Conductive Polymer Hybrid

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Construction of Metal-Organic Framework/Conductive Polymer Hybrid for All-solid-state Fabric Supercapacitor Kai Qi, Ruizuo Hou, Shahid Zaman, Yubing Qiu, Bao Yu Xia, and Hongwei Duan ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b05802 • Publication Date (Web): 11 May 2018 Downloaded from http://pubs.acs.org on May 12, 2018

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ACS Applied Materials & Interfaces

Construction of Metal-Organic Framework/Conductive Polymer Hybrid for All-solid-state Fabric Supercapacitor Kai Qi,†,‡ Ruizuo Hou,† Shahid Zaman,† Yubing Qiu,† Bao Yu Xia,*,† and Hongwei Duan *,‡ †

Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key

Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology (HUST), 1037 Luoyu Road, Wuhan 430074, P. R. China ‡

School of Chemical and Biomedical Engineering, Nanyang Technological University, 70 Nanyang Drive,

637457, Singapore.

KEYWORDS: Metal-organic frameworks, Polypyrrole, Fiber supercapacitors, Flexible devices, Textile electronics

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ABSTRACT: Metal-organic frameworks (MOFs) hold promising potentials in energy storages but are limited by the poor conductivity. In this work, a metal-organic framework/polypyrrole hybrid is constructed by a facile one-pot electrodeposition method in presence of dopamine. An all-solid-state fabric supercapacitor based on this hybrid demonstrates an excellent electrochemical energy storage performance, which achieves a specific capacitance of 10 mF cm-1 (206 mF cm-2), a power density of 132 µW cm-1 (2102 µW cm-2), and an energy density of 0.8 µWh cm-1 (12.8 µWh cm-2). The stable cycling life and the excellent mechanical flexibility over a wide working-temperature range are also achieved, which maintains the capacitance retention of 89% over 10,000 charging/discharging cycles, capacitance decrease of only 4% after 1000 frizzy (360o bending) cycles, and no obvious capacitance loss under 100 repeated heating (100 oC)/cooling (-15 oC) cycles. This fibrous supercapacitor displays promising potential in wearable textile electronics as it can be easily woven into common cotton cloth. Our strategy may shed some valuable lights in the construction of MOF-based hybrids for flexible energy storage electronics.


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INTRODUCTION Wearable and textile electronics present an alluring prospect of smart clothing with human-computer

interaction in the near future. Available energy storage in flexible forms is one of the key challenges to drive the intelligent textiles. An ideal strategy is to directly weave supercapacitive fibers into textiles as the energy storage component, with the advantages of high power, fast charging/discharging rate, and long-term cycling life as well as excellent mechanical flexibility and knittability.1-5 Various kinds of fibrous energy storage devices based on plastic fibers,6 metal wires,7 carbon fibers,8 natural fibers,9 carbon nanotubes yarns,10 and graphene fibers have been established.11 Particularly, carbon fibers (CFs) have been extensively used as talented fibrous electrodes, owing to high conductivity, excellent mechanical properties, lightweight, capability of being woven into fabrics, and more importantly the low cost with large-scale industrial production.3, 12-14 However, due to the undeveloped internal pore structure and low specific surface area (< 30 m2 g-1), carbon fibers has very low capacitance.1 At this instance, several active electrode materials, such as electrical double-layer capacitance (EDLC) based carbon materials,12,

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pseudocapacitive metal oxides/hydroxides18-20 and conductive

polymers,21-23 are prerequisite to incorporate onto carbon fibers for advancing the capacitance.1 The exploration and development of new classes of electrode material for high supercapacitive performance are still thought-provoking, although there are spacious collections of electrochemical energy storage materials. The most major indispensable criterions for electrode materials are their high conductivity, large surface areas or high pseudo-capacitance, and the long-term stability.24 Metal-organic frameworks (MOFs) materials have invoked compounding attentions and indicated outstanding potential advantages in the energy storage applications, due to their enormously high surface areas, controllable pores and nanocrystal structures.25-27 Numerous kinds of MOFs unveiled good pseudocapacitive behavior in alkaline electrolyte,28 therefore a mounting number of MOFs-based supercapacitors have been reported.25-27 Regrettably, due to the little conductivity of MOFs, most of their utilizations in supercapacitors are limited to precursors or templates for carbons or metal oxides.29, 30 An electrically conductive Ni3(HITP)2 MOF was served as the sole electrode material in supercapacitors without any conductive additives.31, 32 However, most of conventional MOFs are basically nonconductive (or extremely low conductivity). An effective strategy is the incorporation of ACS Paragon Plus Environment

