Dumbbell-Shaped Octasilsesquioxanes ... - ACS Publications

Subscriber access provided by LAURENTIAN UNIV

Article

Dumbbell-Shaped Octasilsesquioxanes Functionalized with Ionic Liquids as Hybrid Electrolytes for Lithium Metal Batteries guang yang, Hyukkeun Oh, Chalathorn Chanthad, and Qing Wang Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.7b03229 • Publication Date (Web): 11 Oct 2017 Downloaded from http://pubs.acs.org on October 12, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Chemistry of Materials is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 11

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

Chemistry of Materials

Dumbbell-Shaped Octasilsesquioxanes Functionalized with Ionic Liquids as Hybrid Electrolytes for Lithium Metal Batteries Guang Yang, Hyukkeun Oh, Chalathorn Chanthad, and Qing Wang* Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, USA ABSTRACT: Exploring solid-state electrolytes as alternatives for flammable liquid carbonate electrolyte is considered as one of the key routes toward next-generation lithium polymer batteries assembled with high capacity electrode. In this work, we synthesized an organic-inorganic hybrid solid electrolyte with ionic liquid moieties tethered onto dumbbellshaped octasilsesquioxanes through oligo(ethylene glycol) spacers. The hybrid electrolyte is featured by its high roomtemperature ionic conductivity (1.2×10-4 S/cm at 20 oC with LiTFSI salt), excellent electrochemical stability (4.6 V vs Li+/Li), and great thermal stability. Excellent capability of the hybrid electrolyte to mediate electrochemical deposition and dissolution of lithium has been demonstrated in the symmetrical lithium cells. No short circuit has been observed after more than 500 hrs in the polarization tests. Decent charge/discharge performance has been obtained in the prepared electrolyte based all-solid-state lithium battery cells at ambient temperature.

INTRODUCTION

Lithium ion batteries (LIBs) have been gaining intense attention owing to their broad applications in portable electronics (such as cell phones, laptops) and electric vehicles.1-3 Although the use of lithium as anode to replace the conventional graphite anode is very promising because lithium metal has significant higher theoretical capacity (3860 mA·h/g) and low redox potential (-3.04 V),4, 5 there exists a serious safety issue arisen from liquid electrolyte that needs to be addressed before large capacity lithium metal batteries can be trusted for electrifying our daily life. The currently available organic, liquid carbonate electrolytes need to be substituted by safer electrolytes to prevent unexpected battery accidents such as leakage, combustion and explosion, etc. Additionally, the liquid electrolytes are not able to interfere with formation and growth of the lithium dendrite. Consequently, the replacement of graphite anode with much higher capacity lithium metal anode is severely hindered.6, 7 As important alternatives of liquid electrolyte, solid polymer electrolytes are easy to process and leakage-free.8, 9 The ideal features for solid state electrolytes include excellent chemical and electrochemical stability, facile processability, good compatibility with electrodes, inexpensiveness, and satisfactory mechanical properties in addition to sufficiently high ionic conductivities. Achieving these properties concurrently is a great challenge toward unveiling the broader applications of LIBs.2, 6, 8, 10, 11 The study of all solid-state polymer electrolytes dates back to 1970s when noticeable ionic conductivities of poly(ethylene glycol) (PEO)/Na+ system were realized by

pioneer researchers Wright and Armand.12-14 However, despite of decades of intensive efforts, the ionic conductivities of PEO based solid electrolytes are usually lower than 10-6 S/cm at ambient temperature. Therefore, for the lithium polymer batteries operating at room temperature, a certain amount of liquid electrolytes or organic solvents have to be introduced to the polymer host to boost the room-temperature ionic conductivity.15, 16 More recently, extensive efforts have been placed on plasticizing polymer electrolyte with non-volatile and non-flammable molecules,17, 18 improving the ion transport by creating ion conduction channel in the copolymers,19, 20 incorporating inorganic nanoparticles to form composite electrolytes,21, 22 and developing other alternative polymeric materials with desired electrochemical properties.10, 23 In particular, ionic liquids (ILs) have been intensively investigated as electrolytes or solvents for electrochemical energy devices.24 For example, imidazolium-based ILs possess low viscosity, good thermal stability, and high ionic conductivity (> 10-3 S/cm).25-27 ILs can either function as plasticizers for polymer electrolytes or serve as monomers to be polymerized as poly(ionic liquid) electrolytes. Cations or anions of ILs have also been covalently bonded to polymer backbone or side chain structures as electrolytes.28-30 Unfortunately, most of the IL-grafted polymers and inorganic particles still show unacceptably low conductivities (less than 10-5 S/cm at room temperature in most cases) when considered as ion transport medium for LIBs.29,30-33 In this work, we describe the synthesis and characterization of a dumbbell-shaped organic-inorganic hybrid

ACS Paragon Plus Environment


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

electrolyte (CPOSS-IL) based on polyhedral oligomeric silsesquioxane (POSS) grafted with IL side chains. POSS with an inorganic (SiO1.5)n (n=6, 8, or 10) cage and organic functional groups located at the corners of the cage is a

Page 2 of 11

versatile building block for organic-inorganic hybrids and polymer nanocomposite.34 PEO has been combined with POSS to form the linear, star shaped and crosslinked

Scheme 1. Synthesis of dumbbell-shaped hybrid electrolyte.

2


Page 3 of 11

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


hybrid polymer electrolytes.35-37 More recently, we have reported a hybrid dendritic-like electrolyte derived from ionic liquid grafted POSS, which exhibits outstanding ionic conductivities and electrochemical properties.38 Herein, by using methylene diphenyl diisocyanate as a linker, two monohydroxylated POSS molecules were coupled followed by subsequently attaching ILs onto peripheral of POSS. An impressively high ionic conductivity of 1.2 × 10-4 S/cm has been obtained from the prepared hybrid electrolyte measured at room temperature. Meanwhile, the electrolyte exhibits good electrochemical stability and the ability to support stable lithium deposition. Moreover, it is found that the all-solid-state Li battery cells fabricated from the prepared electrolyte deliver high capacities at room temperature.

peaks of TFSI- anions (1352, 1195, 1135, 1056 cm-1) have been observed in the FTIR spectrum of CPOSS-IL-LiTFSI (Figure S7).39, 40

(a)

