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High-Charge-Density Polymerized Ionic Networks (PINs) Boosting High Ionic Conductivity as Quasi-Solid Electrolytes for High-Voltage Batteries Xiaolu Tian, Yikun Yi, Pu Yang, Pei Liu, Long Qu, Mingtao Li, Yong-Sheng Hu, and Bolun Yang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b19743 • Publication Date (Web): 04 Jan 2019 Downloaded from http://pubs.acs.org on January 8, 2019

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ACS Applied Materials & Interfaces

High-Charge-Density Polymerized Ionic Networks (PINs) Boosting High Ionic Conductivity as QuasiSolid Electrolytes for High-Voltage Batteries Xiaolu Tian,† Yikun Yi,† Pu Yang,† Pei Liu,† Long Qu,† Mingtao Li,*† Yong-sheng Hu,*‡ and Bolun Yang† †School

of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an 710049,

China. ‡Laboratory

for Renewable Energy, Beijing Key Laboratory for New Energy, Materials and

Devices, Institute of Physics, Chinese Academy of Sciences, School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100190, China. *E-mail: [email protected] *Email: [email protected] Keywords： Polymer electrolytes, solid electrolytes, polymerized ionic networks, lithium metal batteries, ionic conductivity

Abstract

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Solid-state electrolytes are actively sought for their potential application in energy storage devices, especially lithium metal rechargeable batteries. However, one of the key challenges toward the solid-state electrolytes is their lower ionic conductivity compared with the liquid electrolytes (10-2 S cm-1 at room temperature), where a large gap still exists. Therefore, the pursuit of high ionic conductivity equal to the liquid electrolyte remains the main objective for the design of the solid-state electrolytes. Here, we show a series of high-charge-density polymerized ionic networks (PINs) as solid-state electrolytes that take inspiration from poly(ionic liquid)s. The obtained quasi-solid electrolyte slice displays astonishingly high ionic conductivity, 5.89×10-3 S cm-1 at 25 oC (the highest conductivity among the state-of-art polymer gel electrolytes and polymer solid electrolytes) and ultra-high decomposition potential, more than 5.2 V vs. Li/Li+, which are attributed to the continuous ion-transport channel formed by ultra-high ion density and enhanced chemical stability endowed by highly cross-linked networks. The Li/LiFePO4 and Li/LiCoO2 batteries (3.0~4.4V) assembled with the solid electrolytes show high stable capacity of around 155 mAh g-1 and 130 mAh g-1. In principle, our work breaks a new path for the design and fabrication of the solid-state electrolytes in various energy conversion devices. 1. Introduction Solid-state lithium-metal batteries are considered to be one of the most promising rechargeable batteries due to their better safety and higher energy density compared with traditional lithium-ion batteries.1 In recent decades, three classes of solid electrolytes including inorganic sold electrolytes (ISEs), solid polymer electrolytes (SPEs), and composite solid electrolytes (CSEs), have attracted immense attention as a potential candidate to improve energy density and safety of lithium-ion batteries.2,3 Practical application of traditional ISEs with high 2 ACS Paragon Plus Environment

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ionic conductivity is hindered by their fragility, unprocessability, and large interfacial resistance.4-9 SPEs, despite of better flexibility, possess a low conductivity at room temperature.10-16 By adding highly conductive inorganic materials into polymeric matrix, the prepared CSEs take advantage of both ISEs and SPEs, and can be processed into conductive electrolytes with well-defined geometric shapes.17-27 Recent studies have synthesized PVDFbased CPEs membranes using Li6.75La3Zr1.75Ta0.25O12 as fillers, with an ionic conductivity of 5×10-4 S cm-1 under room temperature.28 However, CPEs still remains to be increased in the aspect of conductivity compared with the state-of-the-art liquid electrolyte (10-2 S cm-1 at room temperature). Polymerized ionic liquids (PILs), a new class of functional materials, are synthesized by radical polymerization of ionic liquid (IL) monomers, and hence the IL species are combined in each repetitive unit of the polymer backbone.29 PILs have been widely used in the fields of electrochemical devices, carbon-based materials, gas separation, and energy generation as SPEs owing to their unique merits (processibility, high energy density, and high ionic conductivity).3034

