cycling performance (0.064% per cycle capacity decay over 300 cycles) in this electrolyte. The performance enhancing mechanism is further probed and it is attributed to a more robust SEI layer generated on silicon based anode.

2. EXPERIMENTAL SECTION The control electrolyte was composited of 1 M lithium hexafluorophosphate (LiPF6) salt, ethyl methyl carbonate (EMC) and ethylene carbonate (EC) (EMC:EC, 7:3 v/v),


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purchased from Nanjing Mojiesi Energy Technology Co. Ltd. (China). The fluorinated electrolytes were prepared by dissolving 1, 3.5 and 4.3 M LiFSI in FEC/TFEC mixture solvent (3:7 by volume), respectively. All of these electrolytes were confected in a glove box. The glove box is full of nitrogen (H2O, O2 < 0.1 ppm). All of these reagents were applied directly without further purification. The anode was prepared with SiNP, sodium carboxymethyl cellulose binder and carbon black (70: 15: 15, by weight). Cathode electrode was prepared with LiFePO4, polyvinylidene ﬂuoride and carbon black (80: 10: 10, by weight). A galvanostatic charger was used to evaluate electrochemical performance of SiNPs. EIS and cyclic voltammetry (CV) measurements were tested by an electrochemical workstation. Crystal structures of SiNPs and SiNPs electrode were performed via X-ray diffraction (XRD) with a Rigaku Dmaxrc diffractometer. Surface morphologies and size of cycled electrodes were obtained via SU-70 SEM. FTIR analysis of SiNPs was obtained by a NICOLET AVATAR 360 FT-IR spectrometer.

3. RESULTS AND DISCUSSION Figure 1a summarizes the chemical molecule structures of all the solvents investigated in this study, including EC, EMC, LiPF6, FEC, TFEC and LiFSI.12 FEC is proved to be an effective anode-filming additive for Si-based electrodes in previous reports.20, 39 FEC is less flammable than other common cyclic carbonates, such as EC and propylene carbonate (PC), due to the introduction of F atom.5,

24

Above all,

solubility of LiFSI salt in FEC is much higher than that in TFEC. TFEC is a nonflammable solvent,26 however, according to our study, the solubility of LiFSI salt in



TFEC is limited (less than 1 mol L-1). Crystal phase structures of SiNPs and SiNPs anode were characterized by XRD. Figure 1b displays the characteristic peaks of Si and copper, which confirmed that the silicon is pure phase.13, 23 In addition, the morphology of SiNPs with a typical size of about 50 nm was verified by SEM image (Figure S1). The ionic conductivity of different electrolytes was also measured. Figure 1c shows the ionic conductivity of 1 M LiPF6/EC-EMC at room temperature reaching a value of 9.60 mS cm-1. Figure 1d manifests the ionic conductivity of LiFSI/FEC-TFEC electrolytes at diverse concentrations. As we can see, the conductivity slowly increase with LiFSI content increase, then slowly decreases. The ionic conductivity of 3.5 M is 1.21 mS cm1,

and the low conductivity may be ascribed to the high viscosity in concentrated salt

electrolyte.10 To solve this issue without sacrificing the advantages of concentrated electrolyte, it is universal to add some inert solvents with low viscosity into the concentrated electrolyte.40 The flammability of 3.5 M LiFSI/FEC-TFEC and 1 M LiPF6/EC-EMC was examined by a direct igniting test. It can be seen that the common carbonate based electrolytes rapidly caught fire after ignition, while the hybrid fluorinated solvents can’t be ignited (Figure 1e and Figure 1f). These results proved that the 3.5 M LiFSI/FEC-TFEC electrolyte has an inner nonflammable character, which could greatly enhance the safety of batteries.30, 32 CV curves of SiNPs in different electrolytes are also explored (Figure 2). All the CV curves are similar in shape, suggesting the same delithiation/lithiation mechanism.13 The wide peaks ( 0.5 – 2.5 V) in the first cycle are assigned to the SEI layer formation.13, 19, 41

The strong peaks located at (0.01 - 0.18 V) and (~ 0.3 and 0.5 V) are related to the