RESULTS AND DISCUSSION

Synthesis. The synthetic route for CPOSS-IL is shown in Scheme 1. 4,4’-methylene bis(phenyl isocyanate (MDI) was used as the diisocyanate linker for dumbbell-shaped CPOSS. The introduction of two POSS rings into the hybrid electrolyte is expected to yield the electrolyte with high robustness. The urethane bonds formation was achieved upon the reaction between MDI and VPOSSOH. Each halogen atom of trichlorovinylsilane acted as a coupling site with mono-brominated hexaethylene glycol to produce compound 1. With the help of 1,1,3,3tetramethyldisiloxane as a connector, compound 1 was grafted onto the CPOSS structure. After quaternization reaction of imidazole ring with CPOSS-PEO and anion exchange, the dumbbell-shaped hybrid CPOSS-IL was obtained. The successful formation of urethane bonds in CPOSS is confirmed by the NMR and FTIR spectra. The proton signal located at 3.90 ppm in the 1H NMR spectrum (Figure S2) is assigned to the protons on the methylene group between the two aromatic rings. The absorbance at 4.26 ppm comes from the protons of urethane linkages (-NH-CO-O-) whose carbonyl carbon signal can be seen at 153 ppm in the 13C NMR (Figure S3). Moreover, the formation of –NH-CO-O- linkage is verified by the appearance of the peaks at 1734 and 1527 cm-1 assigned to the ester carbonyl bond and the N-H bending vibration, respectively, as shown in the FTIR spectra (Figure 1). The disappearance of stretching vibration of NCO bond at 2280 cm-1 arising from the starting material MDI is suggestive of the completion of reaction. For the synthesis of compound 2, the disappearance of vinyl proton signal at around δ6 ppm in the 1H NMR spectrum (Figure. S4) proves the completion of hydrosilylation reaction. In the 1 H NMR spectrum of CPOSS-IL, the significant suppression of -CH2-Br and -CH2-CH2-Br proton signals at δ3.46 and 3.80 ppm, respectively, in CPOSS-IL indicates the successful coupling of 1-butyl imidazole. Upon doping with LiTFSI, the prepared electrolyte was labeled as CPOSS-IL-LiTFSI. Also, the characteristic absorbance

Figure 1. (a) FTIR spectra of VPOSS-OH, CPOSS, and 1 MDI, (b) H NMR of CPOSS-IL.

Thermal and X-ray analysis. The thermal properties of CPOSS-IL-LiTFSI were investigated by DSC and TGA. Figure S8a presents the DSC profile from 85 to 20 . The glass transition temperature (Tg) of the hybrid was found to be -62 . No endothermic melting transition was found, suggestive of the amorphous nature of the electrolyte. Thermal stability of electrolytes is important because heat can be generated when battery operates. The thermal decomposition temperature was measured by TGA under nitrogen from 25 to above 500 , which reveals excellent thermal stability of CPOSS-IL-LiTFSI. As shown in Figure S8b, the initial 3% weight loss before sharp decomposition mainly comes from the release of absorbed moisture.41 It is interesting to note that the sharp degradation of CPOSS-IL-LiTFSI was found at

3



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

around 230 , which appears to be higher than the decomposition temperatures of hexaethylene glycol (i.e. 162 oC) and OVPOSS (i.e. 195 oC). This is probably due to its high molecular mass and strong molecular interactions in CPOSS-IL-LiTFSI.42, 43 CPOSS-ILLiTFSI shows a 75% weight loss between 230 and 500 and the remaining char residue is likely to be composed of SiO2 and decomposed lithium salt.44 The amorphous characteristic of CPOSS-IL was further confirmed by X-ray diffraction (XRD). Amorphous halo at 2θ=8.1o (d-spacing of 1.1 nm) originating from the inter-distance of POSS can be seen from Figure S9, while the diffraction peak at 2θ=20 o (dspacing of 0.44 nm) is attributable to the amorphous PEO chain. As it is recognized that ion transport takes place predominantly in amorphous phase in polymer electrolytes, the amorphous nature of the hybrid electrolyte is thus beneficial for ionic conductivity.45, 46 Ionic conductivity. The temperature dependence of the ionic conductivity of CPOSS-IL-LiTFSI (the ratio of ethylene oxide unit of the hybrid electrolyte vs. Li+ salt [EO]:[Li]=12:1) is presented in Figure 2. For the purpose of comparison, the dumbbell-shaped organic-inorganic hybrid electrolyte CPOSS-PEOLiTFSI ([EO]:[Li]=12:1) which has no IL segments was prepared and characterized (the structure of CPOSSPEO is shown in Scheme 1). It is found that the conductivity of the hybrid electrolytes increases nonlinearly with temperature. Importantly, the conductivity data measured during the heating and cooling processes are consistent, indicative of remarkable stability of the ion conduction of the electrolytes CPOSSIL-LiTFSI and CPOSS-PEO-LiTFSI over the measured temperature range. Note that the ionic conductivity of CPOSS-IL-LiTFSI is nearly one order of magnitude higher than that of CPOSS-PEO-LiTFSI, e.g. 1.2×10-4 S/cm vs. 5.2×10-5 S/cm at 20 oC. This value is comparable to the dendritic-like electrolyte based on ionic liquid functionalized POSS (i.e. 4.8 x 10-4 S/cm at 25 o C),38 and is impressive for all-solid-state organic/polymer-based electrolytes.10, 32, 47, 48 It is believed that the presence of imidazolium cations interacts with TFSI- anions through coulombic force to liberate more dissociated, mobile Li+ ions from LiTFSI, as evidenced in our previous Raman studies.49, 50

Page 4 of 11

Figure 2. Temperature dependence of Ionic conductivity.

Table 1. Ionic conductivity at room temperature and VTF fitting results. σ (20 oC, S/cm)

Rsquare

B (KJ/mol)

A (S/cm·K1/2)

CPOSS-ILLiTFSI

1.2×10-4

0.999

8.3

4.3

CPOSS-PEOLiTFSI

5.2×10-5

0.999

9.0

3.9

As shown in Figure 2, the conductivity data of the hybrid electrolytes are fitted well by Vogel–Tamman– Fulcher (VTF) equation: σ=AT-1/2exp[-Ea/R(T-T0)], whereas Ea is a constant related to activation energy for ion conduction, A is pre-exponential factor, T0 is the reference temperature and R is the ideal gas constant. Table 1 lists the fitting results. The observed VTF behavior indicates that the ion motion in the hybrid electrolytes is correlated to segmental motion of long chains grafted onto POSS above its Tg. The Ea value of CPOSS-IL-LiTFSI fitted by VTF equation is 8.3 kJ mol-1, which is smaller than the corresponding value of CPOSS-PEO-LiTFSI (i.e. 9 KJ mol1 ), signifying a lower energy barrier for ion transport in CPOSS-IL-LiTFSI when compared with CPOSS-IL-LiTFSI.

Electrochemical characterization. The electrochemical stability of CPOSS-IL-LiTFSI was studied by voltammogram. As shown in Figure 3a. At the low potential region, both negative lithium plating peak (-0.65 V vs. Li+/Li) and positive lithium stripping peak (0.15 V vs. Li+/Li) are observed, confirming efficient movement of Li+ ions through the hybrid electrolyte.31, 49, 51 The small, broad redox peak in the 0 to 1 V vs Li/Li+ range might be related to redox reaction of electrode surface species,52 or parasite reaction of TFSI – anion, or other impurities.31 From the positive scan in the voltammetry curve in Figure 3b, the onset of anodic current was found at 4.6 V vs Li/Li+.

Figure 3. (a) Cyclic voltammogram of CPOSS-IL-LiTFSI, (b) Linear sweep voltammetry of CPOSS-IL-LiTFSI measured at 25 .