It is investigated that the ionic conductivity of PILs is affected by several factors comprising

glass transition temperature, molecular weight, and anion types.35 One way to enhance the ionic conductivity of PILs is to introduce various side chain groups, ethylene oxide groups for instance, to decrease the glass transition temperature.36,37 Another way to increase ionic conductivity of a PIL is through taking the place of BF4- anion with bis(trifluoromethanesulfonyl)imide anion (TFSI-).38 Combining the two strategies, researchers dangled TFSI anions onto the backbones with polyethylene oxide segments, by which the resulted PILs had appropriate conductivity of 10-5 S cm-1 at 30 oC and 10-3 S cm-1 at 90 oC.39,40 In addition, PIL gel membranes have been prepared by ionic liquid incorporated into PIL matrices to level up conductivity performance to 3 ACS Paragon Plus Environment


10-4 S cm-1 at room temperature and simultaneously to alleviate the interfacial resistance between electrode and electrolyte.41 Nevertheless, there is still a wide gap between those new classes of PIL materials and liquid electrolytes. Recent research shows that increased charge density in PILs is favorable to the transport of lithium ions. For example, the ionic conductivity of polycationic PILs reaches over 4×10−5 S cm−1 at room temperature, which outperforms the conductivity of hybrid electrolytes based on monocationic PILs (10-5 S cm-1 at room temperature).42 Additionally, ion-conducting networks derived from poly(1,2,3-triazole)s with increased ionic density exhibit an anhydrous ionic conductivity of over 10−8 S cm−1 at 30 oC.43 Particularly, our previous studies have found that a series of PILs possessing higher ionic content observably enhances the ionic conductivity owing to the construction of close interlaced channels for Li ions that facilitates the transport of mobile ions.44 Such high-charge-density composite electrolytes with ionic conductivity of up to 10−3 S cm−1 at room temperature, however, failed to exhibit stable cycle performance due to their immature assembly processes. Further regrettably, none of these electrolytes was tested in Li metal batteries working under high voltage range despite of their high decomposition voltages (up to 5 V). Since such compound systems are infusive electrolytes for lithium batteries, a new series of PILs electrolytes with high charge density, in pursuit of superior battery performance, are designed to cope with faulty workmanship and incompatibility between electrodes and solid electrolytes. In this work, we continued the previous synthesize strategies that take inspiration from poly(ionic liquid)s: (1) the catalyst-free polyaddition and the simultaneous alkylation with a difunctional cross linking agents, and (2) free radical polymerization of the highly charged monomers and the simultaneous cross-linking reaction. A new series of tunable high-charge4 ACS Paragon Plus Environment

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density polymerized ionic networks (PINs) are fabricated as solid-state electrolytes, up to six ion pairs in each repeating unit. The solid-state electrolyte slice is obtained by the compression of the PINs absorbing certain amounts of ionic liquid under a 15 MPa pressure. The quasi-solid-state electrolytes display excellent ionic conductivity (5.89×10-3 S cm-1 at 25

oC),

high

electrochemical stability (decompose over 5.3 V), and stabilized interfacial compatibility with lithium metal. A Li/LiFePO4 battery comprising PINs electrolyte delivers discharge capacity of around 146 mAh g-1 at 25 oC and maintains a stable capacity after 200 cycles. Moreover, a Li/LiCoO2 battery working under high voltage range (3.0~4.4 V) for 100 cycles exhibits a stable discharge capacity of up to 133 mAh g-1, which precisely verifies the electrochemical stability of PINs electrolytes.



