Omnidirectional Deformable Energy Textile for Human Joint

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Omnidirection Deformable Energy Textile for Human Joint Movement Compatible Energy Storage Joonwon Lim, Dong Sung Choi, Gil Yong Lee, Ho Jin Lee, Suchithra Padmajan Sasikala, Kyung Eun Lee, Seok Hun Kang, and Sang Ouk Kim ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b14981 • Publication Date (Web): 07 Nov 2017 Downloaded from http://pubs.acs.org on November 9, 2017

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ACS Applied Materials & Interfaces

Omnidirection Deformable Energy Textile for Human Joint Movement Compatible Energy Storage Joonwon Lim, Dong Sung Choi, Gil Yong Lee, Ho Jin Lee, Suchithra Padmajan Sasikala, Kyung Eun Lee, Seok Hun Kang and Sang Ouk Kim*

National Creative Research Initiative Center for Multi-Dimensional Directed Nanoscale Assembly, Department of Materials Science and Engineering, KAIST, Daejeon 34141, Republic of Korea *e-mail: [email protected]

KEYWORDS energy storage, supercapacitors, textile, wearable, carbon nanotubes

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ABSTRACT

Omnidirectional deformability is an unavoidable basic requirement for wearable devices to accommodate human daily motion particularly at human joints. We demonstrate omnidirectionally bendable and stretchable textile-based electrochemical capacitor that retains high power performance under complex mechanical deformation. Judicious synergistic hybrid structure of woven elastic polymer yarns with carbon nanotubes and conductive polymers offers reliable electrical and electrochemical activity even under repeated cycles of severe complex deformation modes. The textile-based electrochemical capacitors exhibit omnidirectional stretchability with 93 % of capacitance retention under repeated 50 % omnidirectional stretching condition while demonstrating excellent specific capacitance (412 mF cm-2) and cycle stability (> 2,000 stretch). The wearable power source stably powers red LED under omnidirectional stretching that accompanies human elbow joint motion.


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INTRODUCTION Research attention on wearable electronics is ever-increasing along with the rapid advent of portable or patchable devices.1-7 Ideal prototype of wearable electronics should be bendable, twistable and stretchable to accommodate our daily mechanical motions, while sustaining the device performance in the undeformed states.8-9 In the past decade, significant amount of research efforts has been devoted to the realization of wearable devices, mainly focusing on the engineering of device structures. For instance, buckling of ultrathin inorganic active materials stabilized on pre-strained elastomeric substrates, successfully realizes uniaxially or biaxially stretchable devices.10-14 Fiber-shaped devices can offer high tolerance for complex mechanical deformation modes owing to the intrinsic one-dimensional geometry.15-24 Nonetheless, significant issue still remains unsolved for the realization of genuine wearable power devices; that is, reliable high power performance even under complex omnidirectional deformation.

In the realm of truly wearable devices, omnidirectional deformability needs to be distinguished from simple bendability or uni- / bi-axial stretchability. While conventional stretchability towards one or a few fixed directions can accommodate only a limited range of physical motions, omnidirectional deformable devices ensure a distinctive degree of freedom for physical movement and comfort. Indeed, practical wearable powering devices are expected to accommodate 50 % of omnidirectional strains to tolerate the large deformation occurring particularly at joints, such as knee, elbow and knuckle.25 Sophisticated strategy is expected in the design of materials and/or the layout of devices for the simultaneous attainment of omnidirectional deformability along with high conductivity and energy storage/supply 3 ACS Paragon Plus Environment


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capability.26 Moreover, development of systematic and standardized analytical methodology for the evaluation of omnidirectional deformability is urgently demanded to resolve the ambiguity among previous relevant approaches.27,28

Textile-integration of powering devices is considered a promising platform for upcoming wearable electronics.29-32 Textile platform offers certain inherent flexibility and stretchability arising from the distinct woven structures, even when composed of inelastic rigid materials. Nonetheless, it is still challenging to synchronize the contradictory goals of high stretchability and reliable electrical conductivity,33 which are indispensable requirements for wearable powering textiles as active materials as well as current collectors. To date, most of researches on textile-based power sources have relied on inelastic textile platform.34-39 In a few rare attempts to employ elastic yarns, the resultant devices have suffered from insufficient cycle stability, commonly caused by the fracture or delamination of rigid active components from the elastic yarns, which deteriorate the electrical connectivity over device architecture during multiple repeated deformation cycles.31,40,41