4


Page 5 of 11

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


Electrochemical impedance spectrum (EIS) was utilized to characterize the interfacial stability of CPOSS-ILLiTFSI against lithium anode. Figure S10 is the nyquist plot of Li/CPOSS-IL-LiTFSI/Li cell showing the evolution of semicircle as a function of aging time at room temperature. The bulk resistance (Rb, reflects the electrolyte resistance) is denoted by the left high frequency intercept at real axis of semicircle) and interfacial resistance (Rint, represents the charge transfer resistance of Li++e- =Li reaction at lithium/electrolyte interface and the resistance of the passive layer) is the amplitude of the diameters of the distorted semicircles. Noticeable increase of the Rb value and the semicircle shape were not found over the storage time. The diameter of semicircle increases at the early stage, revealing the formation of passivation film, and then becomes relative stable after 9 days. After fitting with a simplified equivalent circuit model, the Rb and Rint values are extracted from the fitting results and plotted as a function of storage time as shown in Figure S11, where R1 corresponds to the bulk resistance, R2 is the interfacial resistance, and CPE and W are constant phase element and Warburg diffusion element (Li+ diffusion on the electrode/electrolyte interface and electrolyte salt diffusion), respectively.50, 53-55 Lithium transference number (tLi+) of CPOSS-ILLiTFSI was investigated by chronoamperometry in combination with impedance spectroscopy. According to the method reported by Bruce et al.,56 tLi+=Is(V-IiRi)/Ii(V-IsRs), where V is the constant DC voltage applied, Ii and Is are the initial and steady state current, and Ri and Rs are the interfacial resistance before and after DC polarization, respectively. tLi+ was calculated to be 0.37 (Figure S12). For organic liquid electrolyte, IL based electrolytes, and PEOLi salt electrolyte, tLi+ is normally less than 0.35.21, 50, 53-55, 57 This relatively higher tLi+ obtained in CPOSS-IL-LiTFSI can be attributed to reduced TFSI- mobility in CPOSS-ILLiTFSI through coulombic interaction between imidazolium ions and TFSI- and attraction between POSS and TFSI- besides high mobility of Li+.21, 49, 50

Figure 4. Galvanostatic stripping/plating cycles of Li/CPOSS-IL-LiTFSI/Li symmetrical cells with a current 2 2 density of (a) 0.05 mA/cm , (b) 0.075 mA/cm at 25 . Each cycle includes 1-h stripping and 1-h plating. The numbers around the curves are cycle number.

Lithium strip/plate test was completed on the Li/CPOSS-IL-LiTFSI/Li symmetrical cells at current densities of 0.05 and 0.075 mA/cm2 in order to examine the lithium electrodeposition stability (Figure 4). The Li/Li cells were charged and discharged sequentially for a period of one hour. For comparison, the cells with organic liquid electrolyte (1 M LiTFSI in EC/DEC/DMC, 1:1:1 by weight) were also tested. It can be observed that, under the current densities of 0.05 and 0.075 mA/cm2, an initial overpotential decrease is found in Li/CPOSS-IL-LiTFSI/Li, which could be explained by the improvement of the electrolyte/Li contact or the initial disruption of some part of passive layer.58 The overpotential evolution does not show any fluctuations or short circuit, indicative of the excellent capability of CPOSS-IL-LiTFSI to mediate electrochemical deposition and dissolution of lithium. Under higher current density condition (e.g., 0.075 mA/cm2), higher overpotential was observed. Although the voltage hysteresis (the sum of overvoltage of stripping and plating) increases with the cycle numbers for the Li/Li cells, the process is slow especially for relatively low current densities, e.g., 0.05 mA/cm2. The voltage hysteresis increases from 47 mV at the 50th cycle to 58 mV at the 250th cycle. On the other hand, the liquid electrolyte cells exhibit unstable and irregular voltage spikes during the cycling process which were likely related to uneven lithium stripping/plating or dendrite formation (Figure S13).

Battery Cell performance. Galvanostatic cycling measurements of all-solid-state Li/LFP cells based on the hybrid CPOSS-IL-LiTFSI electrolyte were performed at 25 . At C/10, a discharge capacity up to 133 mA·h/g has been obtained. While this value is slightly lower than the discharge capacity reported in our dendritic-like electrolyte (151 mA·h/g),38 this result is still among the highest values achieved so far for all-solid-state polymer lithium battery operating at room temperature.23, 59-62 The promising performance apparently results from the notable ionic conductivity achieved at ambient temperature and outstanding electrochemical stability of CPOSS-ILLiTFSI. Typical charge/discharge behavior is shown in Figure 5b. The charge plateau is clearly identified at around 3.5 V vs Li+/Li and the discharge plateau is seen at around 3.3 V vs Li+/Li, which successfully demonstrates a reversible cycling process. The evolution of discharge capacity and coulombic efficiency with cycle number are plotted in Figure 5a. The enhancement of the specific capacity for the first 13 cycles probably results from contact optimization of the electrode/electrolyte interface.63 The specific delivered capacities at the 1st, 50th, 100th cycle are 121.9, 123.2, and 112.1 mA·h/g, respectively. Stable cycling performance is also indicative of high ionic conductivity of the electrolyte and good compatibility between CPOSS-IL-LiTFSI and the electrodes. It is understood that the capacity fading comes from the degradation of electrode materials, the growth of sol-

5



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

Page 6 of 11

id electrolyte interphase (SEI) consuming electrolyte and lithium, the increase of interfacial resistance, and other irreversible process.48, 60, 64 Correspondingly, the coulombic efficiencies are 97.5%, 99.8%, and 99.8%, respectively. High coulombic efficiency is important for practical applications because it signifies good charge transfer reversibility in battery cells. The coulombic efficiency of the first cycle is lower than those of the subsequent cycles because of the formation of SEI. After the first cycle, the coulombic efficiency value rises to close to 100%, indicative of stable SEI formation between electrode and electrolyte.65, 66 As a demonstration, light-emitting diodes are successfully lighten up by this cell operating at ambient temperature as shown in Figure S14. It should be mentioned that, while intensive efforts have been focused on the development of polymer electrolytes and prototype all-solid-state polymer batteries, operation temperature is often elevated (e.g. 60 oC) in order to boost the ionic conductivity to ensure the operation of the polymer batteries.67-70 To further understand the all-solid-state Li/CPOSSIL-LiTFSI/LFP battery cycling process, the evolution of nyquist plot from EIS of the battery cells is plotted in Figure 5c. It can be seen that the bulk resistance (Rb) which is the intercept at the high frequency shows very slight changes and the interfacial resistance (Rint) of the Li/LFP battery gradually increases to 150 Ω·cm2 at the 50th cycle and 242 Ω·cm2 at the 100th cycle compared with 117 Ω·cm2 of the first cycle. This is probably one of the main reasons that lead to capacity fading because the lithium loss and thickening of SEI layer could hinder the ion movement between electrolyte and electrode.23, 48, 71, 72 Also, the interfacial resistance likely makes the major contribution to the overpotential seen in Figure 5b. Note that the overpotential reported herein is comparable to the literature results in which solid polymer electrolytes were utilized for lithium ion batteries at elevated temperature.73-75 Due to lack of liquids that could facilitate ion/charge transport across the electrode/electrolyte interface, considerable interfacial resistances are always found in all-solid-state batteries even though the ionic conductivity of the electrolyte is high. Thus, innovative approaches are urgently needed in order to address the challenging issue of interfacial resistance in all-solid-state batteries.