Scheme 1. a,b) The synthesis procedure to obtain PIN-1,2 by TMEDA and Multi-bromomethylbenzene. c,d) The synthesis procedure of PIN-3,4 by 4-Vinylpyridine and Multi-bromomethylbenzene


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2. Results and Discussion 2.1 Synthesis and Structure Characterization. Scheme 1 illustrates the synthesis pathways of PIN samples. PIN-1 samples with a cross-linking structure were prepared through a nucleophilic

substitution

of

1,3,5-Tris(bromomethyl)benzene

and

N,N,N',N'-

Tetramethylethylenediamine (TMEDA) without any catalysts, followed by exchanging bromide ions with the TFSI anions into the substrate.45-47 The reactants were mixed to form a transparent solution, and a white precipitate generated in only a few minutes at room temperature under argon atmosphere. The subtlety of this reaction is that the polyaddition and the cross linking are realized simultaneously by a quaternization reaction. The as-solution was immediately heated to 60 oC and 80 oC for further conversion. By another strategy, PIN-4-Br was synthesized via polymerization of 1,3,5-Tris(bromomethyl)benzene monomers densely substituted by 4Vinylpyridine. The polymerization procedure was conducted by hydrothermal methods at 120 oC using azobisisobutyronitrile (AIBN) as initiator, resulting in highly cross-linking matrix.48 Ion exchange from Br- to TFSI anions were carried out for PIN-Br products to get boosted electrochemical stability and superior compatibility capability with ionic liquids. In a typical anion exchange experiment, a number of LiTFSI were added into PIN-Br-water dispersion at a mole ratio of Br- : TFSI- = 1 : 2.5 at 50 oC to ensure a complete replacement of the former Br anions. Figure 1a and 1b show the Fourier transform infrared (FTIR) spectra of PIN-1 and PIN-4 samples. Four peaks attributed to νa(S-N-S), νs(SO2), νa(CF3), and νa(SO2) from TFSI anions appear at 1057, 1134, 1198, and 1345 cm-1 respectively after ion exchange, demonstrating a successful attachment of TFSI anions into the polymer backbone. In Figure 1a, the peak at 1662 7 ACS Paragon Plus Environment


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cm-1 for PIN-1-Br is attributed to the C=O bond in N-methyl-2-pyrrolidinone (NMP) from the incomplete removal after the synthesize procedure of PIN-1-Br. The residual NMP is then removed during the anion exchange process, and as a result the corresponding peak disappears for PIN-1. The same change can be seen in Figure S1 for PIN-2. In Figure 1b, the peak at about 1630 cm-1 is attributed to C-N bond in the pyridine rings. The chemical structure of PIN-4 was further characterized by FTIR (Figure 1b,c), where in addition to the replacement of TFSI-, the peak at 1660 cm-1 corresponding to vinyl group of the monomer of PIN-4 (PIN-4-mono) disappears after radical polymerization (Figure 1c), indicating a complete integrate of vinyl groups into the ionic networks at a polymerization degree of close to 100%. Successful anion exchange and polymerization are also seen in the FTIR spectra of PIN-2,3 samples (Figure S1, S2). The reaction procedure to synthesize PIN-1-Br was further characterized by nuclear magnetic resonance (NMR) measurements. The characteristic absorption in brooethyl located at δ=4.91 ppm is weakened after the substitution of N,N,N',N'-Tetramethylethylenediamine, while the characteristic peak B representing the polymerized production at 4.57 ppm is gradually strengthened during the synthesis (Figure 1d, Figure S3). The degree of polymerization is estimated to reach to 61% after 27 h at 80 oC according to the peak area ratio of A and B. The structure of PIN-1 was investigated at the molecular level by

13C

nuclear magnetic resonance

(NMR) spectra (Figure 1e). In PIN-1 spectrum, peak A, B at 118.2 and 121.4 ppm is assigned to the carbon on the benzene ring, and peak C, D, E at 49.0, 17.6, 30.6 ppm, is attributed to the carbons bonded to positive charged nitrogen atom, respectively. Signal F is considered the carbon in TFSI anion with a high chemical shift of 174.4 ppm, which should be the impact of


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fluorine atoms with high electronegativity. Moreover, the solid-state NMR spectrum of PIN-4 is shown in Figure S4, which indicates a successful synthesis of PIN-4 electrolyte.