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conductive polymers (CPs), which can act as the circuits of electrons transportation linking isolated MOFs crystals, providing extra pseudocapacitance.33 Combinations of MOFs and CPs have been previously reported. For example, PANI-ZIF-67 on carbon cloth was used as electrodes for a supercapacitor device with areal capacitance of 35 mF cm-2.33 Another supercapacitor device based on PEDOT-GO/UiO-66 coated carbon nanotube films demonstrated the areal capacitance of 30 mF cm-2.34 However, the MOF/CP hybrids of these works were fabricated mainly on the plane substrates (e.g. carbon cloth, ITO glass, conductive film, nickel foam) through firstly casting the MOFs slurry, followed by electropolymerization of CPs onto MOFs-coated substrates. Obviously, only the surface MOFs can be linked with CPs to induce nonuniform hybrids by this twostep approach. Moreover, such method of coating MOFs slurry is not workable for the ultrafine and long fiber substrates. There was a one-pot electrodeposition method to achieve MOFs/PANI hybrid coating onto a stainless steel thin wire in an aqueous electrolyte of aniline monomers and MOF crystals.35 However, few MOF particles were distinguished in the coating, probably due to the lack of effective binders, thus the electrochemical storage performance would be yet unsatisfied. Herein, we design a facile one-pot strategy to achieve a uniform MOF/CP hybrid coated on fibrous substrates (UiO-66/PPY on carbon fibers) for high-performance all-solid-state flexible fiber supercapacitors. This hybrid is realized through a one-pot electrodeposition process in the presence of dopamine. Specifically, dopamine (DA), which can perform as an adhesive agent due to the chemical structure of catecholamine and also be electropolymerized to polydopamine (PDA) with many striking properties in adhesion,36-38 is expected as the significant electrolyte additive for binding action. The assembled UiO-66/PPY hybrid based fabric fiber supercapacitor demonstrated a great potential for an effectively fibrous energy storage component with highperformance capacitive property, excellent mechanical flexibility, wide working temperatures and long-term cycling stability, which is ultimately capable of being woven into wearable and textile electronics.

RESULTS AND DISCUSSION


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Figure 1. (a) Fabrication illustration of UiO-66/PPY based flexible fiber supercapacitor device. SEM images of carbon fibers (b, c), UiO-66/PPY coated carbon fibers (d, e), and surface and inside of gel electrolyte coated fiber electrodes (f, g). Digital photo (h) and SEM image (i) of the fiber supercapacitor.

The fabrication process of the MOF/CP hybrid based fiber supercapacitor is shown in Figure 1a (see Experimental Section, Supporting Information, SI). A bundle (diameter of ~70 µm) of commercial carbon fibers (each individual fiber diameter of ~7 µm) acts as the fibrous substrate for the deposition of MOF/CP hybrid and current collector in fiber supercapacitor (Figures 1b, 1c). A Zr-based MOF (UiO-66 with particle size of ~500 nm, Figure S1a, SI) and conductive polymer of polypyrrole (PPY) are selected as the energy storage electrode materials. UiO-66/PPY hybrid is uniformly deposited onto carbon fibers (denoted as CFs@UiO-66/PPY) by the one-pot electropolymerization method in presence of dopamine additive. Scanning electron microscopy (SEM) images show that UiO-66/PPY hybrid is well coated across the surface of each carbon fiber (Figures 1d, 1e). Here, PPY is not only coated onto the surfaces of UiO-66 particles but also filled into the interparticle open space and acted as conductive links between the isolated UiO-66 crystals.33 Specifically, dopamine as the electrolyte additive may be the key to realize the one-pot electrodeposition of uniform UiO-66/PPY hybrid through electropolymerization of dopamine and incorporation of polydopamine into the composite as the ACS Paragon Plus Environment

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binder, which can be evidenced by the same electrodeposition procedure without dopamine involved, denoted as CFs@UiO-66/PPY (no DA), only few UiO-66 crystals sporadically decorated on the typical cauliflower-like surface of polypyrrole (Figures S1, SI). After the electrodeposition of UiO-66/PPY hybrid, fiber electrodes are further coated with PVA/LiCl gel (Figures 1f, 1g), which is acted as the solid-state electrolyte and the separator in the fiber supercapacitor. Finally, a fiber supercapacitor is obtained by twisting two gel-coated fiber electrodes together (Figures 1h, 1i).