Figure 5. (a) Cycling stability test of Li/CPOSS-ILLiTFSI/LFP cell at 0.1 C, (b) Charge-discharge curves of Li/LFP cell assembled with CPOSS-IL-LiTFSI at 0.1 C, (c) Nyquist plot of Li/CPOSS-IL-LiTFSI/LFP cell after 1, 50, and 100 cycles at 0.1 C, measured at half discharge state. All tests were done at 25 .

Conclusion

In summary, we have developed a new class of organic/inorganic hybrid electrolyte based on ILgrafted dumbbell-shaped POSS for the all-solid-state lithium batteries operating at ambient temperature. The resulting electrolyte exhibits excellent thermal stability and a low Tg promoting Li+ conduction. High ionic conductivities, e.g. 1.2×10-4 S/cm at 20 , have been obtained in the hybrid electrolyte, which is among the highest values obtained in solid-state organic/polymer electrolytes measured at ambient temperature. In addition, the electrolyte exhibits great electrochemical stability (up to 4.6 vs Li+/Li) and excellent compatibility with lithium electrode during cycling. No short circuit has been observed after more than 500 hrs in the polarization tests of Li/Li symmetrical cell. The all-solid-state Li/LFP cells using CPOSS-IL-LiTFSI as electrolyte display decent

6


Page 7 of 11

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


charge/discharge performance when operating at room temperature. This is remarkable since most of the current solid-state polymer cells can only operate efficiently at elevated temperatures, e.g. ≥60 oC. Although much work still remains to be done in order to enhance overall cell performances such as battery performance at higher rates and large current densities, we believe CPOSS-IL offers a promising structure platform to develop next-generation electrolyte for all-solid-state lithium batteries operating at ambient temperature.

EXPERIMENTAL SECTION

Materials. Octavinyl polyhedral oligomeric silsesquioxane (OVPOSS) was purchased from Hybrid Plastics (>97%), dried o at 60 C overnight before use. Triflic acid (Aldrich, 98%). Sodium carbonate (ACS grade, EMD). Sodium sulfate (ACS grade, EMD). Mono-hydroxyl heptavinyl substituted POSS (VPOSS-OH) was synthesized according to the reported 76 method . 4,4’-methylene bis(phenyl isocyanate) (MDI, 98%, Aldrich). 1,1,3,3-tetramethyldisiloxane (97%, Aldrich). Hexaethylene glycol (hEG, 97%, Aldrich). Dibutyltin dilaurate (95%, Aldrich). Anhydrous dichloromethane and anhydrous toluene were purchased from Aldrich. Ethyl acetate (EtOAc, ACS grade, EMD). Karstedt catalyst solution in xylene (2%, Aldrich). 1-butyl imidazole (98%, Aldrich). lithium bis(trifluorome-thanesulfonyl) imide (LiTFSI, Aldrich). Synthesis of CPOSS. In a 100 mL flask with a magnetic stir bar, VPOSS-OH (0.48 g, 0.74 mmol) and MDI (92.5 mg, 0.37 mmol) dissolved in anhydrous toluene (40 mL) were added under the protection of nitrogen atmosphere at room temperature. The reaction mixture was heated up to 90 and 15 µL of dibutyltin dilaurate was added to the solution. The reaction was kept for 5 h and toluene was evaporated under reduced pressure. Yellow powder was obtained after 1 drying under vacuum at 60 . H NMR (300 MHz, 25 , CDCl3) δ: 7.12 (m, protons from the MDI aromatic ring), 3.90 (s, -C-CH2-C-), 4.30 (s, Si-CH2-CH2-O-), 0.86 (s, Si-CH2-CH213 O-), 1.29 and 1.59 (protons from catalyst) . C NMR (CDCl3) δ: 153.4 (-N-COO-CH2-), 136.6, 136.4, 136.2, 136.1, 136.0, 130.1, 130.0, 129.6, 129.4, 129.3, 121.7, 118.9, 61.4 (-CH2-O-CO-), 40.63 -1 (C-CH2-C), 14.1 (-Si-CH2-). FTIR (KBr, cm ): 1734 (ν, C=O), 1091 (ν, Si-O-Si). 1526 (δ, N-H bending).

Synthesis of 17-bromo-3,6,9,12,15-pentaoxaheptadecan-1-ol. Hexaethylene glycol (5 g, 17.71 mmol), triphenyl phosphine (2.33 g, 8.86 mmol) were dissolved in 25 mL dichloromethane in a 100 mL flask. The solution was purged with N2 for 40 min before CBr4 (2.935 g, 8.86 mmol) was added. The reaction mixture was stirred for 4 h at room temperature. The solvent was then evaporated under vacuum and the crude product was purified by column chromatography with chloroform/methanol eluent (95:5, v/v). The final 1 product was obtained as slight yellow oil. (81% yield) H NMR (CDCl3) δ: 3.16 (s,-OH), 3.46 (t, -CH2-Br), 3.58-3.68 (m,13 O-CH2-), 3.79 (t, -CH2-CH2-Br); C NMR (CDCl3) δ: 30.1, 61.6, 70.2-70.7 (br), 73.0 (-CH2-CH2-Br).

Synthesis of vinyl tris17-bromo-3,6,9,12,15-pentaoxaheptadecan-1-ol silane (1). 17-bromo-3,6,9,12,15pentaoxaheptadecan-1-ol (2.8 g, 0.008 mol) and triethyla-