In this work, we present omnidirectionally deformable textile-based electrochemical capacitors, capable of stable power storage/supply under complex mechanical deformation. A straightforward reliable interfacial treatment method is developed for the commercially available woven elastic polymer yarns based on the solution deposition of carbon nanotubes (CNTs) and the interfacial synthesis of conductive polymer (polyaniline, PANI) layers. Simple capacitor structures consisting of symmetric stacking of the hybrid textiles attain highly stable reliable energy storage and supply 4 ACS Paragon Plus Environment

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under severe complex deformation conditions along with ready adaptability to our typical clothes. We also propose a standardized quantitative evaluation method for the omnidirectional stretchability in the functional device structures as well as in the materials level.

EXPERIMENTAL METHODS Preparation of CNT/textile Aqueous CNT ink was prepared by dispersing MWCNTs with sodium dodecylbenzenesulfonate (SDBS) as surfactant. The mass ratio of CNTs to SDBS was 1 to 5 for aqueous CNT ink of various concentration. Tip-sonication of 20 W was applied to the CNT ink for 1 hour and the resultant CNT ink was centrifuged at 8000 rpm for 1 hour to remove non-dispersed CNT clusters. Stretchable textile made of polyurethane and polyester copolymer was immersed in the as-prepared CNTs ink for 10 minutes and then dried out on hot-plate at 50 ℃ for 2 hours. The CNT-coated stretchable textile (CNT/textile) was washed out with deionized water with vigorous shaking to remove unattached and agglomerated CNT particles on the textile. Subsequent washing with 2 M nitric acid was conducted to completely remove SDBS surfactants adsorbed on the surface of CNTs. Same process was repeated to increase the loading amount of CNT on the stretchable textile.

Preparation of PANI/CNT/textile 0.2 M aniline in 1 M hydrochloric acid (HCl) aqueous solution (20 mL) was prepared for in-situ polymerization of PANI. High purity ethanol (4 mL) was added to the prepared aniline solution. CNT/textile was immersed in ethanol for tens-of-second to improve wettability and then placed into the reaction solution containing aniline monomer for 3 hours in ice bath. 0.1 M ammonium 5 ACS Paragon Plus Environment


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persulfate (APS) in 1 M HCl (20 mL) solution was slowly added drop by drop into the reaction bath. The degree of in-situ polymerization of PANI was controlled by adjusting reaction time. After polymerization reaction, synthesized PANI/CNT/textile was thoroughly washed with ethanol with vigorous shaking to remove undesired PANI particles on the surface of PANI/CNT/textile, and dried out on the hot-plate at 50 ℃ for 2 hours.

Measurement of electrical stability under uniaxial stretching Specimens were stretched by homemade stretching test equipment. Both ends of specimens were clipped by holders with platinum foils for electrical contact for measuring electrical property. The magnitude of applied tensile strain was defined as following formula; The magnitude of applied tensile strain (%) = 100 × (L-L0) / L0 , where L0 and L denote the length of specimen before and after applied tensile strain, respectively. Electrical stability under uniaxial stretching was evaluated with the variation of electrical resistance, as defined as R/R0 where R0 and R denote electrical resistance before and after applied tensile strain, respectively.

Measurement of electrical stability under omnidirectional stretching Omnidirectional stretchability was evaluated by investigating the variation of R/R0 under omnidirectional stretching. Specimens were held by homemade stretching test equipment. All edges of specimen were clipped by holders, and platinum foils are placed at two sides facing each other for electrical contact for measuring electrical property. Omnidirectional stretching was generated by sphere shape strain loader pressing specimen. The degree of applied omnidirectional strains was controlled by adjusting vertical location of sphere loader. The 6 ACS Paragon Plus Environment

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magnitude of omnidirectional strains was defined with the identical formula with that of uniaxial stretching condition. L0 and L denote the sectional line length passing through a tangential point between specimen and sphere loader before and after omnidirectional stretching, respectively. Electrical stability under omnidirectional stretching was evaluated with the variation of electrical resistance (Romni/R0).