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are related to the lithium alloying and dealloying with Si.19, 23, 42 The electrochemical performance of SiNPs anode in different electrolytes was estimated using half-cell test (Li||SiNPs). The first discharge-charge electrochemical performance in 1 M LiPF6/EC-EMC and in 1, 3.5 and 4.3 M LiFSI/FEC-TFEC electrolytes was presented (Figure 3a). The initial discharge capacities in common carbonate electrolyte and in 1, 3.5 and 4.3 M LiFSI/FEC-TFEC electrolyte are 3400, 3611, 3480 and 2482 mAh g-1, respectively, corresponding to 62%, 66%, 76% and 73% CEs, which suggests that CE could also be improved by fluorinated electrolyte.23, 39 The irreversible capacity is well-known ascribed to the formation of SEI film.13,

39

Furthermore, a decline of discharge capacity in 4.3 M LiFSI/FEC-TFEC electrolyte can be assigned to the lower conductivity and higher viscosity in concentrated electrolyte.23, 32, 34, 39

The charge-discharge profile of SiPNs anode in 3.5 M LiFSI/FEC-TFEC

electrolyte is overlapped well (Figure 3c, Figure S2, Figure S3, Figure S4), indicating a stable cycling performance.13 Figure 3b compares the discharge capacities in different electrolytes. After 50 cycles, the capacity in common carbonate electrolyte decreases to 1327 mAh g-1 ( 39% capacity retention) due to the huge volume expansion.39 In contrast, the discharge capacity in 1, 3.5 and 4.3 M LiFSI/FEC-TFEC electrolytes remain 1989, 2105 and 1578 mAh g-1 (55%, 60% and 63% capacity retention). In addition, CE of SiNPs in 3.5 M LiFSI/FEC-TFEC electrolyte grows rapidly to nearly 100% (Figure 3d), which illustrates the irreversible lithium alloying and dealloying reactions, which may be ascribed to a stable SEI film.10 To further compare the electrochemical charge-discharge performances of SiNPs in different electrolytes, rate



test (1000, 2000 and 5000 mA g-1) were performed (Figure 4a, Figure 4b, Figure 4c). Capacity in common carbonates electrolyte fades rapidly from 3084 to 658 mAh g-1 after 60 cycles, whereas the capacity in 3.5 M LiFSI/FEC-TFEC electrolyte still retains 1981 mAh g-1. Notably, the most impressive feature of SiNPs in 3.5 M LiFSI/FECTFEC electrolyte is its cycling stability. After 300 cycles (Figure 4c, Figure S5), no significant capacity fades is observed (0.064% capacity loss rate per cycle and 99.8% CE). As a result, the SiNPs in 3.5 M LiFSI/FEC-TFEC electrolyte exhibits a best cycling performance among these electrolytes. Figure 4d compares capacities of SiNPs in common carbonates and 1, 3.5, 4.3 M LiFSI/FEC-TFEC electrolytes at different rates. It is obviously seen that rate performance in 1 M LiFSI/FEC-TFEC electrolyte is the best. Capacities of 3300, 2828, 2359, 1912, 1703, 1312, 2802 mAh g-1 at 500, 1000, 2000, 4000, 5000 and 8000 mA g-1 are delivered in 1 M LiFSI/FEC-TFEC electrolyte, respectively. The excellent rete performance may be ascribed to the higher ionic conductivity and the stable F-rich SEI film.7, 10, 30-31 Furthermore, to validate the feasibility of 3.5 M LiFSI/FEC-TFEC electrolyte in practical applications, LiFePO4 cathode is also tested using a half cell (Li||LiFePO4). The CV plots of LiFePO4 are displayed in Figure 5a. The peaks located at ~ 3.2 and 3.6 V is well-known ascribed to the reversible transformation of Fe2+/Fe3+, respectively.43 Additionally, perfect overlap manifests the excellent capacity retention of LiFePO4 in 3.5 M LiFSI/FEC-TFEC electrolyte.43 The capacity-potential graphs are shown in Figure 5b. In the first scan, it delivers a charge and discharge capacities of 133 and 136 mAh g-1 with a high CE of 97%. The LiFePO4 retains a 95% capacity retention even