mine (1.6 g, 0.016 mol) was dissolved in 40 mL toluene in a 100 mL flask with magnetic stirrer. In an inert N2 atmosphere, trichlorovinylsilane (0.437 g, 2.67 mmol) was added at room temperature. The reaction lasted for 3 h at ambient temperature before 50 mL of EtOAc was added to dilute the reaction mixture. After washed with water and dried over Na2SO4. The organic layer was concentrated and dried under 1 vacuo overnight to give the product. (84 % yield) H NMR (CDCl3) δ: 3.43 (t, -CH2-Br), 3.58-3.68 (m, -O-CH2-), 3.79 (-OCH2-CH2-Br), 3.89 (t, -Si-O-CH2-), 5.9-6.1 (m, CH2=CH-Si-), 13 C NMR (CDCl3) δ: 30.1, 62.4 (-Si-O-CH2, 70.8-71.9 (signal overlap), 72.7 (-CH2-CH2-Br), 137.4 (CH2=CH-Si-). Synthesis of Compound 2. To a solution of compound 1 (1 g, 0.92 mmol) dissolved in anhydrous toluene (10 mL) in a flame dried 50 mL flask equipped with a magnetic stir bar, 0.616 g (4.6 mmol) of 1,1,3,3-tetramethyldisiloxane was added at room temperature. Karstedt catalyst solution in xylene (15 µL) was then added. The solution was stirred for 2 days at 60 under nitrogen protection. The solvent and unreacted 1,1,3,3-tetramethyldisiloxane was then removed under re1 duced pressure to give light yellow oil. H NMR (CDCl3) δ: 3.46 (t, -CH2-Br), 3.58-3.68 (m,-O-CH2-), 3.80 (t, -O-CH213 CH2-Br); 0.08 (s, -Si-CH3). C NMR (CDCl3) δ: 72.5 (-O-CH2CH2-Br), 70.2-70.6 (signal overlap), 61.6 (-Si-O-CH2-CH2-), 30.4 (-O-CH2-CH2- Br), 0.2, -0.7 (-OSi(CH3)2-H), 0.65 (Si(CH3)2-O-). Synthesis of CPOSS-PEO. To a solution of compound 2 (1 g, 0.8 mmol) dissolved in anhydrous toluene (10 mL) in a 50 mL flask, CPOSS (0.09g, 0.057 mmol) was added at room temperature. The solution was purged with N2 for 40 min before Karstedt catalyst was added. The reaction proceeded o for 2 days at 60 C and the solvent was evaporated under 1 reduced pressure to give yellow material. H NMR (CDCl3) δ: 3.46 (t, -CH2-Br), 3.58-3.68 (m,-O-CH2-), 3.80 (t, -CH2-CH2Br); 0.08 (s, -Si-CH3). Synthesis of CPOSS-IL. CPOSS-PEO (0.8 g, 0.042 mmol) was dissolved in 15 mL anhydrous acetonitrile in a 50 mL flask followed by adding 1-butyl imidazole (223 mg, 1.8 mmol) to the solution. The reaction mixture was stirred in 50 o C for 12 h and LiTFSI was added. After removal of acetonitrile, the product was redissolved in dichloromethane and the solution was filtrated and concentrated to give light 1 brown material. H NMR (CDCl3) δ: 0.08 (s, -Si-CH3); 0.99 (t, -CH2-CH3); 1.38 (m, -CH2-CH2-CH3); 1.88 (m, -CH2-CH2CH3); 3.58-3.69 (m, -O-CH2-); 4.29 (t, O-CH2-CH2-N-); 4.65 (t, -N-CH2-CH2-); 7.78 (s, -N- CH=CH-N-); 10.26 (s, -N=CH-1 N-). FTIR (KBr, cm ): characteristic bands for TFSI :1352, 1195, 1135, 1056. 1565 (ν, C=N) (Figure S7).

Characterization. 1H and 13C NMR measurements were carried out on a Bruker AM-300 nuclear magnetic resonance spectrometer. Fourier transform infrared (FTIR) spectra were obtained using Bruker Vertex 70 spectrometer. Differential scanning calorimetry (DSC) was performed on TA Q100 DSC instrument at a heating and cooling rate of 10 °C/min from -85 to 30 °C. Thermogravimetric analysis (TGA) was performed on TA Instrument model Q50 at a heating rate of 10 °C/min under N2 from 25- 650 °C. X-ray diffraction (XRD) was performed on a Rigaku DMAX-Rapid Microdiffractometer using CuKα radiation. The software routines were used to evaluate

7



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

the scattering intensity as a function of the diffraction o o angle, 2θ, in the range of 4 -30 . The ionic conductivity (σ) of the polymer electrolyte samples was analyzed by electrochemical impedance spectroscopy (EIS). Samples were sandwiched between two stainless steel (SS) blocking electrodes separated by a teflon oring spacer (125 µm thick). Criterion Temperature Bench-top Chamber was used to simulate environmental temperature. The ionic conductivity was calculated based on σ=L/RbS, σ is the ionic conductivity (S/cm), L is the polymer electrolyte thickness, Rb is the bulk resistance and S is the contactinng 2 area (0.785 cm ). Cell impedance values were obtained on Solatron 1260 impedance/gain phase analyzer over the frequency range from 1 MHz to 100 mHz, 20 mV AC voltage. + + The Li ion transference number (tLi ) was measured by combined DC polarization and AC impedance method (1 + MHz to 100 mHz, 20 mV DC potential). tLi was calculated 56 according to method reported by Bruce and Vincent . A combination of AC impedance and DC polarization meas+ urements has been used for the determination of tLi of pol77-79 ymer-IL-Li salt system. A very small dc pulse was applied to the Li/Li symmetrical cell and the initial current and steady state current was measured. Also, to consider the resistance of the passivation layers before and after the polarization, the same symmetrical cell was subjected to AC im+ pedance test. The equation can be written as tLi =Iss(ΔVI0R0)/I0(ΔV-IssRss). I0 and Iss are initial and steady state current. R0 and Rss are initial and steady state resistance. ΔV is the DC pulse voltage to polarize the cell. A DC voltage of 30 mV was chosen to polarize the cell. Cyclic voltammetry and linear sweep voltammetry (LSV) were performed at room temperature on PAR Potentiaostat/Galvanostat Model 263A with Li/polymer electrolyte/stainles steel 2032 coin cells (stainless steel working electrode and lithium foil counter and reference electrode). Scan rate: 1 mV/s. For the electrolyte preparation and coin cells assembly, CPOSS-IL was dissolved in anhydrous THF (11% w/v) first. LiTFSI was then weighted and added to the above solution (2 mol of IL tethered PEO chains: 1 mol of LiTFSI). The solution was stirred overnight to let the solvent fully dissolve the salt. LFP (Sud-Chemie) cathode was prepared by spreading slurries containing 80 wt% of LFP, 10 wt% of super P, 10 wt% of CPOSS-IL in 1-methyl2-pyrrolidone (NMP) onto 15 μm aluminum foil. The 2 areal density was ca. 2.8 mg/cm . The dried cathode 2 sheets were punched into 1 cm diameter (0.785 cm ) o disks, vacuum dried at 80 C completely, weighted, and transferred into glove box for coin cell assembly. Lithium foils (MTI, 250 µm thick) were used as the anode. The prepared polymer solution was dropped on the anode and dried under vacuum to remove the solvent. The prototype buttons cell CR2032 was assembled with ring shaped 125 μm thick Teflon ring as spacer. The cell performance tests were completed on a Neware CT-3008 battery tester at constant current and the cut-off voltage + was between 2.5 V to 3.9 V vs Li /Li.

ASSOCIATED CONTENT

Supporting Information. NMR, FTIR, DSC, TGA, XRD, impedance, chronoamperometry, LED pictures. This material

is available free http://pubs.acs.org.