Material information and evaluation method for electrochemical performance of supercapacitors are provided in Supporting Information.

RESULTS AND DISCUSSION Omnidirectionally deformable energy textile preparation. Figure 1a illustrates our synthetic route. Highly stretchable textiles woven from elastic polyester-polyurethane copolymer yarns were immersed in aqueous dispersion of CNTs with amphiphilic surfactants (Figure S1). The immersion condition was precisely optimized for a desired uniform and conformal coating quality (Figure 1bd, Figure S2). Several repeated CNT coating cycles (typically 5 times) dramatically decrease the sheet resistance of textile down to 20 Ω/□ (Figure S3). Subsequently, PANI conductive polymer layer was grown from the entire surface of CNT/textile (Figure 1e-g, Figure S4 and S5). Aniline monomers are sufficiently absorbed on the CNT coated textile surface before polymerization so that the following solution polymerization leads to a conformal coating of PANI layer (Figure S4).42,43 PANI forms dense surface layer and plugs the cavities among CNTs and the base textile (Figure S5). The polyester-polyurethane textile used here possesses aromatic moieties that can share π-π interaction with CNTs and PANI chains.44 Besides, -NH- functional groups of PANI may cause hydrogen bondings with the C=O groups of polyester-polyurethane textile to 7 ACS Paragon Plus Environment


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accommodate reliable interfacial adhesion even under severe complex deformation (Figure S6).45 The interfacial interactions enhanced the mechanical property of the textile (Figure S7).

Energy textile under bending, twisting and uniaxial stretching. Any kind of complex mechanical deformation, including those at human skin or clothing can be considered as a combination of bending, twisting and stretching modes. Electrical conductivity of our conductive textiles was characterized under those three different modes. Figure 2a and b show the electrical stabilities of PANI/CNT/textile and CNT/textile (without PANI layer) under bending and twisting, illustrated by the variation of relative resistance, i.e. R/R0, where R0 and R correspond to the electrical resistance before and after deformation, respectively. Interestingly, severe bending to a small radius of 0.1 cm and strong twisting to 180° cause a minor enhancement of electrical conductivity. While the preexisting electrical junctions among CNTs reinforced by PANI layer are well maintained, additional physical electrical contacts can be supplemented under the geometric buckling or wrinkling of textile. The electrical property of our energy textile is also endurable for repeated deformation cycles. After 10,000 cycles of bending or twisting, only a 2 % increase in the electrical resistance was measured (Figure S8).

Figure 2c compares the uniaxial stretchability of PANI/CNT/textile and CNT/textiles, evaluated by the variation of Runi/R0 under tensile stretching toward X-, Y-, or XY-direction, as defined in Figure 2d. For the 50 % of X-, Y- and XY-directional stretching of CNT/textiles, R/R0 values were measured to be 2.06, 1.64 and 1.11, respectively. This direction dependency is obviously ascribed to the anisotropic woven structure of textile. Figure 2d compares the configurational modification 8 ACS Paragon Plus Environment

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of yarns and bundles under stretching towards different directions, observed by scanning electron microscopy (SEM). Given the intrinsic electrical properties of each component, the overall electrical conductivity of textile is determined by the areal density of conductive components (CNTs and PANI) as well as effective electrical junctions between them. The characteristic angle between neighboring woven bundles, denoted by the inner angle of V-shape (insets in Figure 2d), strongly depends on the stretching direction.31 A smaller angle may offer a tighter contact among CNT junctions with larger contact area and lead to an enhanced electrical connectivity. The angles for XY- and Y-directional stretching were 31° and 61°, which is smaller than unstretched state (66°). By contrast, X-directional stretching leads to a large increase in angle (77°) as well as sparse configuration of bundles.

As shown in Figure 2c, the electrical stability under stretching is remarkably improved by in-situ polymerized PANI layer (Figure S9). PANI/CNT/textile exhibited 1.15, 1.06 and 0.94 of Runi/R0 values at the 50 % of X-, Y- and XY-directional stretching, respectively. Conformal coating of PANI improves the electrical connectivity among CNT strands as well as PANI/CNT/polymer yarns by filling the voids among them. It also enhances the mechanical stability of electrical contact junctions and tightens the overlap among woven yarns. The synergistic effect from CNT and PANI coating strengthens the electrical connectivity and prevents the delamination and fracture of composite structure even under severe complex deformation (Figure S10-S12).