Figure 1. a) FT-IR spectrum of PIN-1 samples before and after anion exchange. b) FT-IR of PIN-4-Mono and PIN-4 samples. c) Detailed FT-IR spectrum peak change after polymerization of PIN-4. d) 1H NMR spectrum of PIN-1-Br (in D6-DMSO) during the reaction. e)

13C

NMR

spectrum of PIN-1 (in D6-DMSO). The thermal stability of PIN electrolytes was characterized by thermogravimetric analysis (TGA), as shown in Figure 2a. PIN-1,2,3 samples show similar one-step thermal decomposition behaviors at a temperature of 350 oC, but PIN-4 shows two-step decomposition behavior at the 9 ACS Paragon Plus Environment


temperature of 250 oC and 410 oC, respectively, which is also above the melting point of lithium. As the PIN-3 and PIN-4 polymers decompose at around 300 oC in their first-step thermal decomposition according to the thermogravimetric analysis, the PIN-3,4 samples were treated at 300 oC under argon atmosphere, and the productions were characterized by Fourier transform infrared spectra, as is presented in Figure S5. For PIN-3 sample, the peak A at around 830 cm-1 corresponding to C-H bond in 1,3,5-substituted benzene disappears after 300 oC heat treatment, and a new peak B appears at around 810 cm-1, corresponding to C-H bond in disubstituted benzene. This suggests the breaking of C-C bond between the substituent groups and benzene rings at 300 oC. Similarly for PIN-4, new peak C appears at 870 cm-1 corresponding to the C-H bond in multi- substituted benzene rings, suggesting the decomposition of hexakis-substituted benzene. Figure 2b shows the X-ray diffraction (XRD) of all PIN products, where PIN-1 exhibit a strong broad peak at 19.2o, and two weak broad peaks at 12.8o and 38.7o. Similarly, PIN-3 and PIN-4 samples exhibit strong broad peaks at 18.5o and 19.4o, and weak broad peaks at 36.9o and 39.8o, respectively. For PIN-2, the pattern shows a single broad peak at 22.6o. The broad peaks of all PIN products indicate their amorphous polymer structures. Figure 2c and 2d are the scanning electron microscopy (SEM) images for PIN-1 and PIN-4 samples, where PIN-1 product exhibits agglomerated-particle-like morphology with an average diameter of 1.16 µm. Unlike PIN-1, PIN-4 sample show bulk morphology with rough surfaces. The SEM images of PIN-2 and PIN-3 samples are shown in Figure S5 of the Supplementary Information, where they exhibit similar bulk morphology as PIN-4.


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Figure 2. a) TGA curves of PINs electrolytes in N2 atmosphere; scan rate: 10 oC/min-1. b) XRD patterns of PINs electrolytes. c) SEM images for PIN-1 sample. d) SEM images for PIN-4 sample. LiTFSI dissolved in EMIM-TFSI at a concentration of 1 mol kg-1 was absorbed into PINs solid particles and was pressed under a 12 MPa pressure to fabricate quasi-solid-state electrolytes (PIN@LiTFSI-EMIMTFSI) in pursuit of reduced interfacial resistance toward the electrode material and higher ionic conductivity (Figure 3a, Table S1, Supporting Information). The quasisolid electrolytes consist of polymer matrix coupled with ionic liquid by electrostatic force. In comparison to traditional PIL-based electrolytes, in which ionic liquids were doped at a ratio of 65 wt%-95 wt%, our prepared PINs could absorb significantly more IL (up to 130 wt%) as the polymer host.49,50 Such a better performance in IL absorption is probably due to the highly 11 ACS Paragon Plus Environment