Page 8 of 11 of

charge

via

the

Internet

at

AUTHOR INFORMATION Corresponding Author * E-mail: [email protected]

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENT This work was supported by US National Science Foundation.

REFERENCES 1. Goodenough, J. B.; Park, K.-S. The Li-ion rechargeable battery: a perspective. J. Am. Chem. Soc. 2013, 135, 1167-1176. 2. Manthiram, A.; Yu, X.; Wang, S. Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2017, 2, 16103. 3. Scrosati, B.; Garche, J. Lithium batteries: Status, prospects and future. J. Power Sources 2010, 195, 2419-2430. 4. Lu, Y.; Tu, Z.; Archer, L. A. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater. 2014, 13, 961-969. 5. Zhu, Z.; Hong, M.; Guo, D.; Shi, J.; Tao, Z.; Chen, J. All-solidstate lithium organic battery with composite polymer electrolyte and Pillar [5] quinone cathode. J. Am. Chem. Soc. 2014, 136, 16461-16464. 6. Kalhoff, J.; Eshetu, G. G.; Bresser, D.; Passerini, S., Safer electrolytes for lithium-ion batteries: State of the art and perspectives. ChemSusChem 2015, 8, 2154-2175. 7. Xu, K. Electrolytes and interphases in Li-ion batteries and beyond. Chem. Rev. 2014, 114, 11503-11618. 8. Bouchet, R.; Maria, S.; Meziane, R.; Aboulaich, A.; Lienafa, L.; Bonnet, J.-P.; Phan, T. N.; Bertin, D.; Gigmes, D.; Devaux, D. Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries. Nat. Mater. 2013, 12, 452457. 9. Meyer, W. H. Polymer electrolytes for lithium-ion batteries. Adv. Mater. 1998, 10, 439-448. 10. Wong, D. H.; 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. Natl. Acad. Sci. U. S. A. 2014, 111, 3327-3331. 11. Oh, H.; Xu, K.; Yoo, H. D.; Kim, D. S.; Chanthad, C.; Yang, G.; Jin, J.; Ayhan, I. A.; Oh, S. M.; Wang, Q. Poly (arylene ether)based single-ion conductors for lithium-ion batteries. Chem. Mater. 2015, 28, 188-196. 12. Wright, P. V. Electrical conductivity in ionic complexes of poly (ethylene oxide). Polym. Int. 1975, 7, 319-327. 13. Fenton, D.; Parker, J.; Wright, P. Complexes of alkali metal ions with poly (ethylene oxide). polymer 1973, 14, 589. 14. Armand, M.; Chabagno, J. In Duclot, Extended Abstract, Second International Conference on Solid Electrolytes, St. Andrews, Scotland, 1978. 15. Li, Q.; Chen, J.; Fan, L.; Kong, X.; Lu, Y. Progress in electrolytes for rechargeable Li-based batteries and beyond. Green Energy & Environment 2016, 1, 18-42. 16. Wang, Q.; Song, W.-L.; Fan, L.-Z.; Song, Y. Facile fabrication of polyacrylonitrile/alumina composite membranes based on triethylene glycol diacetate-2-propenoic acid butyl ester gel

8


Page 9 of 11

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


polymer electrolytes for high-voltage lithium-ion batteries. J. Membr. Sci. 2015, 486, 21-28. 17. Kim, G.-T.; Appetecchi, G. B.; Alessandrini, F.; Passerini, S. Solvent-free, PYR 1A TFSI ionic liquid-based ternary polymer electrolyte systems: I. Electrochemical characterization. J. Power Sources 2007, 171, 861-869. 18. Porcarelli, L.; Gerbaldi, C.; Bella, F.; Nair, J. R. Super soft allethylene oxide polymer electrolyte for safe all-solid lithium batteries. Sci. Rep. 2016, 6, 19892. 19. Singh, M.; Odusanya, O.; Wilmes, G. M.; Eitouni, H. B.; Gomez, E. D.; Patel, A. J.; Chen, V. L.; Park, M. J.; Fragouli, P.; Iatrou, H. Effect of molecular weight on the mechanical and electrical properties of block copolymer electrolytes. Macromolecules 2007, 40, 4578-4585. 20. Rojas, A. A.; Inceoglu, S.; Mackay, N. G.; Thelen, J. L.; Devaux, D.; Stone, G. M.; Balsara, N. P. Effect of lithium-ion concentration on morphology and ion transport in single-ionconducting block copolymer electrolytes. Macromolecules 2015, 48, 6589-6595. 21. Croce, F.; Appetecchi, G.; Persi, L.; Scrosati, B. Nanocomposite polymer electrolytes for lithium batteries. Nature 1998, 394, 456-458. 22. Zhou, W.; Wang, S.; Li, Y.; Xin, S.; Manthiram, A.; Goodenough, J. B. Plating a dendrite-free lithium anode with a polymer/ceramic/polymer sandwich electrolyte. J. Am. Chem. Soc. 2016, 138, 9385-9388. 23. Choi, K. H.; Cho, S. J.; Kim, S. H.; Kwon, Y. H.; Kim, J. Y.; Lee, S. Y. Thin, deformable, and safety-reinforced plastic crystal polymer electrolytes for high-performance flexible lithium-ion batteries. Adv. Funct. Mater. 2014, 24, 44-52. 24. MacFarlane, D. R.; Tachikawa, N.; Forsyth, M.; Pringle, J. M.; Howlett, P. C.; Elliott, G. D.; Davis, J. H.; Watanabe, M.; Simon, P.; Angell, C. A. Energy applications of ionic liquids. Energy Environ. Sci. 2014, 7, 232-250. 25. Osada, I.; de Vries, H.; Scrosati, B.; Passerini, S. Ionic-iiquidbased polymer electrolytes for battery applications. Angew. Chem. Int. Ed. 2016, 55, 500-513. 26. Armand, M.; Endres, F.; MacFarlane, D. R.; Ohno, H.; Scrosati, B. Ionic-liquid materials for the electrochemical challenges of the future. Nat. Mater. 2009, 8, 621-629. 27. Green, M. D.; Long, T. E. Designing imidazole-based ionic liquids and ionic liquid monomers for emerging technologies. Polym. Rev. 2009, 49, 291-314. 28. Green, M. D.; Choi, J.-H.; Winey, K. I.; Long, T. E. Synthesis of imidazolium-containing ABA triblock copolymers: role of charge placement, charge density, and ionic liquid incorporation. Macromolecules 2012, 45, 4749-4757. 29. Mecerreyes, D. Polymeric ionic liquids: Broadening the properties and applications of polyelectrolytes. Prog. Polym. Sci. 2011, 36, 1629-1648. 30. Weber, R. L.; Ye, Y.; Schmitt, A. L.; Banik, S. M.; Elabd, Y. A.; Mahanthappa, M. K. Effect of nanoscale morphology on the conductivity of polymerized ionic liquid block copolymers. Macromolecules 2011, 44, 5727-5735. 31. Zhang, H.; Liu, C.; Zheng, L.; Feng, W.; Zhou, Z.; Nie, J. Solid polymer electrolyte comprised of lithium salt/ether functionalized ammonium-based polymeric ionic liquid with bis (fluorosulfonyl) imide. Electrochim. Acta 2015, 159, 93-101. 32. Sato, T.; Morinaga, T.; Marukane, S.; Narutomi, T.; Igarashi, T.; Kawano, Y.; Ohno, K.; Fukuda, T.; Tsujii, Y. Novel solid-state polymer electrolyte of colloidal crystal decorated with ionicliquid polymer brush. Adv. Mater. 2011, 23, 4868-4872. 33. Matsumi, N.; Sugai, K.; Miyake, M.; Ohno, H. Polymerized ionic liquids via hydroboration polymerization as single ion