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after 130 cycles (Figure 5c). Except for the excellent cycling performance, an outstanding rate property is also obtained (Figure 5d). From above results, it can be concluded that 3.5 M LiFSI/FEC-TFEC electrolyte could be used as a promising candidate electrolyte for silicon based batteries. The outstanding electrochemical performance of SiNPs in 3.5 M LiFSI/FEC-TFEC electrolyte is further probed. The morphology of initial SiNPs electrode, is provided in Figure S6, which was homogeneously distributed. However, after 50 cycles, severe shedding of active materials and large cracks can be seen in SiNPs with common carbonate based electrolyte, which is ascribed to the huge volume expansion and shrink during lithiation/delithiation process (Figure 6a).31,

33

As a contrast, a smooth

morphology was observed with 3.5 M LiFSI/FEC-TFEC electrolyte (Figure 6b), revealing a stable electrode framework.31 which may effectively prevent the SiNPs from losing contact with current collector and cost extra SEI layer.33 The EIS measurement was also investigated for SiNPs anode in carbonate electrolyte and 3.5 M LiFSI/FEC-TFEC electrolyte after 10 and 50 cycles. The semicircle in high-frequency region are related to the composite resistance of SEI film and charge transfer (Rct). The slope line in low-frequency region is consistent with the Warburg resistance. As shown in Figure 6c, compared to cells cycled in carbonate solvent, the fluorinated electrolyte demonstrated a higher Rct impedance in 10th cycle due to higher impedance of LiF in the SEI film and the lower electrolyte conductivity.24 However, the Rct resistance in carbonate solvent rapidly increase after 50 cycles, whereas no obvious resistance changes in fluorinated electrolyte (Figure 6d). The lower resistance change in



fluorinated electrolyte can be ascribed to the stable F-rich SEI film which can prevent the continuous electrolyte decomposition. In addition, the concentrated LiFSI salt could reduce the free electrolyte molecules, which also help reduce electrolyte decomposition. The synthetic advantages enable the stable cycling performance of silicon anode. The lower impedance indicates that the extra growth of SEI is restrained,31 which agrees with the results of SEM images. Based on these results, we can deduce that the SEI features can preserve initial morphology of SiNPs and effectively self-limit extra growth of SEI. In other words, it can mitigate the crack propagation and improve the cycling stability of SiNPs.29 The structure of SEI layer components was also explored with FTIR. The SiNPs anodes after 50 cycles obtained from carbonate electrolyte and 3.5 M LiFSI/FEC-TFEC electrolyte are compared. Figure 6e shows the FTIR spectra of SEI layers from 600 to 2500 cm-1. For the anode cycled in common carbonate electrolytes, ROCO2Li, Li2CO3 and polycarbonates compounds are detected, which is the typical chemical composition of SEI layer.44 For SEI formed in fluorinated electrolyte, it contains not only the abovementioned products, but also ethylene-oxide-based polymers and sulfur-based compounds, corresponding to the peaks at 1152 cm-1 and 1108, 992, 901cm-1.29, 44-45 The present of ethylene-oxide-based polymers can be derived from the FEC solvent decomposition.33,

45-46

FEC may decompose to obtain vinylene carbonate (VC) and

vinoxyl species.45, 47 Then the present of poly(VC) and poly (ethylene oxide) can be ascribed to the polymerization of VC and vinoxyl species.44-48 The flexible polymer may further buffer the volume change.45 In addition, organic sulfates-containing from


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the LiFSI may also help forming a more stable SEI layer.29, 49

4. CONCLUSION In summary, we demonstrate a non-flammable fluorinated carbonates based concentrated electrolyte. Besides significantly improved safety, silicon-based anode exhibits an outstanding cycling performance and improved CE in this electrolyte. A high reversible capacity and 0.064% capacity fading rate per cycle are delivered. Our results reveal that the robust SEI layer which is formed from fluorinated carbonates with high concentrated salt is the key factor for the superior capacity retention.



Figure 1. (a) Chemical molecular structures of EC, EMC, LiPF6, FEC, TFEC and LiFSI. (b) XRD patterns of SiNPs and SiNPs electrode. (c) The ionic conductivities of different electrolytes. (d) Concentration dependences of the ionic conductivities of LiFSI/FEC-TFEC electrolyte at room temperature. Flammability tests of (e) 1 M LiPF6/EC-EMC and (f) 3.5 M LiFSI/FEC-TFEC electrolyte.


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Figure 2. CV plots of SiNPs in (a) 1 M LiPF6/EC-EMC, (b) 1, (c) 3.5 and (d) 4.3 M LiFSI/FEC-TFEC electrolyte. The scanning speed is 0.1mV s-1 (0.01-3V).