Figure 2. (a) Typical CV curves of electrodeposition process of UiO-66/PPY onto carbon fibers (inset is the first segment of CV curves for synthesis with and without dopamine). (b) FT-IR spectra of UiO-66/PPY, PPY, PDA, and UiO-66. (c) Powder X-ray diffraction (XRD) patterns of simulated UiO-66, as-synthesized UiO-66, and CFs@UiO-66/PPY. (d) Nitrogen adsorption/desorption isotherms of fiber electrodes CFs@UiO-66/PPY and CFs@PPY.

In cyclic voltammograms (CV) curves of the electrodeposition process with dopamine (Figure 2a), the anodic peak (0.4-0.6 V) indicates the electropolymerization of dopamine to polydopamine (Figure 2a inset).39 The chemical composition of UiO-66/PPY hybrid is further characterized by fourier-transformed infrared spectrum (FT-IR). In the spectrum of UiO-66/PPY, peaks at 1400 cm-1 (C-O bond of C-OH group of carboxylic acid), 1500 cm-1 (C=C in aromatic compound), 1575 cm-1 (C=O in carboxylates), and 3430 cm-1 (O-H in carboxylates) generally are ascribed to the main functional groups on BDC organic linkers of UiO-66 (Figure ACS Paragon Plus Environment

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2b).40 The peaks at 920 and 1170 cm-1 are attributed to C-H in-plane bending vibration in pyrrole ring of PPY.21 Meanwhile, the peaks at 1620 cm-1 (overlap of C=C resonance vibration in the aromatic ring and the N-H bending) and 2920/2850 cm-1 (aliphatic C-H stretching vibrations of CH2) are due to polydopamine,41,

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supporting the polymerization and incorporation of polydopamine into the UiO-66/PPY hybrid. The powder Xray diffraction (XRD) patterns of fiber electrode CFs@UiO-66/PPY is consistent with that of the pristine UiO66 (Figure 2c), indicating the similar structural integrity of UiO-66 crystallinities and topologies after hybridizing. Nitrogen adsorption measurements are performed to investigate the specific surface area of the whole fiber electrode CFs@UiO-66/PPY (Figure 2d), which is calculated to be 125 m2 g-1, much higher than 16 m2 g-1 of only PPY coated carbon fibers electrode CFs@PPY, suggesting the porous nature of CFs@UiO66/PPY endowed from UiO-66.

Figure 3. Electrochemical measurements of the fiber electrodes: (a) CV curves at a scan rate of 10 mV s-1 for various fiber electrodes, (b) CV curves at different scan rates for CFs@UiO-66/PPY, (c) Galvanostatic charging/discharging curves at a ACS Paragon Plus Environment

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current density of 50 µA cm-1 for various fiber electrodes, (d) Galvanostatic charging/discharging curves at different current densities for CFs@UiO-66/PPY, (e) Electrochemical impedance spectroscopy (EIS) and (f) cycling stability measured at a scan rate of 100 mV s-1 over 1000 cycles for CFs@UiO-66/PPY.

The electrochemical capacitance performance of fiber electrode CFs@UiO-66/PPY was studied in 3 M KCl electrolyte by three-electrode system with cyclic voltammetry (CV) and galvanostatic charging/discharging measurements. Before tests, the optimized loading of UiO-66/PPY hybrid onto carbon fibers was firstly investigated at various electrodeposition CV segments (Figure S2, SI). The length capacitance increases with electrodeposition CV increasing from 10 to 60 segments. In contrast, the areal capacitance decreases over 40 segments, suggesting that capacitive contribution by higher loading of UiO-66/PPY hybrid becomes less efficient. More stacking of UiO-66/PPY hybrid could increase length capacitance, but also increase the thickness of active hybrid layer, thus hinder the ions diffusion and reduce the efficiency of capacitive energy storage. Therefore, the fiber electrode CFs@UiO-66/PPY with electrodeposition CV of 40 segments is selected in the following studies, which exhibits both relatively high specific length and higher areal capacitances. CV curves at 10 mV s-1 of fiber electrodes CFs@UiO-66/PPY, CFs@UiO-66/PPY (no DA), CFs@PPY-PDA, and CFs@PPY are compared in Figure 3a. Similar capacitive behaviors as well as the morphologies of CFs@PPYPDA and CFs@PPY indicate no obvious effect of the electropolymerization of dopamine and the incorporation of polydopamine into PPY (Figure S1, SI). The capacitance of CFs@UiO-66/PPY (no DA) is lower than that of CFs@UiO-66/PPY, supportive to the SEM morphology (Figure S1b, SI). Higher capacitance for CFs@UiO66/PPY is derived from the synergistic effect of hybridizing UiO-66 and PPY, which is promoted from the EDLC through porosity of UiO-66 and conductivity of PPY as well as the pseudocapacitance of PPY. Based on the CV curves at various scan rates from 5 to 100 mV s-1 (Figure 3b), the length capacitance of CFs@UiO66/PPY decreases from 15 to 8 mF cm-1, corresponding to the gravimetric capacitance of whole fiber electrode from 90 to 50 F g-1 (Figure S3a, SI). Galvanostatic charging/discharging (Figure 3c) and corresponding capacitances (Figure S3b, SI) of fiber electrodes CFs@UiO-66/PPY, CFs@UiO-66/PPY (no DA), CFs@PPYPDA, and CFs@PPY also demonstrate the same results as CV analysis. Charging/discharging curves of CFs@UiO-66/PPY at different current densities of 50-400 µA cm-1 in Figure 3d exhibit a decent capacitive ACS Paragon Plus Environment