conductive polymer electrolytes. Macromolecules 2006, 39, 6924-6927. 34. Kuo, S.-W.; Chang, F.-C., POSS related polymer nanocomposites. Prog. Polym. Sci. 2011, 36, 1649-1696. 35. Kim, S.-K.; Kim, D.-G.; Lee, A.; Sohn, H.-S.; Wie, J. J.; Nguyen, N. A.; Mackay, M. E.; Lee, J.-C. Organic/inorganic hybrid block copolymer electrolytes with nanoscale ion-conducting channels for lithium ion batteries. Macromolecules 2012, 45, 9347-9356. 36. Maitra, P.; Wunder, S. L. POSS based electrolytes for rechargeable lithium batteries. Electrochem. Solid-State Lett. 2004, 7, A88-A92. 37. Pan, Q.; Smith, D. M.; Qi, H.; Wang, S.; Li, C. Y. Hybrid electrolytes with controlled network structures for lithium metal batteries. Adv. Mater. 2015, 27, 5995-6001. 38. Yang, G.; Chanthad, C.; Oh, H.; Ayhan, I. A.; Wang, Q. Organic–inorganic hybrid electrolytes from ionic liquidfunctionalized octasilsesquioxane for lithium metal batteries. J. Mater. Chem. A 2017, 5, 18012-18019. 39. Kuo, P.-L.; Tsao, C.-H.; Hsu, C.-H.; Chen, S.-T.; Hsu, H.-M. A new strategy for preparing oligomeric ionic liquid gel polymer electrolytes for high-performance and nonflammable lithium ion batteries. J. Membr. Sci. 2016, 499, 462-469. 40. Li, M.; Yang, B.; Wang, L.; Zhang, Y.; Zhang, Z.; Fang, S.; Zhang, Z. New polymerized ionic liquid (PIL) gel electrolyte membranes based on tetraalkylammonium cations for lithium ion batteries. J. Membr. Sci. 2013, 447, 222-227. 41. Rohan, R.; Sun, Y.; Cai, W.; Pareek, K.; Zhang, Y.; Xu, G.; Cheng, H. Functionalized meso/macro-porous single ion polymeric electrolyte for applications in lithium ion batteries. J. Mater. Chem. A 2014, 2, 2960-2967. 42. Yang, X.; Zhong, Z.; Huang, Y. The effect of PEG molecular weights on the thermal stability and dissolution behaviors of griseofulvin-PEG crystalline inclusion complexes. Int. J. Pharm 2016, 508, 51-60. 43. Beyler, C. L.; Hirschler, M. M. Thermal decomposition of polymers. SFPE handbook of fire protection engineering 2002, 2, 111-131. 44. Markovic, E.; Ginic-Markovic, M.; Clarke, S.; Matisons, J.; Hussain, M.; Simon, G. P. Poly (ethylene glycol)octafunctionalized polyhedral oligomeric silsesquioxane: synthesis and thermal analysis. Macromolecules 2007, 40, 26942701. 45. Lascaud, S.; Perrier, M.; Vallee, A.; Besner, S.; Prud'Homme, J.; Armand, M. Phase diagrams and conductivity behavior of poly (ethylene oxide)-molten salt rubbery electrolytes. Macromolecules 1994, 27, 7469-7477. 46. Khurana, R.; Schaefer, J. L.; Archer, L. A.; Coates, G. W. Suppression of lithium dendrite growth using cross-linked polyethylene/poly (ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries. J. Am. Chem. Soc. 2014, 136, 7395-7402. 47. Zeng, X.-X.; Yin, Y.-X.; Li, N.-W.; Du, W.-C.; Guo, Y.-G.; Wan, L.-J. Reshaping lithium plating/stripping behavior via bifunctional polymer electrolyte for room-temperature solid Li metal batteries. J. Am. Chem. Soc. 2016, 138, 15825-15828. 48. Kaneko, F.; Wada, S.; Nakayama, M.; Wakihara, M.; Koki, J.; Kuroki, S. Capacity fading mechanism in all solid-state lithium polymer secondary batteries using PEG-borate/aluminate ester as plasticizer for polymer electrolytes. Adv. Funct. Mater. 2009, 19, 918-925. 49. Zhang, P.; Li, M.; Yang, B.; Fang, Y.; Jiang, X.; Veith, G. M.; Sun, X. G.; Dai, S. Polymerized ionic networks with high charge density: Quasi-solid electrolytes in lithium-metal batteries. Adv. Mater. 2015, 27, 8088-8094.

