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Engineered Interfaces in Hybrid Ceramic-Polymer Electrolytes for use in All-Solid-State Li Batteries Parameswara Rao Chinnam, and Stephanie L. Wunder ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.6b00609 • Publication Date (Web): 09 Dec 2016 Downloaded from http://pubs.acs.org on December 10, 2016
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ACS Energy Letters
Engineered Interfaces in Hybrid Ceramic-Polymer Electrolytes for use in All-Solid-State Li Batteries Parameswara Rao Chinnam† and Stephanie L. Wunder†,* †Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122, United States Abstract Composites of inorganic lithium ion conducting glass ceramics (LICGC) and organic polymers may provide the best combination of properties for safe solid separators in lithium or lithium ion batteries to replace the currently used volatile liquid electrolytes. A key problem for their use is the high interfacial resistance that develops between the two, increasing the total cell impedance. Here we show that the application of a thin conformal SiO2 coating onto a LICGC, followed by silanization with (CH3CH2O)3Si-(OCH2CH2)-OCH3 in the presence of LiTFSI results in good adhesion between the SiO2 and the LICGC, a low resistance interface, and good wetting of Li0. Further, the crosslinked polymer formed on the surface of the silanated SiO2 interface formed from excess (CH3CH2O)3-Si-(OCH2CH2)-OCH3 prevents corrosion of the LICGC by Li0 metal. The use of SiO2 as a “glue” enables compatibilization of inorganic ceramics with other polymers and introduction of interfacial pendant anions.
The need for safe lithium /lithium ion batteries (LIBs), particularly for large scale energy storage and for electric (EV) or hybrid (HEV) electric vehicle applications, has motivated the search for solid separators that would enable the use of metallic Li0 for increased energy density1-3. Currently, there are two approaches to the development of solid separators. One is the synthesis of inorganic ceramic materials4. These can achieve conductivities similar to those of liquid electrolytes (> 10-3 S/cm), are single ion conductors (SICs), i.e. only the cation is mobile, have shear moduli that can withstand dendrite growth5-7, but are brittle with low fracture energies2, 8, poor rate capabilities, high-impedance grain boundary and inter-particle interfacial resistance in compacted disks9, and cannot form conformal surfaces with the electrode particles during charging and discharging, which effectively leads to a high interfacial resistance. The other approach is the development of solid polymer electrolytes (SPEs), which are flexible and adhere better to electrolyte particles, but have much lower ionic conductivities (< 10-5 S/cm)10, 11, moduli that do not prevent Li dendrite growth12, and concentration gradients that promote dendrite 1 ACS Paragon Plus Environment
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growth, unless the polymers contain the anions, forming polymer SICs13. However, conductivity of these SICs is very low (< 10-5 S/cm). In order to mitigate the problems inherent in both inorganic and polymer SPEs, blending of the two to form a hybrid system would be ideal. What has stymied the development of hybrid LICGC-polymer solid electrolytes is the inability to successfully control the interface between the two materials. Organic polymers and ionic ceramics are inherently incompatible, so there is a barrier to the migration of ions across this interface (i.e. there is a high interfacial resistance). Further there are not many ways to modify the ceramic surface to make it compatible and enhance conductivity with organic species14. At large volume fractions of LICGC, σtotal → σLICGC is almost never realized and the polymer appears to act as a binder for the grains with conductivities 10-100 fold less than the LICGC. This decrease has been attributed to an inability of the Li+ (or Na+) ions to cross the ceramic-polymer interface, with one factor a lack of intimate interfacial contact between the phases14 15. Both good contact15, 16 and covalent bonding17 have been shown to decrease interfacial resistance. The above results lead us to investigate a more general approach to form an interface that would be applicable to a wider range of hybrid systems, and one that would also prevent LICGC corrosion by Li0. In particular, we sputter coated a 200 nm thick SiO2 coating onto a Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2, a commercial LICGC, and silanated it with CH3O-(CH2CH2O)x-(CH2)3Si(OCH2CH3)3 (PEG-silane) in the presence of LiTFSI (Figure 1). SEM (Figure 1, Figure S1 and S2) and AFM (Figure S3) images of the SiO2 layer clearly show a conformal coating of the SiO2 on the LICGC, while top views of this coating suggest that it is deposited with ~ 100 nm grains between which are channels. After silanization, a smooth “polymer” coating, formed from hydrolysis and cross-linking of the PEG-silane, can be observed (Figure 1, Figure S2). A film made with the PEG-silane in the presence of LiTFSI (O/Li = 12/1) was a selfstanding soft rubber. DSC data (Figure S4) show that the crosslinking reaction suppresses the original PEG-silane crystallinity, and increases the glass transition temperature (Tg) from –87 0C to ~ -60 0C. For comparison, the SiO2-LICGC was also soaked in tetraglyme (G4) and G4/LiTFSI (O/Li = 4/1) (Figure 1).