charged structures with strong intermolecular forces.49 Consequently, the interacted structure emancipates Li+ for higher mobility in the highly charged electrolytes. Raman Spectrum of PIN-4@LiTFSI-EMIMTFSI was conducted to investigate the incorporation in EMIM-TFSI additive electrolyte, as shown in Figure 3c. In the region between 500 and 1400 cm-1, the characteristic bending bands of TFSI anions are observed, assigned to CF3 antisymmetric bending (551 cm-1), CF3 symmetric bending (744 cm-1, 1244 cm-1), SO2 symmetric stretching (1136 cm-1) and two SO2 antisymmetric stretching modes (1293 cm-1 , 1332 cm-1) in TFSI anions. Further strong bands are (N)CH2 and (N)CH3 C-N stretching at 1004 cm-1 in EMIM cations, indicating a successful introduction of EMIM-TFSI ionic liquid into the hybrid. Similarly, the Raman spectrum of PIN-1@LiTFSI-EMIMTFSI is presented in Figure S7, which also demonstrate the successful incorporation of EMIM-TFSI ionic liquid. Shoulder peaks are barely seen in the Raman spectrum, suggesting a homogeneous distribution of TFSI- and EMIM+ in the electrolyte. 2.2 Interaction of the PIN Backbone with TFSI Anions. It can be seen from the photographs (Figure 3b), as an example, that the PIN-4 sample was pressed into a solid electrolyte membrane and became darker after absorbing ionic liquid to form PIN-4@LiTFSIEMIMTFSI electrolytes. To deeply investigate the electrostatic interaction between the polymer backbone and TFSI-, N1s X-ray photoelectron spectroscopy (XPS) measurements were conducted, in that nitrogen element was contained in both the backbone with positive charge and TFSI anions. The N1s peaks of the PIN-4 samples show two peaks at 399.4 eV and 402.3 eV, which are attributed to the pyridinum N+ in the polymer matrix and N− in TFSI anions, respectively (Figure 3d). The N1s XPS spectrum of PIN-4@LiTFSI-EMIMTFSI (1/1.3, wt/wt) exhibits a stronger N− peak compared with PIN-4, because more N− atoms were contained in the 12 ACS Paragon Plus Environment

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sample after it was mixed with LiTFSI. The only one peak originated from N− species in TFSI anions suggests that LiTFSI are evenly distributed in PIN-4 hybrid system. Both the two peaks shift negatively by ≈0.5 eV in comparison to those of PIN-4 spectrum, suggesting the negative charge of N which may be due to an increased electron cloud density when extra TFSI anions are added into the sample (Figure 3e). Furthermore, the two adjacent peaks in both spectrum indicate a well coexistence of different N species. The N1s peaks in PIN-1,2,3@LiTFSI-EMIMTFSI XPS spectrum (Figure S8) exhibit similar expand and negative shift as that in PIN-4@LiTFSIEMIMTFSI XPS spectrum. In conclusion, such highly charged PINs products with a strong matrix combined with ionic compounds could be a good candidate for the fabrication of solid electrolytes.



Figure 3. a) Illustration of PIN-2@LiTFSI-EMIMTFSI composite electrolytes. b) Images of a PIN-4 solid slice and PIN-4@LiTFSI-EMIMTFSI. c) Raman spectrum of PIN-4@LiTFSIEMIMTFSI electrolytes. d,e) N1s XPS curves of PIN-4 and PIN-4@LiTFSI-EMIMTFSI. Electrochemical stabilities of the PIN electrolyte samples at 25 oC were characterized by linear sweep voltammetry (LSV), as shown in Fig 4a. PIN-1,3,4 samples are electrochemically stable up to 5.0 V vs. Li/Li+, while PIN-2 decomposes at about 4.4 V vs. Li/Li+. Particularly, the decomposition voltage of PIN-4 reaches up to 5.3 V vs. Li/Li+, which is suitable for the application of PIN-4 in high-voltage batteries as a polymer electrolyte. In consideration of the decomposing voltage, it is reasonable that for those PINs linked by tetramethylethylenediamine (PIN-1 and 2), PIN-1 with three substitution groups shows better electrochemical stability than PIN-2 with six substitution groups, which is owing to weaker steric hindrance of PIN-1 molecular structure. And for PINs linked by C-C bond (PIN-3 and 4), the number of substitution groups seem to have little effect on their stability. 2.3 Ionic conductivity of the PINs. Considering that ionic conductivity is one of the key properties for the electrochemical performance of electrolytes, the ionic conductivity as a function of temperature for PIN@LiTFSI-EMIMTFSI electrolyte samples was evaluated by AC impedance techniques, and in comparison, the ionic conductivity of PINs incorporated with N,Ndiethyl-N-(2-methoxyethyl)-N-methylammonium