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behavior with a triangle-type sharp and high reversibility as well as small voltage drop. Moreover, the phenomenon of potential platform in charging/discharging is caused by a pseudocapacitance characterization of charge transfer reaction or electrochemical absorption/desorption process at the electrode/electrolyte interface. At a low current density, the charge transfer reaction is more thorough and the electrolyte ions can enter more active surface areas to make them be fully charged, so the potential platform is more obvious with longer time than that at a high current density.21, 43, 44 The EIS Nyquist plot of CFs@UiO-66/PPY shows a very small depressed semicircle related to high conductivity for charge transfer process at the original high-frequency region (Figure 3e). The equivalent series resistance (ESR) calculated from the high-frequency intercept of the semicircle on the real axis is 6.8 Ω cm-1. At the low-frequency region, a closely vertical line indicates a good capacitive behavior corresponding to the charge storage with little ions diffusion resistance and closer to an ideal capacitor.12, 21 CFs@UiO-66/PPY fiber electrode also exhibits a stable cycling performance, which retains 96% of its initial capacitance over 1000 cycles at a scan rate of 100 mV s-1 (Figure 3f). Capacitance of CFs@PPY-PDA also retains as high as 90%, while the capacitance retention of CFs@UiO-66/PPY (no DA) is only 82% and still on the downward trend over 1000 CV cycles (Figure S4, SI). It would be speculated that the electropolymerization of dopamine and incorporation of polydopamine may also enhance the cycling stability for the whole composite.41, 45


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Figure 4. Electrochemical performance of the fiber supercapacitor device: (a) CV curves and (b) length and areal capacitances at different scan rates. (c) Galvanostatic charging/discharging curves and (d) length and areal capacitances at different current densities. (e) Electrochemical impedance spectroscopy (EIS). (f) Ragone plots with length and areal energy and power densities, compared with some fiber supercapacitors (FS) in references.

The assembled all-solid-state flexible fiber supercapacitor device based on CFs@UiO-66/PPY is further investigated by a two-electrode system. All the specific capacitances are calculated based on the whole fiber device. As the CV scan rate increases from 5 to 100 mV s-1 (Figure 4a), the length capacitance decreases from 10 to 4.5 mF cm-1, corresponding to the areal capacitance from 206 to 93 mF cm-2 (Figure 4b). Length capacitance, the vital criterion to reflect the effective specific capacitance of the fibrous device in applications of flexibly wearable electronics, of our device is much higher than many other prior fibrous devices reported (Figure S5a, SI), demonstrating a promising potential of this MOF/CP (UiO-66/PPY) hybrid based fiber ACS Paragon Plus Environment

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supercapacitor. The gravimetric and volumetric capacitances at different scan rates were also calculated (Figure S5b, SI). Galvanostatic charging/discharging curves shown in Figure 4c exhibit a good capacitive behavior of linear profile, symmetrical triangular shape and low voltage drop. The corresponding length, areal, gravimetric and volumetric capacitances at different discharging current densities are calculated and shown in Figures 4d (Figure S5c, SI). The ESR of the device is calculated as 8.1 Ω cm-1 and the quasi-vertical straight line at lowfrequency in EIS also indicates a good capacitive behavior (Figure 4e). Ragone plots with length and areal power and energy densities demonstrates that the maximum power density of 132 µW cm-1 (2102 µW cm-2) and the highest energy density of 0.8 µWh cm-1 (12.8 µWh cm-2) are achieved, which are much better than some other fiber supercapacitor devices in the previous literatures reported (Figure 4f).7, 12, 46-52 Ragone plots with gravimetric and volumetric power and energy densities were also calculated (Figure S5d, SI).