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Figure 1. (top) schematic of fabrication of SiO2 coated LICGC (SiO2-LICGC) functionalized with a PEG-silanetests in show the presence of LiTFSI, showing (A) the tetraglyme (G4),is silanated (B) 2Conductivity that low interfacial resistance canstructures be obtainedofwhen LICGC-SiO 2 oxide)=9-1212/1)propyl] (PEG-silane) and = (C) with[ethoxy(polyethylene PEG-silane/LiTFSI (O/Li or infusedtrimethoxysilane with a mixture of G4/LiTFSI (O/Li 4/1). -4 o bis(trifluoromethane)sulfonimide lithium salt (LiTFSI); (bottom) SEM images of SiO -LICGC (A) Conductivities (1.5×10 S/cm at 30 C) of pure LICGC from electrochemical impedance2 spectroscopy side view showing 200 nmwith SiOdata (B) by topthe view showing granular 2 coating; (EIS) data (Figure S5)conformal are in agreement provided supplier (Ohara Inc). porous structure of SiO2 and (C) after silanization with PEG-silane /LiTFSI (O/Li = 12/1). Temperature ( oC) 112
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Figure 2. (left) Z′′ vs Z′ at 30 0C for pure G4/LiTFSI (O/Li = 4/1) (∗─∗─∗); and SiO2-LICGC (i) soaked in G4 (♦─♦─♦); (ii) soaked in G4/LiTFSI (O/Li = 4/1) (●─●─●); and (iii) silanated with PEG-silane/LiTFSI (O/Li = 12/1) (▲─▲─▲); (right) dependence of log (1/Rtot), where Rtot = Rbulk + Rinterface on temperature for LICGC (■─■─■), and SiO2-LICGC (ii) soaked in G4/LiTFSI (O/Li = 4/1) (●─●─●) and (iii) silanated with PEG-silane/LiTFSI (O/Li = 12/1) (▲─▲─▲). The area of each sample was kept at 0.25 cm2. Stainless steel blocking electrodes For the SiO2-LICGC infused with: (i) G4, (ii) G4/LiTFSI (O/Li = 4/1) and (iii) silanated with PEGsilane/LiTFSI (O/Li = 12/1), all of the high frequency intercepts are the same, and correspond to the bulk conductivity of the LICGC, 1.5×10-4 S/cm at 30oC. The equivalent circuits used for analysis of the EIS spectra are presented in Figure S6. As expected, in the absence of lithium ions in the interfacial region (i) the interfacial impedance is very high. When the LiTFSI is added (ii), the interfacial impedance decreases significantly, with a temperature dependence shown in Figure 2. Most encouraging is the impedance of the SiO2 silanated with PEG-silane/LiTFSI (O/Li = 12/1) (iii), which is even slightly less than that of the liquid G4/LiTFSI (O/Li = 4/1). Since Rtot = Rbulk + Rinterface, this shows that an immobile material (i.e. the PEG covalently attached to SiO2) of low resistance (similar to a liquid) can be used to shuttle Li+ ions across the interface. The PEG-silane/LiTFSI (O/Li = 12/1) appears to fill the interstices of the deposited SiO2 (Figure 1C), providing a critically important conduction path for the Li+ ions. For comparison, the impedance data for tetraglyme (G4)/LiTFSI (O/Li = 4/1) shows as expected only a slanted straight line (Figure 2), due to electrode polarization, with no semicircle from interfacial resistance. What is even more encouraging is that the SiO2-LICGC (Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2 is unstable with respect to Li0), when silanated with PEG-silane/LiTFSI (O/Li = 121) wets the Li0 anode and 3 ACS Paragon Plus Environment