bis(trifluoromethylsulphonyl)imide

(DEMETFSI) were tested under the same conditions. The results are presented in Figure 4b. It is apparent that PIN-1,3,4 with good electrochemical stability also perform well in ionic conductivity (up to 5.89×10−3 S cm−1 at 25 oC, the highest conductivity among the state-of-art polymer gel electrolytes and polymer solid electrolytes, according to an ionic conductivity level comparison of the state-of-art polymer electrolytes in Figure S9) which could be the contribution 14 ACS Paragon Plus Environment

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of highly charged PIN structure that facilitates Li+ transportation. Additionally, since the ionic conductivity of LiTFSI-EMIMTFSI liquid electrolyte is much higher than that of the LiTFSIDEMETFSI, the PIN@LiTFSI-EMIMTFSI hybrid electrolytes, as a whole, possess superior conductivity performance compared with the PIN@LiTFSI-DEMETFSI. The ionic conductivity of PIN-2 is at a level of 5.01×10−5 S cm−1, significantly lower than the former ones, might be the result of the stereoscopic effect of space and incomplete polymerization. It can also be seen that the ionic conductivity of PIN-1,3,4 increases with increasing temperature ranging from 25 oC-40 oC.

Motivated migration of carrier ions and segmental motion of polymer backbone at higher

temperatures are responsible for this increase. As the temperature increases higher than 50 oC, the ionic conductivity of PIN-1,3,4 appears a slight decline, probably owing to partial ionic liquid leakage from matrix at high temperature. It should be noted that all of PIN-1,3,4@LiTFSIEMIMTFSI electrolytes afford excellent ionic conductivity above 5.0×10−3 S cm−1 at room temperature, and particularly PIN-1@LiTFSI-EMIMTFSI shows excellent conductivity of 5.89×10−3 S cm−1, much higher than reported polymer-based solid or gel electrolytes. The increasing ionic conductivities under higher temperature roughly follow Arrhenius behavior, and the corresponding activation energies were calculated by the least-squares method to be 2.18 eV, 0.489 eV, 0.630 eV, 1.36 eV, 1.24 eV, 1.43 eV and 1.81 eV for PIN1,2,3,4@LiTFSI-EMIMTFSI and PIN-1,3,4@LiTFSI-DEMETFSI electrolytes, respectively (Figure S10). Note that for those PINs hybrid electrolytes which show conductivity decrease at over 50 oC as a result of ionic liquid leakage, the decreased ionic conductivity were unaccounted in the activation energy analysis. In comparison of the activation energy of other polymer electrolytes, for example solid polymer electrolytes (PEO-TiO2, 2.7 eV), PEO-based composite polymer ionic liquids (3.15 eV), and gel-polymer-based nanocomposites (2.27 eV), the PINs 15 ACS Paragon Plus Environment