Figure 3. Electrochemical performance of SiNPs anode at 500 mA g-1 (0.01 - 3 V). (a) Initial discharge/charge profiles. (b) Cycling performance. (c) Discharge/charge curves in 3.5 M LiFSI/FEC-TFEC electrolyte. (d) Coulombic efficiencies.


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Figure 4. Electrochemical performance of SiNPs anode in different electrolytes (0.013V). Cycling capability at (a) 1000 mA g-1, (b) 2000 mA g-1 (in the first three cycles at 500 mA g-1), (c) 5000 mA g-1 (in the first three cycles at 500 mA g-1). (d) Rate property.



Figure 5. Electrochemical performance of LiFePO4 cathode in 3.5 M LiFSI/FEC-TFEC electrolyte (2-3.8 V). (a) CV profiles at 0.1 mV s-1. (b) Charge/discharge curve. (c) Cycling capability. The current density is 20 mA g-1. (d) Rate property.


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Figure 6. SEM images of SiNPs anodes cycled in (a) 1 M LiPF6/EC-EMC and (b) 3.5 M LiFSI/FEC-TFEC electrolyte. EIS spectra of SiNPs anodes after (c)10th cycles and (d) 50th cycles in 1 M LiPF6/EC-EMC and 3.5 M LiFSI/FEC-TFEC electrolyte. (e) FTIR pattern of SiNPs electrode in 1 M LiPF6/EC-EMC and 3.5 M LiFSI/FEC-TFEC electrolyte.



ASSOCIATED CONTENT Supporting information. SEM image, electrochemical performance. Corresponding Author *E-mail: [email protected]

Acknowledgment This work was supported by Shandong Provincial Natural Science Foundation (China, ZR2017MB001), Shandong Provincial Science and Technology Key Project (2018GGX104002), The State Key Program of National Natural Science of China (Nos.61633015), The Young Scholars Program of Shandong University (2016WLJH03) and the Project of the Taishan Scholar (No. tsqn201812002 and No. ts201511004).

REFERENCES (1) Zheng, J.; Ji, G.; Fan, X.; Chen, J.; Li, Q.; Wang, H.; Yang, Y.; DeMella, K. C.; Raghavan, S. R.; Wang, C. High-Fluorinated Electrolytes for Li-S Batteries. Advanced Energy Materials 2019, 1803774. (2) Tarascon, M. A. a. J.-M. Building better batteries. Nature 2008, 451 (652-657). (3) Guo, Y.-G.; Hu, J.-S.; Wan, L.-J. Nanostructured Materials for Electrochemical Energy Conversion and Storage Devices. Advanced materials 2008, 20 (15), 2878-2887. (4) Xu, G.; Pang, C.; Chen, B.; Ma, J.; Wang, X.; Chai, J.; Wang, Q.; An, W.; Zhou, X.; Cui, G.; Chen, L. Prescribing Functional Additives for Treating the Poor Performances of High-Voltage (5 V-class) LiNi0.5Mn1.5O4/MCMB Li-Ion Batteries. Advanced Energy Materials 2018, 8 (9), 1701398. (5) Zhang, Z.; Hu, L.; Wu, H.; Weng, W.; Koh, M.; Redfern, P. C.; Curtiss, L. A.; Amine, K. Fluorinated Electrolytes for 5 V Lithium-ion Battery Chemistry. Energy & Environmental Science 2013, 6 (6), 1806. (6) Ni, J.; Han, Y.; Gao, L.; Lu, L. One-pot Synthesis of CNT-wired LiCo0.5Mn0.5PO4 Nanocomposites. Electrochemistry Communications 2013, 31, 84-87. (7) Feng, J.; An, Y.; Ci, L.; Xiong, S. Nonflammable Electrolyte for Safer Non-aqueous Sodium Batteries. Journal of Materials Chemistry A 2015, 3 (28), 14539-14544. (8) Ni, J.; Zhao, Y.; Liu, T.; Zheng, H.; Gao, L.; Yan, C.; Li, L. Strongly Coupled Bi2S3@CNT Hybrids for Robust Lithium Storage. Advanced Energy Materials 2014, 4 (16), 1400798.