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dramatically reduces the ability of Li0 metal to corrode the LICGC. Figure 3 shows a comparison of interfacial resistance, using Li0 metal non-blocking electrodes, as a function of time for (ii) and (iii). The equivalent circuits used to analyze the EIS data are presented in Figure S7. For (ii), G4/LiTFSI (O/Li = 4/1) infused into the SiO2-LICGC, only one semicircle is initially observed, which is the contribution of the bulk and interfacial resistance. With time, more semicircles appear that increase in diameter, and are the result of the continuous reaction of the LICGC with lithium, generating electronic and ionic conduction pathways in the electrolyte so that the cell shorts (in 60 h). By contrast, for (iii), the SiO2LICGC/PEG-silane (O/Li = 12/1), Rinterface increases for 60 h and then decreases. This same behavior is observed with a different stabilized time (~10 h) for the pure G4/LiTFSI (O/Li = 4/1), since G4/LiTFSI (without LICGC) is stable towards Li0. Thus, while the liquid G4/LiTFSI in the SiO2 did not protect the LICGC from Li corrosion, the crosslinked and chemically attached PEG-silane did prevent this Li0 corrosion. At 60 0C Rtotal = Rbulk + Rinterface decreases 13 fold and Rinterface deceases 6fold (Figure S8) compared with 25 0C.
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Cyclic charge/discharge (CCD) experiments using a Li0/separator/Li0 cell (separator = SiO2-LICGC-PEGsilane/LiTFSI (O/Li = 12/1)( Figure 4A), indicate that the first four cycles are erratic, possibly due to the plating of Li at the interface, which improves contact and results in stable cycling for the next 13 cycles. EIS data for this cell (Figure 4B) shows that both the bulk and interfacial resistance increase with cycling. This is attributed to penetration of Li0 dendrites through the thin crosslinked PEG-silane/LiTFSI polymer coating (< 10 nm) and subsequent reaction of the L0 dendrites with the LICGC. In order to prevent Li0 dendrite penetration, a thick polymer layer on top of the (PEG/LiTFSI)-SiO2- LICGC is required, as already demonstrated with 100 µm crosslinked acrylates on other LICGCs18.
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Figure 4. (A) The results of CCD for Li0/separator/Li0, 0.015 mA/cm2 at 25 oC with 1 hour charging/discharging; (B) Impedance spectra of Li0/separator/Li0 cell after CCD at 0, 10 and 17 cycles. Separator = SiO2-LICGC silanated with PEG-silane in presence of LiTFSI (O/Li = 12/1) In summary, hybrid ceramic-polymer electrolytes were formed by sputter coating a ~ 200 nm thick SiO2 layer onto a LICGC and silanating the SiO2 with PEG-silane in the presence of LiTFSI. A low interfacial resistance, slightly lower than that for liquid G4/LiTFSI soaked into the SiO2, was obtained. The silanated SiO2/LiTFSI (unlike G4/LiTFSI soaked into the SiO2) protected the LICGC from corrosion by Li0 metal. The thin (< 10 nm) conformal polymer coating formed by hydrolysis/crosslinking of the PEG-silane was not sufficient to prevent eventual dendrite penetration during CCD experiments, but can be improved by increasing the thickness of this layer or application of a thick polymer film. The application of a thin SiO2 coating to any inorganic ceramic SICs provides a general means to bond these ceramics to PEO-based polymers, and to incorporate other functionalities such as single ion conductivity into the interface (via the incorporation of silane coupling agents with pendant anions). Experimental Preparation of separators: The LICGC was Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2, with a proprietary composition, which has a Nasicon crystal structure, was a gift from Ohara glass, Corp. The SiO2 was deposited on both sides of the LICGC by low temperature electron beam evaporation with ion assisted 5 ACS Paragon Plus Environment
