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Fast Ion Transport Pathway Provided by Polyethylene Glycol Confined in Covalent Organic Frameworks Zhenbin Guo, Yuanyuan Zhang, Yu Dong, Jie Li, Siwu Li, Pengpeng Shao, Xiao Feng, and Bo Wang J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b13551 • Publication Date (Web): 18 Jan 2019 Downloaded from http://pubs.acs.org on January 18, 2019

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Journal of the American Chemical Society

Zhenbin Guo,# Yuanyuan Zhang,# Yu Dong, Jie Li, Siwu Li, Pengpeng Shao, Xiao Feng,* and Bo Wang* Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Key Laboratory of Cluster Science, Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, People’s Republic of China Supporting Information Placeholder

Covalent organic frameworks (COFs) with well-tailored channels are able to accommodate ions and offer their conduction pathway. However, due to strong Coulombic interaction and the lack of transport medium, directly including lithium salts into the channels of COFs results in limited ion transport capability. Herein, we propose a strategy of incorporating low-molecularweight polyethylene glycol (PEG) into COFs with anionic, neutral, or cationic skeletons to accelerate Li+ conduction. The PEG confined in the well-aligned channels retains high flexibility and Li+ solvating ability. The ion conductivity of PEG included in a cationic COF can reach 1.78 × 10–3 S cm–1 at 120 oC. The simplicity of this strategy as well as the diversity of crystalline porous materials holds great promise to design highperformance all-solid-state ion conductors.

Polymeric crystalline porous materials including covalent organic frameworks (COFs)1 and metal–organic frameworks (MOFs)2 exhibit great potential in gas sorption3 and separation,4 energy storage,5 sensing,6 electronic device,7 and catalysis.8 In addition to their electrical insulation nature, the open channels with good tunability ensure them to serve as an ideal platform to investigate the ion transport behaviors inside atomically precise skeletons, which is of fundamental importance for achieving solid electrolytes with high ion conduction ability. Despite difficulties, several pioneering works have been reported to improve their ion conductivities, for examples, designing MOFs with open metal sites, preparing cationic COF nanosheets, mechanically shaping COFs into well orientation, covalently anchoring flexible chains to the pore walls, etc.9 However, these ion conductors usually involve some liquid electrolytes remaining in the channels to accelerate ion pair dissociation and ion transport. These organic liquids will inevitably bring safety risks caused by the vaporization, leakage and flammability at elevated temperature.10 A versa-

tile strategy to facilitate ion conduction, which can take full advantages of the diversity of crystalline porous materials without tedious synthetic procedure, is highly desired yet largely unexplored. Compared with MOFs, COFs that are constructed by covalent linking of pure organic building units benefit from better electrochemical stability and smaller environmental footprint.1c, 11, 12 Herein, we report a strategy to efficiently promote Li+ movement by incorporating low-molecular-weight polyethylene glycol (PEG, Mw = 800) into the channels of COFs without any solvent residue, allowing fast and stable ion conduction in a wide temperature range (Figure 1a). Unlike poly(ethylene oxide) (PEO) with Mw up to several hundreds of thousands that suffered from high content of crystalline region and consequently a limited ionic conductivity (~10−7 S cm−1 at r.t.), PEG adopts much higher chain dynamics and provides a great chance to reach high ion conduction rate with the aid of a large donor number (oxygen atoms) for the Li+.13 Nevertheless, PEG undergoes a phase change from elastic to viscous state within the working temperature range of ion conductor, posing a huge obstacle for its practical applications. We intended to encapsulate PEG into the COFs because the polymers inside the channels make it possible to alter their thermal behavior.14 In our previous work, we reported a three-dimensional (3D) anionic cyclodextrin-based COF (CD-COF-Li) showing high ion conductivity in a quasi-solid-state with organic liquids left.15 CD-COF-Li without any solvation molecules is Li+ insulated; in this study, we find the ion conductivity can be significantly boosted to 10−5 S cm−1 at r.t. by accommodating PEG. However, its low lithium ion transference number (TLi+) of 0.20 would cause an anion charge gradient and polarization across the medium, leading to inevitable performance failure. The large contribution from anion conduction is because of the immobilization of Li+ in anionic skeleton; therefore, we further include PEG into two neutral COFs (COF-5,1a COF-30016) and a cationic COF (EB-COF-ClO411d)

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(Figure 1b). Indeed, the ion conductivities are remarkably increased, which can be attributed to the enrichment of ion hoping pathways provided by PEG. Specifically, the ion conductivity of PEG-Li+@EB-COF-ClO4 reaches 1.78 × 10−3 S cm−1 at 120 oC. To the best of our knowledge, this value is the highest of all polymeric crystalline porous materials based all-solid-state conductors without any solvents. The TLi+ of PEG-Li+@EBCOF-ClO4 is up to 0.60 due to its cationic framework. The performance of PEG-Li+@EB-COF-ClO4 does not exhibit any deterioration after 48-h working at 90 oC.