Page 18 of 22

Page 19 of 22 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


(9) J.-M. Tarascon, M. A. Issues and Challenges Facing Rechargeable Lithium Batteries. Nature 2001, 15 (17), 359-367. (10) Zeng, Z.; Murugesan, V.; Han, K. S.; Jiang, X.; Cao, Y.; Xiao, L.; Ai, X.; Yang, H.; Zhang, J.-G.; Sushko, M. L.; Liu, J. Non-flammable Electrolytes with High Salt-tosolvent Ratios for Li-ion and Li-metal Batteries. Nature Energy 2018, 3 (8), 674-681. (11) Ni, J.; Huang, Y.; Gao, L. A High-Performance Hard Carbon for Li-ion Batteries and Supercapacitors Application. Journal of Power Sources 2013, 223, 306-311. (12) He, M.; Su, C.-C.; Feng, Z.; Zeng, L.; Wu, T.; Bedzyk, M. J.; Fenter, P.; Wang, Y.; Zhang, Z. High Voltage LiNi0.5Mn0.3Co0.2O2/Graphite Cell Cycled at 4.6 V with a FEC/HFDEC-Based Electrolyte. Advanced Energy Materials 2017, 7 (15), 1700109. (13) An, Y.; Fei, H.; Zeng, G.; Ci, L.; Xiong, S.; Feng, J.; Qian, Y. Green, Scalable, and Controllable Fabrication of Nanoporous Silicon from Commercial Alloy Precursors for High-Energy Lithium-Ion Batteries. ACS nano 2018, 12 (5), 4993-5002. (14) Szczech, J. R.; Jin, S. Nanostructured Silicon for High Capacity Lithium Battery Anodes. Energy Environ. Sci. 2011, 4 (1), 56-72. (15) Qiu, F.; Li, X.; Deng, H.; Wang, D.; Mu, X.; He, P.; Zhou, H. A Concentrated Ternary‐Salts Electrolyte for High Reversible Li Metal Battery with Slight Excess Li. Advanced Energy Materials 2018, 9 (6), 1803372. (16) Ni, J.; Li, Y. Carbon Nanomaterials in Different Dimensions for Electrochemical Energy Storage. Advanced Energy Materials 2016, 6 (17), 1600278. (17) Ni, J.; Zhou, H.; Chen, J.; Zhang, X. Improved Electrochemical Performance of Layered LiNi0.4Co0.2Mn0.4O2 via Li2ZrO3 Coating. Electrochimica Acta 2008, 53 (7), 3075-3083. (18) Zhang, L.; Ni, J.; Wang, W.; Guo, J.; Li, L. 3D Porous Hierarchical Li2FeSiO4/C for Rechargeable Lithium Batteries. Journal of Materials Chemistry A 2015, 3 (22), 11782-11786. (19) Zhai, W.; Ai, Q.; Chen, L.; Wei, S.; Li, D.; Zhang, L.; Si, P.; Feng, J.; Ci, L. Walnut-Inspired Microsized Porous Silicon/Graphene Core–Shell Composites for High-Performance Lithium-ion Battery Anodes. Nano Research 2017, 10 (12), 42744283. (20) Choi, N.-S.; Yew, K. H.; Lee, K. Y.; Sung, M.; Kim, H.; Kim, S.-S. Effect of Fluoroethylene Carbonate Additive on Interfacial Properties of Silicon Thin-film Electrode. Journal of Power Sources 2006, 161 (2), 1254-1259. (21) Bordes, A.; Eom, K.; Fuller, T. F. The Effect of Fluoroethylene Carbonate Additive Content on the Formation of the Solid-electrolyte Interphase and Capacity Fade of Li-ion Full-cell Employing Nano Si–graphene Composite Anodes. Journal of Power Sources 2014, 257, 163-169. (22) Tian, Y.; An, Y.; Feng, J. Flexible and Freestanding Silicon/MXene Composite Papers for High-Performance Lithium-Ion Batteries. ACS applied materials & interfaces 2019, 11 (10), 10004-10011. (23) Salah, M.; Murphy, P.; Hall, C.; Francis, C.; Kerr, R.; Fabretto, M. Pure Silicon Thin-film Anodes for Lithium-ion Batteries: A Review. Journal of Power Sources 2019, 414, 48-67. (24) Xia, J.; Nie, M.; Burns, J. C.; Xiao, A.; Lamanna, W. M.; Dahn, J. R. Fluorinated