9



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

50. Lu, Y.; Moganty, S. S.; Schaefer, J. L.; Archer, L. A. Ionic liquid-nanoparticle hybrid electrolytes. J. Mater. Chem. 2012, 22, 4066-4072. 51. Li, M.; Zhu, W.; Zhang, P.; Chao, Y.; He, Q.; Yang, B.; Li, H.; Borisevich, A.; Dai, S. Graphene-analogues boron nitride nanosheets confining ionic liquids: A high-performance quasiliquid solid electrolyte. Small 2016, 12, 3535-3542. 52. Abraham, K.; Jiang, Z.; Carroll, B. Highly conductive PEO-like polymer electrolytes. Chem. Mater. 1997, 9, 1978-1988. 53. Chinnam, P. R.; Zhang, H.; Wunder, S. L. Blends of pegylated polyoctahedralsilsesquioxanes (POSS-PEG) and methyl cellulose as solid polymer electrolytes for lithium batteries. Electrochim. Acta 2015, 170, 191-201. 54. Balo, L.; Gupta, H.; Singh, V. K.; Singh, R. K. Flexible gel polymer electrolyte based on ionic liquid EMIMTFSI for rechargeable battery application. Electrochim. Acta 2017, 230, 123-131. 55. Xu, K. Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chem. Rev. 2004, 104, 4303-4418. 56. Evans, J.; Vincent, C. A.; Bruce, P. G. Electrochemical measurement of transference numbers in polymer electrolytes. Polymer 1987, 28, 2324-2328. 57. Agostini, M.; Rizzi, L. G.; Cesareo, G.; Russo, V.; Hassoun, J. Characteristics of a graphene nanoplatelet anode in advanced lithium-ion batteries using ionic liquid added by a carbonate electrolyte. Adv. Mater. Interfaces 2015, 2, 1500085. 58. Kim, G.-T.; Appetecchi, G. B.; Carewska, M.; Joost, M.; Balducci, A.; Winter, M.; Passerini, S. UV cross-linked, lithiumconducting ternary polymer electrolytes containing ionic liquids. J. Power Sources 2010, 195, 6130-6137. 59. Rohan, R.; Pareek, K.; Cai, W.; Zhang, Y.; Xu, G.; Chen, Z.; Gao, Z.; Dan, Z.; Cheng, H. Melamine–terephthalaldehyde– lithium complex: a porous organic network based single ion electrolyte for lithium ion batteries. J. Mater. Chem. A 2015, 3, 5132-5139. 60. Hu, Q.; Osswald, S.; Daniel, R.; Zhu, Y.; Wesel, S.; Ortiz, L.; Sadoway, D. R. Graft copolymer-based lithium-ion battery for high-temperature operation. J. Power Sources 2011, 196, 56045610. 61. Zhang, J.; Zhao, J.; Yue, L.; Wang, Q.; Chai, J.; Liu, Z.; Zhou, X.; Li, H.; Guo, Y.; Cui, G. Safety-reinforced poly(propylene carbonate)-based all-solid-state polymer electrolyte for ambienttemperature solid polymer lithium batteries. Adv. Energy Mater. 2015, 5, 1501082. 62. Zhou, D.; He, Y. B.; Liu, R.; Liu, M.; Du, H.; Li, B.; Cai, Q.; Yang, Q. H.; Kang, F. In situ synthesis of a hierarchical all-solidstate electrolyte based on nitrile materials for high-performance lithium-ion batteries. Adv. Energy Mater. 2015, 5, 1500353. 63. Shin, J.-H.; Henderson, W. A.; Passerini, S. PEO-based polymer electrolytes with ionic liquids and their use in lithium metal-polymer electrolyte batteries. J. Electrochem. Soc. 2005, 152, A978-A983. 64. Yun, Y. S.; Kim, J. H.; Lee, S.-Y.; Shim, E.-G.; Kim, D.-W. Cycling performance and thermal stability of lithium polymer cells assembled with ionic liquid-containing gel polymer electrolytes. J. Power Sources 2011, 196, 6750-6755. 65. Zhang, H.; Han, H.; Cheng, X.; Zheng, L.; Cheng, P.; Feng, W.; Nie, J.; Armand, M.; Huang, X.; Zhou, Z. Lithium salt with a super-delocalized perfluorinated sulfonimide anion as conducting salt for lithium-ion cells: Physicochemical and electrochemical properties. J. Power Sources 2015, 296, 142-149. 66. Stepniak, I. Compatibility of poly(bisAEA4)-LiTFSI– MPPipTFSI ionic liquid gel polymer electrolyte with Li4Ti5O12 lithium ion battery anode. J. Power Sources 2014, 247, 112-116.

Page 10 of 11

67. He, D.; Kim, D. W.; Park, J. S.; Cho, S. Y.; Kang, Y. Electrochemical properties of semi-interpenetrating polymer network solid polymer electrolytes based on multi-armed oligo (ethyleneoxy) phosphate. J. Power Sources 2013, 244, 170-176. 68. Daigle, J.-C.; Vijh, A.; Hovington, P.; Gagnon, C.; HamelPâquet, J.; Verreault, S.; Turcotte, N.; Clément, D.; Guerfi, A.; Zaghib, K. Lithium battery with solid polymer electrolyte based on comb-like copolymers. J. Power Sources 2015, 279, 372-383. 69. Rolland, J.; Brassinne, J.; Bourgeois, J.-P.; Poggi, E.; Vlad, A.; Gohy, J.-F. Chemically anchored liquid-PEO based block copolymer electrolytes for solid-state lithium-ion batteries. J. Mater. Chem. A 2014, 2, 11839-11846. 70. Daigle, J.-C.; Asakawa, Y.; Vijh, A.; Hovington, P.; Armand, M.; Zaghib, K. Exceptionally stable polymer electrolyte for a lithium battery based on cross-linking by a residue-free process. J. Power Sources 2016, 332, 213-221. 71. Leng, Y.; Ge, S.; Marple, D.; Yang, X.-G.; Bauer, C.; Lamp, P.; Wang, C.-Y. Electrochemical cycle-life characterization of high energy lithium-ion cells with thick Li(Ni0.6Mn0.2Co0.2)O2 and graphite electrodes. J. Electrochem. Soc. 2017, 164, A1037-A1049. 72. Wu, F.; Chen, N.; Chen, R.; Zhu, Q.; Qian, J.; Li, L. “Liquid-insolid” and “solid-in-liquid” electrolytes with high rate capacity and long cycling life for lithium-ion batteries. Chem. Mater. 2016, 28, 848-856. 73. Hu, J.; Wang, W.; Peng, H.; Guo, M.; Feng, Y.; Xue, Z.; Ye, Y.; Xie, X., Flexible organic–inorganic hybrid solid electrolytes formed via thiol–acrylate photopolymerization. Macromolecules 2017, 50, 1970-1980. 74. Mindemark, J.; Sun, B.; Törmä, E.; Brandell, D. Highperformance solid polymer electrolytes for lithium batteries operational at ambient temperature. J. Power Sources 2015, 298, 166-170. 75. Tan, R.; Gao, R.; Zhao, Y.; Zhang, M.; Xu, J.; Yang, J.; Pan, F. Novel organic–inorganic hybrid electrolyte to enable LiFePO4 quasi-solid-state Li-ion batteries performed highly around room temperature. ACS Appl. Mater. Interfaces 2016, 8, 31273-31280. 76. Feher, F.; Wyndham, K.; Baldwin, R.; Ziller, J.; Lichtenhan, J. Methods for effecting monofunctionalization of (CH2=CH)8Si8O 12. Chem. Commun. 1999, 1289-1290. 77. Li, Z.; Xia, Q.; Liu, L.; Lei, G.; Xiao, Q.; Gao, D.; Zhou, X. Effect of zwitterionic salt on the electrochemical properties of a solid polymer electrolyte with high temperature stability for lithium ion batteries. Electrochim. Acta 2010, 56, 804-809. 78. Kimura, K.; Matsumoto, H.; Hassoun, J.; Panero, S.; Scrosati, B.; Tominaga, Y. A quaternary poly(ethylene carbonate)-lithium bis(trifluoromethanesulfonyl) imide-ionic liquid-silica fiber composite polymer electrolyte for lithium batteries. Electrochim. Acta 2015, 175, 134-140. 79. Zhu, C.; Cheng, H.; Yang, Y. Electrochemical characterization of two types of PEO-based polymer electrolytes with roomtemperature ionic liquids. J. Electrochem. Soc. 2008, 155, A569A575.

10


Page 11 of 11

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


Table of Content 331x126mm (150 x 150 DPI)


Dumbbell-Shaped Octasilsesquioxanes ... - ACS Publications

Recommend Documents