Figure 2. a) PXRD patterns of EB-COF-ClO4, PEGLi+@EB-COF-ClO4, w-EB-COF-ClO4, PEG/Li+/EB-COFClO4 and PEG. b) Nitrogen sorption profiles of EB-COFClO4, PEG-Li+@EB-COF-ClO4 and w-EB-COF-ClO4. c) Pore size distribution of EB-COF-ClO4 and PEG-Li+@EBCOF-ClO4. d) DSC curves of PEG, PEG-Li+@EB-COFClO4 and PEG/Li+/EB-COF-ClO4.

Figure 1. a) Schematic illustrations of Li+ transport in COFs. b) Structural representations of CD-COF, COF-5, COF-300 and EB-COF.

CD-COF adopts a 3D anionic skeleton with rra topology, where tetratopic boron atoms are linked by octatopic γ-CD struts to yield 3D open channels with micropore cavities along crystallographic a, b, and c directions (Figure S1a).15 COF-5 and EB-COF are both 2D COFs that form a hexagonal array of 1D channels, while the skeleton of the former is neutral and the latter is cationic (Figure S1b,1c).1a, 11d COF-300 possesses dia-c7 topology with sevenfold interpenetrated network, yielding 1D open channels along the [001] direction (Figure S1d).16 The successful preparations of these COFs are evidenced by powder X-ray diffraction (PXRD), N2 sorption isotherms, Fourier transform infrared (FT-IR) spectra, and elemental analyses (EA) (Figure S2–S4 and S8– S10; Table S1–S4). The PEG-Li+@COFs were prepared as follows: COFs were loaded with PEG and LiClO4 in acetonitrile, and the solvent was then completely removed to give dry powder of PEG-Li+@COFs. The PEG/COF feeding ratio and the loading amount of LiClO4 were optimized. EA (C, H, N) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) results confirm the element ratios in the PEG-Li+@COF inclusions (Table S1– S4) are consistent with the feedings. In addition to the EA results, FT-IR spectra and thermogravimetric analysis all demonstrate that no solvent residues are remained in the PEG-Li+@COF electrolytes (Figure S4, S5, S10 and S11).

The incorporation of PEG into the channels of the COFs was confirmed by PXRD, N2 sorption, differential scanning calorimetry (DSC) measurement and scanning electron microscopy (SEM). Take EB-COF-ClO4 as an example, the peak at 3.3o corresponding to the (100) facets is obviously weakened in the PXRD pattern of PEG-Li+@EB-COF-ClO4, resulting from the disorder induced by the flexible PEG chains inside the 1D channels (Figure 2a). After the removal of PEG and LiClO4 from the COF by washing with solvent (denoted as wEB-COF-ClO4), the peak intensity of (100) facets is recovered, illustrating the underlying structure of the COF was retained during the whole process. Compared with the patterns of pure PEG and mechanically mixed sample of PEG, LiClO4 and EB-COF-ClO4 (denoted as PEG/Li+/EB-COF-ClO4), a broad peak at ~26o is emerged for PEG-Li+@EB-COF-ClO4, which may be attributed to the formation of microscopically ordered alignment of PEG chains in the confined and wellorganized channels to some extent. The weakened intensity of the peak at 3.3o for PEG/Li+/EB-COF-ClO4 may result from the partial PEG insertion into the channels of EB-COF-ClO4. The porosity is significantly diminished in PEG-Li+@EB-COF-ClO4 yet can be fully recovered after PEG removal as evaluated by the nitrogen sorption isotherms measured at 77 K (Figure 2b). The reduction of pore volume upon encapsulating PEG is supposed to be attributed to the occupancy of PEG in the channels and/or fully wrapped COF particle surfaces (Figure 2c). To further confirm whether the PEG is inside the channels or outside the surfaces, we performed DSC measurements (Figure 2d). EB-COF-ClO4 doesn’t show any endothermic/exothermic peaks during the test at the temperature range from -10 to 120 oC (Figure S6). PEG 800 itself exhibits a thermal transition around 30 oC due to the phase transition from elastic to viscous state. In