electrolytes show lower activation energy, indicating a smaller activation barrier for ion transfer in PINs composite electrolyte interface.51 Lithium redox in the PIN-4@LiTFSI-EMIMTFSI electrolyte as a sample was then determined by cyclic voltammograms (CVs) test with a Li/electrolyte/Ni cell, as seen in Figure 4c. It can be clearly observed that the plating and stripping of lithium occur on the nickel electrode. In the first cycle for the PIN-4-based electrolyte, the cathodic peak corresponding to the plating of lithium is about –0.25 V versus Li/Li+; and the anodic peak at 0.27 V versus Li/Li+ in the returning scan corresponds to the stripping of lithium. The Li redox in the PIN@LiTFSIEMIMTFSI electrolytes could be assigned to the formation of a solid electrolyte interface (SEI) on the nickel electrode. The CV curves exhibit slight decrease in the first few cycles, and tends to be stable in the 8-10th cycles, indicating the stability of the SEI film. Notably, the anodic peak at 1.22 V versus Li/Li+ is due to the formation of Li–Ni alloys. The reversible Li redox test suggests that the PIN-4@LiTFSI-EMIMTFSI electrolytes could meet the requirement of lithium ions transportation. To investigate the stability of PIN hybrid electrolytes to Li metal, the Li stripping/plating experiments were performed in a Li/PIN-4@LiTFSI-EMIMTFSI/Li cell. The voltage response of PIN-4@LiTFSI-EMIMTFSI was measured at room temperature for more than 140 hours under a constant current density of 0.1 mA cm-2, as shown in Fig 4d. Each cycle of the plate/strip procedure was maintained for 0.5 h during the first 47 hours and for 4 h in the following test time. It can be seen from the first few stripping/plating cycles that there is no vibration and the cell potential keeps low and stable (43 mV and 100 mV respectively in the two procedures) during the whole test, suggesting a homogeneous penetration procedure of ionic liquid in the PIN electrolyte. The stable cycling behavior of PIN-4@LiTFSI-EMIMTFSI also reveals the stable 16 ACS Paragon Plus Environment

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lithium stripping/plating cycling performance with restrained lithium dendrite growth. It is noteworthy that in common Li stripping/plating tests for traditional organic electrolytes, the voltage response curves in each cycle generally undergo an instant rise during charge procedure, followed by a stable platform and an instant falling, corresponding to the fast migration of Li+ from electrolyte part to the electrode, the formation of Li stripping/plating balance and the return of Li species back to electrolyte, respectively. But in our experiment, the voltage signals steadily increase until the end of the charge step and then instantly drop down without a short pause, probably due to the polarization phenomenon during Li+ transportation. As a lot of cations such as EMI+ are contained in the composite electrolyte system, Li ions need additional time to reach the electrode, resulting in the curve shape in Fig 4d, which is also seen by other researches.52-54 2.4 Battery Performance. In consideration of the high electrochemical stability of PIN electrolytes (a decomposition voltage of up to 5V), as an example, PIN-3@LiTFSI-DEMETFSI electrolyte were assembled in lithium batteries with modified LiCoO2 cathode, which worked under higher voltage level ranging from 3.0 V to 4.4 V. The charge-discharge performance are presented in Figure 4f. The Li/PIN-3@LiTFSI-DEMETFSI/LiCoO2 battery shows an initial discharge capacity of 109 mAh g-1 at the current rates of 0.1C, and the discharge capacity increases to around 120 mAh g-1 in the first 50 cycles. Subsequently the discharge capacity increases steadily to around 130 mAh g-1 after 52 cycles and slightly decreases after 86 cycles. Li/LiFePO4

batteries

with

PINs@LiTFSI-DEMETFSI

and

PINs@LiTFSI-EMIMTFSI

electrolytes were fabricated to characterize their cycling performances. In Figure S11, S12, and Figure 4e, the batteries with PIN-1@LiTFSI-EMIMTFSI, PIN-3@LiTFSI-DEMETFSI and PIN4@LiTFSI-DEMETFSI exhibit favorable pristine discharge capacity of 155, 134 and 127 mAh g−1, respectively. Although the initial coulombic efficiency of PIN-1@LiTFSI-EMIMTFSI 17 ACS Paragon Plus Environment


battery is only 90.0%, it swiftly increases up to 98.5% after the second cycle, and similar increase is also seen in Li/PIN-3@LiTFSI-DEMETFSI/LiFePO4 cell. This could be the result of improved penetration of ionic liquid and formation of a transition layer between PIN electrolyte and Li metal, which decreases the interfacial impedance of electrolyte/electrode. Further, Li/LiFePO4 batteries with the electrolytes of PINs@LiTFSI-DEMETFSI and PINs@LiTFSIEMIMTFSI display quite stable cycling performance (Figure S11, S12 and Figure 4g). In conclusion, both subsequent battery capacity and coulombic efficiencies of each battery remain stable after 250 cycles. As is indicated from the above-mentioned results, the quasi-solid composite electrolytes based on PINs with good battery performance are promising for the application of solid electrolyte for Li metal batteries.