Electrolyte for 4.5 V Li(Ni0.4Mn0.4Co0.2)O2/Graphite Li-ion Cells. Journal of Power Sources 2016, 307, 340-350. (25) Smart, M. C.; Ratnakumar, B. V.; Ryan-Mowrey, V. S.; Surampudi, S.; Prakash, G. K. S.; Hu, J.; Cheung, I. Improved Performance of Lithium-ion Cells with the Use of Fluorinated Carbonate-based Electrolytes. Journal of Power Sources 2003, 119-121, 359-367. (26) Pham, H. Q.; Lee, H.-Y.; Hwang, E.-H.; Kwon, Y.-G.; Song, S.-W. Nonflammable Organic Liquid Electrolyte for High-safety and High-energy Density Li-ion Batteries. Journal of Power Sources 2018, 404, 13-19. (27) Pham, H. Q.; Hwang, E. H.; Kwon, Y. G.; Song, S. W. Approaching the Maximum Capacity of Nickel-rich LiNi0.8Co0.1Mn0.1O2 Cathodes by Charging to High-voltage in A Non-flammable Electrolyte of Propylene Carbonate and Fluorinated Linear Carbonates. Chemical communications 2019, 55 (9), 1256-1258. (28) Bouibes, A.; Takenaka, N.; Fujie, T.; Kubota, K.; Komaba, S.; Nagaoka, M. Concentration Effect of Fluoroethylene Carbonate on the Formation of Solid Electrolyte Interphase Layer in Sodium-Ion Batteries. ACS applied materials & interfaces 2018, 10 (34), 28525-28532. (29) Chang, Z. H.; Wang, J. T.; Wu, Z. H.; Gao, M.; Wu, S. J.; Lu, S. G. The Electrochemical Performance of Silicon Nanoparticles in Concentrated Electrolyte. ChemSusChem 2018, 11 (11), 1787-1796. (30) Wang, J.; Yamada, Y.; Sodeyama, K.; Watanabe, E.; Takada, K.; Tateyama, Y.; Yamada, A. Fire-extinguishing Organic Electrolytes for Safe Batteries. Nature Energy 2017, 3 (1), 22-29. (31) Zhang, R.; Bao, J.; Wang, Y.; Sun, C. F. Concentrated Electrolytes Stabilize Bismuth-Potassium Batteries. Chemical science 2018, 9 (29), 6193-6198. (32) Shi, P.; Zheng, H.; Liang, X.; Sun, Y.; Cheng, S.; Chen, C.; Xiang, H. A highly concentrated phosphate-based electrolyte for high-safety rechargeable lithium batteries. Chemical communications 2018, 54 (35), 4453-4456. (33) Xu, C.; Lindgren, F.; Philippe, B.; Gorgoi, M.; Björefors, F.; Edström, K.; Gustafsson, T. Improved Performance of the Silicon Anode for Li-Ion Batteries: Understanding the Surface Modification Mechanism of Fluoroethylene Carbonate as An Effective Electrolyte Additive. Chemistry of Materials 2015, 27 (7), 2591-2599. (34) Hosaka, T.; Kubota, K.; Kojima, H.; Komaba, S. Highly Concentrated Electrolyte Solutions for 4 V Class Potassium-ion Batteries. Chemical communications 2018, 54 (60), 8387-8390. (35) Yang, H.; Guo, C.; Chen, J.; Naveed, A.; Yang, J.; Nuli, Y.; Wang, J. An Intrinsic Flame-Retardant Organic Electrolyte for Safe Lithium-Sulfur Batteries. Angewandte Chemie 2019, 58 (3), 791-795. (36) Liu, X.; Jiang, X.; Zeng, Z.; Ai, X.; Yang, H.; Zhong, F.; Xia, Y.; Cao, Y. High Capacity and Cycle-Stable Hard Carbon Anode for Nonflammable Sodium-Ion Batteries. ACS applied materials & interfaces 2018, 10 (44), 38141-38150. (37) Hagos, T. T.; Thirumalraj, B.; Huang, C. J.; Abrha, L. H.; Hagos, T. M.; Berhe, G. B.; Bezabh, H. K.; Cherng, J.; Chiu, S. F.; Su, W. N.; Hwang, B. J. Locally Concentrated LiPF6 in a Carbonate-Based Electrolyte with Fluoroethylene Carbonate