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plasma deposition, by TwinStar Optics, Coatings & Crystals. The SiO2-LICGC was silanated with 2[methoxy(polyethyleneoxy)propyl]trimethoxysilane, CH3O-(CH2CH2O)x-(CH2)3Si(OCH2CH3)3, x = 912, 90% purity (PEG-silane), from Gelest, Inc. in the presence of LiTFSI, using an O/Li = 12/1 ratio. In order to silanate the 200 nm SiO2 layer, the PEG-silane or PEG-silane /LiTFSI was dissolved in 95% EtOH and 5% water to which a few drops of formic acid were added, and stirred overnight. The solution was heated on a hot plate to remove much of the solvent. The SiO2-LICGC was soaked in this concentrated solution, the excess wiped off, and then it was cured in a vacuum oven at 100 0C for 72 h. Films of the sample (without the SiO2-LICGC) were made by evaporating the material the same way in a vial or on a glass slide. Characterization: Differential scanning calorimetry (DSC) data was obtained on a TA Instruments
Hi-Res DSC 2920 at 10◦C/min under N2. Scanning electron microscopy (SEM) images were obtained with the Quanta 450F (FEI Co.) using secondary (SE) and backscatter (BS) detectors. Electrochemical Measurements: The conductivity of the pure LICGC was tested between stainless steel (SS) electrodes, using carbon paste to make electrical contact. The ionic conductivities of SiO2-LiCGC soaked with LiG4TFSI, G4 and silanated with PEG-silane+LiTFSI were measured directly with stainless steel electrodes without using carbon paste. Ionic conductivities were measured by AC impedance spectroscopy using a Gamry potentiostat/galvanostat/ZRA (model interface 1000) in the frequency range from 0.01 to 1 MHz, and applied perturbation voltage of 10 mV. Control of the equipment was through Gamry framework software and the data were analyzed with Gamry Echem analysis software purchased from Gamry. Interfacial stability was obtained using the appropriate electrolyte, G4/LiTFSI (O/Li = 4/1), SiO2-LiCGC soaked with G4/LiTFSI (O/Li = 4/1) and silanated with PEG-silane+LiTFSI with symmetric nonblocking lithium electrodes in a CR2032 coin cell at 25oC. The interfacial resistance was measured under open circuit potential. Cyclic charge/discharge (CCD) was conducted on Li/SiO2-LICGC silanated with PEG-silane in presence of LiTFSI (O/Li = 12/1)/Li using a potentiostat (Gamry interface 1000) at 25oC with 0.015 mA/cm2 for one hour charging and discharging for 17 cycles. The cell impedance was measured using EIS between 1MHz to 0.1Hz at 0, 10 cycles and 17 cycles. ASSOCIATED CONTENT *Supporting Information The supporting Information is available free of charge on the ACS Publications website. AFM and SEM images of LICGC-SiO2; DSC thermograms; Nyquist plots and equivalent circuits (PDF) AUTHOR INFORMATION
Corresponding Author *
[email protected] Author contributions PRC and SLW contributed equally to this work Notes The authors declare no competing financial interest ACKNOWLEDGMENTS 6 ACS Paragon Plus Environment