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Figure 4. a) LSV curves of PINs composite electrolytes (SS/PIN@LiTFSI-EMIMTFSI/Li cells, scan rate: 10 mV s-1). b) Temperature dependence of the ionic conductivity of PIN@LiTFSIEMIMTFSI and PIN@LiTFSI-DEMETFSI electrolytes. c) CV curves for PIN@LiTFSIEMIMTFSI electrolytes. Working electrode: nickel; counter electrode and reference electrode: lithium; scan rate: 10 mV s−1. d) Voltage profiles for PIN-4@LiTFSI-EMIMTFSI at a current density of 0.1 mA cm-2 at room temperature. e,f) Charge–discharge curves of Li/PIN-4@LiTFSIDEMETFSI/LiFePO4 and Li/PIN-3@LiTFSI-DEMETFSI/LiCoO2 cells at 25 oC. g,h) Discharge capacity and coulombic efficiency as functions of cycle number for Li/PIN-4@LiTFSI-



DEMETFSI/LiFePO4 and Li/PIN-3@LiTFSI-DEMETFSI/LiCoO2 cells at room temperature. Charge–discharge current rate is 0.1C.

3. Conclusion To sum up, an interesting series of PINs with densely charged network structures is synthesized through easy strategies including nucleophilic substitution followed by radical polymerization and anions exchange reactions. The PINs-host electrolytes containing EMIMTFSI or DEMETFSI ionic liquid and LITFSI salt possess remarkable ionic conductivities at room temperature (5.89×10−3 S cm−1) and high electrochemical stability (decompose at over 5 V). One of the key steps of this strategy is the introduction of PINs as the electrolyte matrix, which provides not only facile channels for Li+ transportation in the quasi-solid system, but also strengthened mechanical structures of the electrolyte membrane. Meanwhile, PINs with high charge density provides abundant, weakly electrostatic coordinating sites during Li+ migration. In terms of battery tests, the corresponding Li/LiFePO4 cells have discharge capacity of up to 157 mAh g-1 at 0.1 current rates, and good stability after 250 cycles. The Li/LiCoO2 cells working under high voltage also have favorable stability and discharge capacity (about 130 mAh g-1 after 100 cycles). Considering the excellent electrochemical performance, PIN-based quasisolid electrolytes possess enormous potential to be a candidate for high voltage lithium batteries. ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at DOI:


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Experimental methods of PINs materials, characterization details, additional data from FTIR spectrum, solid-state NMR spectrum, SEM images, ionic conductivity level comparison histogram and battery tests of PINs electrolytes AUTHOR INFORMATION Corresponding Author *[email protected] *[email protected] Notes The authors declare no competing financial interest. ACKNOWLEDGMENT This work was supported by the Nature Science Foundation of Shaan Xi Province for Significant Basic Research (2017ZDJC-30), and the Fundamental Research Funds for the Central Universities (2018ZDCXL-GY-08-06). REFERENCES (1) Janek, J.; Zeier, W. G. A Solid Future for Battery Development. Nature Energy 2016, 1, 16141. (2) Fan, L.; Wei, S.; Li, S.; Li, Q.; Lu, Y. Recent Progress of the Solid-State Electrolytes for High-Energy Metal-Based Batteries. Adv. Energy Mater. 2018, 8, 170265711. (3) Cheng, X.; Zhang, R.; Zhao, C.; Wei, F.; Zhang, J.; Zhang, Q. A Review of Solid Electrolyte Interphases on Lithium Metal Anode. Adv. Sci. 2016, 3, 15002133. 21 ACS Paragon Plus Environment


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