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sharp contrast, no obvious endothermic/exothermic peak is found in the DSC profile of PEG-Li+@EB-COF-ClO4, indicating the majority of PEG is accommodated inside the COF channels.17 In comparison, PEG/Li+/EB-COFClO4 exhibits similar thermal behavior with bulk PEG. The lower intensity of the peak of PEG/Li+/EB-COFClO4 compared with that of bulk PEG further confirms the partial occupation of PEG in the channels.18 The SEM images also demonstrate that the morphologies of the COF particles do not show much differences after PEG encapsulation (Figure S7). Besides the cationic framework, it is shown that PEG was successfully included inside the channels of all other three COFs, including anionic framework and two neutral frameworks (Figure S8–S14). Based on the above characterizations, we can conclude that the majority of PEG is incorporated inside the channels, while there might be possibilities of partial insertion and coating on the surface. Nevertheless, the PEG penetrated the channels provides efficient pathways for Li+ conduction.

Figure 3. a) Arrhenius plots of PEG-Li+@EB-COF-ClO4 (orange), PEG-Li+@CD-COF-Li (blue), PEG-Li+@COF300 (red), PEG/Li+/EB-COF-ClO4 (gray), PEG-Li+@COF5 (purple), and Li+@CD-COF-Li (green) ionic conductivity. b) Ion conductivities and TLi+ of PEG-Li+@COFs and Li+@COFs at 30 oC. The red area indicates the contribution of Li+ conduction and the orange area shows the contribution from anion conduction. c) and d) The EIS spectra of PEG-Li+@EB-COF-ClO4 and LiPF6-EC-DMC@EB-COFClO4 during continuous running at 90 oC.

To study the Li+ conduction, the powder samples of PEG-Li+@COFs were mechanically pressed into pellets for electrochemical tests. The electrochemical impedance spectroscopy (EIS) of PEG-Li+@COFs pellets were obtained from 30 to 120 oC (Figure S15–S18). The ion conductivities of PEG-Li+@CD-COF-Li, PEGLi+@COF-300, PEG-Li+@COF-5, and PEG-Li+@EBCOF-ClO4 are calculated to be 2.60 × 10–5, 1.40 × 10–6, 3.60 × 10–8, and 1.93 × 10–5 S cm–1 at 30 oC (Figure 3b) and 1.30 × 10–4, 9.11 × 10–5, 3.49 × 10–5, and 1.78 × 10–3

S cm–1 at 120 oC, respectively. COFs with ionic network, i.e. EB-COF-ClO4 and CD-COF-Li, exhibit higher ion conductivity than those with neutral framework, which can be explained by the interactions between the charged framework and Li salt promoting the dissociation of ionic pairs. PEG/Li+/EB-COF-ClO4 gives lower ion conductivities of 6.80 × 10–7 S cm–1 at 30 oC compared with PEG-Li+@EB-COF-ClO4, indicating COF structures that are wrapped with PEG chains are not only excluded from the ion conduction process but also dampen the conduction pathway of PEG. As a control, incorporating Li salts alone at same loading into the channels of COFs was studied (denoted as Li+@COFs) (Figure 3b). It is worth mentioning that no ion conduction behavior is observed in the EIS spectra of Li+@EB-COF-ClO4, Li+@COF-300 and Li+@COF-5 even at 120 oC. Li+@CD-COF-Li gives a conductivity of only 7.81 × 10–7 S cm–1 at 120 oC. Unlike the previous study on Li+@COFs in which the residual solvents assist the Li salt dissociation and ion transport (Table S5), the incorporated flexible PEG chains in this case act as transport medium, giving a conductivity comparable or even better than that of liquid-included Li+@COFs. As shown in Figure 3a, the conductivities at varied temperatures follow Arrhenius law with activation energy as low as 0.17, 0.20 and 0.35, and 0.21 eV for PEG-Li+@CD-COF-Li, PEG-Li+@COF-300, PEG-Li+@COF-5, and PEGLi+@EB-COF-ClO4, respectively. These activation energy values are comparable to those of quasi-solid electrolyte with organic solvents.9a, 9d, 9f, 19 These results all demonstrate that the local segmental motion of PEG chains inside the channels can sufficiently promote Li+ conduction in a liquidlike manner in the microscopic environment. It should be noted that the small amount of the partially inserted and/or surface-coated PEG could also facilitate the inter-particle ion transport. For practical applications, TLi+ as well as thermal stability should be also taken into account as an important factor for evaluating the performance of electrolytes. The average TLi+ was obtained by using a BruceVincent-Evans (BVE) method (Figure 3b). PEGLi+@CD-COF-Li has a high ion conductivity but a low TLi+ of 0.20 (Figure S19), owing to its anionic skeleton that can fix Li+ and facilitate anion conduction. PEGLi+@COF-300 and PEG-Li+@COF-5 own neutral skeleton and the TLi+ are calculated to be 0.44 and 0.40, respectively (Figure S20 and S21). On the contrary, PEGLi+@EB-COF-ClO4 possesses a cationic skeleton, which can trap anion and accelerate Li+ transport, and its TLi+ can reach 0.60 (Figure S22). All the four PEGLi+@COFs are thermally stable at least up to 300 oC (Figure S5 and S11). We carried out continuous conductivity tests on PEG-Li+@EB-COF-ClO4 and LiPF6-ECDMC@EB-COF-ClO4 pellets at 90 oC using a coin-cell setup with two stainless-steel electrodes as current collector, and the former showed no resistance changes after 48 h while the latter coin cell burst apart after 2 h