Page 20 of 22

Page 21 of 22 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


as a Diluent for Anode-Free Lithium Metal Batteries. ACS applied materials & interfaces 2019, 11 (10), 9955-9963. (38) Chen, S.; Zheng, J.; Yu, L.; Ren, X.; Engelhard, M. H.; Niu, C.; Lee, H.; Xu, W.; Xiao, J.; Liu, J.; Zhang, J.-G. High-Efficiency Lithium Metal Batteries with FireRetardant Electrolytes. Joule 2018, 2 (8), 1548-1558. (39) Kim, H.; Lee, E.-J.; Sun, Y.-K. Recent Advances in the Si-based Nanocomposite Materials as High Capacity Anode Materials for Lithium Ion Batteries. Materials Today 2014, 17 (6), 285-297. (40) Zou, X.; Xiong, P.; Zhao, J.; Hu, J.; Liu, Z.; Xu, Y. Recent Research Progress in Non-aqueous Potassium-ion Batteries. Physical chemistry chemical physics : PCCP 2017, 19 (39), 26495-26506. (41) Chan, C. K.; Peng, H.; Liu, G.; McIlwrath, K.; Zhang, X. F.; Huggins, R. A.; Cui, Y. High-performance Lithium Battery Anodes Using Silicon Nanowires. Nature nanotechnology 2008, 3 (1), 31-35. (42) Feng, J.; Zhang, Z.; Ci, L.; Zhai, W.; Ai, Q.; Xiong, S. Chemical dealloying synthesis of porous silicon anchored by in situ generated graphene sheets as anode material for lithium-ion batteries. Journal of Power Sources 2015, 287, 177-183. (43) Yang, K.; Deng, Z.; Suo, J. Synthesis and Characterization of LiFePO4 and LiFePO4/C Cathode Material from Lithium Carboxylic Acid and Fe3+. Journal of Power Sources 2012, 201, 274-279. (44) Chen, L.; Wang, K.; Xie, X.; Xie, J. Enhancing Electrochemical Performance of Silicon Film Anode by Vinylene Carbonate Electrolyte Additive. Electrochemical and Solid-State Letters 2006, 9 (11), A512. (45) Jin, Y.; Kneusels, N. H.; Marbella, L. E.; Castillo-Martinez, E.; Magusin, P.; Weatherup, R. S.; Jonsson, E.; Liu, T.; Paul, S.; Grey, C. P. Understanding Fluoroethylene Carbonate and Vinylene Carbonate Based Electrolytes for Si Anodes in Lithium Ion Batteries with NMR Spectroscopy. Journal of the American Chemical Society 2018, 140 (31), 9854-9867. (46) Philippe, B.; Dedryvere, R.; Gorgoi, M.; Rensmo, H.; Gonbeau, D.; Edstrom, K. Improved Performances of Nanosilicon Electrodes Using the Salt LiFSI: A Photoelectron Spectroscopy Study. Journal of the American Chemical Society 2013, 135 (26), 9829-9842. (47) Jin, Y.; Kneusels, N. H.; Magusin, P.; Kim, G.; Castillo-Martinez, E.; Marbella, L. E.; Kerber, R. N.; Howe, D. J.; Paul, S.; Liu, T.; Grey, C. P. Identifying the Structural Basis for the Increased Stability of the Solid Electrolyte Interphase Formed on Silicon with the Additive Fluoroethylene Carbonate. Journal of the American Chemical Society 2017, 139 (42), 14992-15004. (48) Dalavi, S.; Guduru, P.; Lucht, B. L. Performance Enhancing Electrolyte Additives for Lithium Ion Batteries with Silicon Anodes. Journal of The Electrochemical Society 2012, 159 (5), A642-A646. (49) Xu, G.; Wang, X.; Li, J.; Shangguan, X.; Huang, S.; Lu, D.; Chen, B.; Ma, J.; Dong, S.; Zhou, X.; Kong, Q.; Cui, G. Tracing the Impact of Hybrid Functional Additives on a High-Voltage (5 V-class) SiOx-C/LiNi0.5Mn1.5O4 Li-Ion Battery System. Chemistry of Materials 2018, 30 (22), 8291-8302.



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Non-flammable Fluorinated Carbonate Electrolyte with High Salt-to

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