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The financial support of the National Science Foundation under award CBET 1437814 is gratefully acknowledged. The authors thank Dr. Dmitriy A. Dikin for help with the SEM images and acknowledge the CoE-NIC facility at Temple University funded on DoD DURIP Award N0014-12-1-0777 from ONR. The authors also thank Professor Katherine Willet’s postdoc, Dr. Padmanabh Joshi, for help in obtaining AFM imaging. References (1) Goodenough, J. B.; Kim, Y. Challenges for Rechargeable Li Batteries. Chem. Mater. 2010, 22, 587603. (2) Goodenough, J. B.; Park, K. S. The Li-Ion Rechargeable Battery: A Perspective. J. Am. Chem. Soc. 2013, 135, 1167-1176. (3) Bouchet, R. Batteries: A stable lithium metal interface. Nat. Nanotechnol. 2014, 9, 572-573. (4) Knauth, P., Inorganic solid Li ion conductors: An overview. Solid State Ionics 2009, 180, (14–16), 911-916. (5) Monroe, C.; Newman, J. The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces. J. Electrochem. Soc. 2005, 152, A396-A404. (6) Li, Z.; Huang, J.; Liaw, B. Y.; Metzler, V.; Zhang, J. B. A review of lithium deposition in lithium-ion and lithium metal secondary batteries. J. Power Sources 2014, 254, 168-182. (7) Thangadurai, V.; Narayanan, S.; Pinzaru, D. Garnet-type solid-state fast Li ion conductors for Li batteries: critical review. Chem. Soc. Rev. 2014, 43, 4714-4727. (8) Lee, H.; Yanilmaz, M.; Toprakci, O.; Fu, K.; Zhang, X. W. A review of recent developments in membrane separators for rechargeable lithium-ion batteries. Energy Environ. Sci. 2014, 7, 3857-3886. (9) Tenhaeff, W. E.; Rangasamy, E.; Wang, Y. Y.; Sokolov, A. P.; Wolfenstine, J.; Sakamoto, J.; Dudney, N. J. Resolving the Grain Boundary and Lattice Impedance of Hot-Pressed Li7La3Zr2O12 Garnet Electrolytes. Chemelectrochem 2014, 1, 375-378. (10) Ling, Z. J.; He, X. M.; Li, J. J.; Jiang, C. Y.; Wan, C. R. Recent advances of all-solid-state polymer electrolyte for Li-ion batteries. Prog. Chem. 2006, 18, 459-466. (11) Dias, F. B.; Plomp, L.; Veldhuis, J. B. J. Trends in polymer electrolytes for secondary lithium batteries. J. Power Sources 2000, 88, 169-191. (12) Kalnaus, S.; Sabau, A. S.; Tenhaeff, W. E.; Dudney, N. J.; Daniel, C. Design of composite polymer electrolytes for Li ion batteries based on mechanical stability criteria. J. Power Sources 2012, 201, 280287. (13) Thomas, K. E.; Sloop, S. E.; Kerr, J. B.; Newman, J. Comparison of lithium-polymer cell performance with unity and nonunity transference numbers. J. Power Sources 2000, 89, 132-138. (14) Nairn, K. M.; Best, A. S.; Newman, P. J.; MacFarlane, D. R.; Forsyth, M. Ceramic-polymer interface in composite electrolytes of lithium aluminium titanium phosphate and polyetherurethane polymer electrolyte. Solid State Ionics 1999, 121, 115-119. (15) Tenhaeff, W. E.; Perry, K. A.; Dudney, N. J. Impedance Characterization of Li Ion Transport at the Interface between Laminated Ceramic and Polymeric Electrolytes. J. Electrochem. Soc. 2012, 159, A2118-A2123. (16) Tenhaeff, W. E.; Yu, X.; Hong, K.; Perry, K. A.; Dudney, N. J. Ionic Transport Across Interfaces of Solid Glass and Polymer Electrolytes for Lithium Ion Batteries. J. Electrochem. Soc. 2011, 158, A1143A1149. (17) Wong, D. H. C.; Thelen, J. L.; Fu, Y.; Devaux, D.; Pandya, A. A.; Battaglia, V. S.; Balsara, N. P.; DeSimone, J. M. Nonflammable perfluoropolyether-based electrolytes for lithium batteries. Proc. Nat. Acad. Sci. U.S.A. 2014, 111, 3327-3331.
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(18) Zhou, W. D.; Wang, S. F.; Li, Y. T.; Xin, S.; Manthiram, A.; Goodenough, J. B. Plating a DendriteFree Lithium Anode with a Polymer/Ceramic/Polymer Sandwich Electrolyte. J. Am. Chem. Soc. 2016, 138, 9385-9388.
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