(Figure 3c,3d and S23). The incorporation of PEG makes it possible to be applied in high temperature working environment, avoiding the volatilization of organic electrolyte. In summary, we reported an applicable and facile method to promote the ion conduction in COFs by incorporating low-molecular-weight PEG into their open channels. Specifically, the ion conductivity of PEGLi+@EB-COF-ClO4 reaches 1.78 × 10–3 S cm–1 at 120 oC. To the best of our knowledge, this value is the highest of all polymeric crystalline porous materials based all-solid-state conductors without any residue solvents. Crystalline porous materials provide an ordered and confined space that can not only encapsulate PEG/Li+ but also tune their thermal behaviors as well as promote dissociation of Li ion pairs, which may serve as a promising platform for studying the ion conduction behaviors. Due to the thermal robustness, free of solvent residue feature and high ion conductivity, they show great potentials as solid-state electrolytes with wide operating temperature for practical applications.

The Supporting Information is available free of charge on the ACS Publications website. Experimental details and data (PDF)

*[email protected] *[email protected] ‡Z.G. and Y.Z. contributed equally. The authors declare no competing financial interest.

This work was financially supported by National Natural Science Foundation of China (Grant No. 21490570, 21674012, 21625102, 21471018); Beijing Municipal Science and Technology Project (Grant No. Z181100004418001) and Beijing Institute of Technology Research Fund Program.

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Figure 1. a) Schematic illustrations of Li+ transport in COFs. b) Structural representations of CD-COF, COF5, COF-300 and EB-COF.



Figure 2. a) PXRD patterns of EB-COF-ClO4, PEG-Li+@EB-COF-ClO4, w-EB-COF-ClO4, PEG/Li+/EB-COF-ClO4 and PEG. b) Nitrogen sorption profiles of EB-COF-ClO4, PEG-Li+@EB-COF-ClO4 and w-EB-COF-ClO4. c) Pore size distribution of EB-COF-ClO4 and PEG-Li+@EB-COF-ClO4. d) DSC curves of PEG, PEG-Li+@EB-COF-ClO4 and PEG/Li+/EB-COF-ClO4.


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Figure 3. a) Arrhenius plots of PEG-Li+@EB-COF-ClO4 (orange), PEG-Li+@CD-COF-Li (blue), PEG-Li+@COF300 (red), PEG/Li+/EB-COF-ClO4 (gray), PEG-Li+@COF- 5 (purple), and Li+@CD-COF-Li (green) ionic conductivity. b) Ion conductivities and TLi+ of PEG-Li+@COFs and Li+@COFs at 30 oC. The red area indicates the contribution of Li+ conduction and the orange area shows the contribution from anion conduction. c) and d) The EIS spectra of PEG-Li+@EB-COF-ClO4 and LiPF6-EC-DMC@EB-COF- ClO4 during continuous running at 90 oC.


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