Figure 5. Flexible and feasible performance of the fiber supercapacitor device: Capacitance retentions at different bending angles (a), different bending times under straight and frizzy cycles (b), different temperatures (c), and different cyclic numbers ACS Paragon Plus Environment

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of repeated heating/cooling (d). (e) Cycling stability of the device measured at a discharging current density of 200 µA cm-1 (at straight condition, 25 oC) for 10,000 cycles. (f) LED lighting using three fiber supercapacitors connected in series (corresponding to 15 cm in active length) and the supercapacitor fibers woven into a common cotton cloth.

Furthermore, to evaluate the practical flexible performance of such fiber device, it was operated under straight, different bending angles and frizzy conditions to test the flexible property (Figure 5a). The capacitance of the device exhibits only a small decrease of less than 5% upon bending at different angles and frizzy tests (CV tested at 25 oC). At the continuous frizzy cycles, CV curves (tested at straight condition, 25 oC) show no obvious deterioration and after 1000 frizzy cycles, the device still retains 96% of its initial capacitance (Figure 5b), performing its excellent mechanical flexibility. The working-temperature-dependent (-15 to 100 oC) capacitances were also investigated (Figure 5c). It is clear that the capacitance (CV tested at straight condition) increases with the working temperature increasing from -15 to 100 oC, due to the fact of higher ion conductivity and faster electrode reactions at higher temperatures. The capacitances of fiber supercapacitor at -15 oC and 100 o

C account for ~70% and ~105% of the value at 25 oC respectively, implying that the device possesses a wide

working temperature performance with a high capacitance efficiency at a low temperature and a good stability at a high temperature. At repeated heating (100 oC)/cooling (-15 oC) process, the fiber supercapacitor shows no degradation in capacitive property (CV tested at straight condition, 25 oC) after 100 heating/cooling cycles (Figure 5d), demonstrating its excellent temperature-stability. More importantly, this fiber supercapacitor also exhibits a stable long-term charging/discharging cycling performance, which maintains the capacitance retention of 89% over 10,000 cycles at a charging/discharging current density of 200 µA cm-1 (Figure 5e). To evaluate the feasibility of this device, three series-connected devices with an active length of each 5 cm were charged by three AA batteries in series for 30 s and successfully lighted up a red light-emitting diode (LED), as shown in Figure 5f. In addition, due to the good flexibility, our supercapacitor fibers can be easily woven into textiles such as a common cotton cloth for powering small electronic devices (Figure 5f), suggesting the feasible application of such MOF-based supercapacitor fibers for energy storage in the textile electronics.

CONCLUSIONS


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In summary, this study demonstrates a facile strategy to design and fabricate a MOF/CP hybrid for allsolid-state fabric fiber supercapacitor. Electropolymerization of dopamine and incorporation of polydopamine into the composite as a binder could be the key to realize the one-pot electrodeposition of uniform UiO-66/PPY hybrid. Higher capacitance is derived from the synergistic effect of hybridizing UiO-66 and PPY, which benefited from the EDLC through porosity of UiO-66 and conductivity of PPY as well as the pseudocapacitance of PPY. The assembled all-solid-state fiber supercapacitor based on CFs@UiO-66/PPY exhibits an outstanding capacitive behavior, excellent mechanical flexibility, wide temperature performance, and stable long-term cycling life. The flexible supercapacitor fiber can be easily woven into common cotton cloth, confirming its high feasibility as an energy storage component in textile electronics. This work paves the way for not only a novel construction of MOF/CP hybrid materials but also a promising paradigm of powered systems in flexible and wearable textile electronics.

ASSOCIATED CONTENT

Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami. Additional experimental section and spectroscopic, microscopic and electrochemical characterization (PDF)

AUTHOR INFORMATION

Corresponding Authors *E-mail (B. Y. Xia): [email protected]. *E-mail (H. Duan): [email protected]. Notes The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS

This work is financially supported by Ministry of Education-Singapore (RG49/16) and National 1000 Young Talents Program of China. The authors thank the financial support by the Innovation Foundation of Shenzhen Government (JCYJ20160408173202143), Fundamental Research Funds for the Central University ACS Paragon Plus Environment

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(2017KFXKJC002), Natural Science Foundation of Hubei Committee (2016CFA001) and Fundamental Research Funds of Huazhong University of Science and Technology (3004013109, 0118013089, and 2017KFYXJJ164). We also acknowledge the support of Analytical and Testing Center of Huazhong University of Science and Technology for XRD, SEM, FT-IR measurements.

REFERENCES

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Table of Contents

Metal-organic framework/polypyrrole hybrid is constructed for an all-solid-state fibrous supercapacitor, demonstrating a promising feasibility in energy storage for textile electronics.


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Conductive Polymer Hybrid

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