Omnidirectional stretchability of energy textile. Omnidirectional stretchability of our energy textile was quantitatively evaluated, as illustrated in Figure 3a. For an equivalent tensile stretching 9 ACS Paragon Plus Environment


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towards every direction, we used a solid sphere tensile loader. The sphere-loaded textile surface generates isotropic tensile strains from the tangent points with sphere surface to every direction. The applied tensile strain can be quantified by the ratio of initial length (L0) to a length increment (L-L0) of specimen. The magnitude of stretching was simply controlled by the vertical location of spherical loader. Investigation on the variation of electrical stability (Romni/R0) along with the degree of omnidirectional stretching rationally quantifies the omnidirectional stretchability of a specimen. Notably, this evaluation method also facilitates the diverse stretching situations with different surface curvatures by employing different radius of sphere loader (Figure S13). For instance, stretching and bending motions on the knee, the elbow and the knuckle have different surface curvatures. The radius of curvature of sphere loader used in this work was 11 mm, which can cover human’s motions on knee, shoulder and elbow, on which the radii of curvatures are known to be 20 mm and over.46,47

According to the suggested methodology, we evaluated the omnidirectional stretchability of PANI/CNT/textile. Polymer-free textile (CNT/textile) was investigated again as a reference to verify the reinforcing effect from PANI layer. Figure 3b shows SEM image of omnidirectionally stretched PANI/CNT/textile. Figure 3c presents that PANI/CNT/textile exhibits a very small increase of Romni/R0 up to 20 %, followed by gradual decline even below the initial resistance value. Noteworthy that the variation of Romni/R0 shows a similar trend with that of Runi/R0 for unidirectional tensile stretching (Figure S14). The exact resistance variation follows the order of Runi-XY/R0 < Romni/R0 < Runi-X/R0. Approximately, omnidirectional stretching can be regarded as the summation of tensile stretching over all radial directions. The equivalent circuit may be 10 ACS Paragon Plus Environment

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simply displayed with the parallel circuits of all radical resistor components (Figure S15). According to Ohm’s law, the smallest resistor governs the total resistance of a parallel electric circuit. Consequently, the Romni/R0 stretching follows the minimum R/R0 curve for unidirectional stretching, i.e., the Runi-XY/R0 for XY-directional stretching. CNT/textile showed a similar tendency in the electrical behavior. However, electrical stability is noticeably poor without PANI layer. Figure 3d shows the cycle stability for repeated omnidirectional stretching. PANI/CNT/textile is highly reliable even after the repeated 50 %-omnidirectional stretching up to 2,000 cycles (Romni/R0 increase: 5 %).

Energy storage/supply capability of textile-based electrochemical capacitors under omnidirectional stretching. Electrochemical performances of PANI/CNT/textile- and CNT/textile-based electrochemical capacitors were characterized in a symmetric device configuration. The devices were composed of textile separators infiltrated with polyvinyl alcohol (PVA)/H3PO4 aqueous gel electrolyte, sandwiched between two textile electrodes (Figure 4a, Figure S16). Cyclic voltammetry (CV) and galvanostatic charge/discharge cycles were measured between 0-0.8 V. Figure 4b shows the CV curves for scan rates from 5 to 40 mV s-1. Compared to CNT/textile capacitor, PANI/CNT/textile-capacitor shows substantially large inner area of CV curve, owing to the redox activity of PANI layer.48,49 Figure S17 presents the typical charge/discharge profiles for current densities from 0.2 to 0.8 mA cm-2 (current: 0.5 to 2 mA). The specific areal capacitance of PANI/CNT/textile-capacitor reaches 412 mF cm-2 at 0.5 mA cm-2, which is about eightyfold enhancement from CNT/textile-capacitor (Figure 4c). The specific gravimetric capacitance of PANI/CNT/textile-capacitor was also calculated to be 211 F g-1 at 0.2 mA cm-2, comparable to those of high performance PANI-based electrochemical 11 ACS Paragon Plus Environment


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capacitors (without mechanical deformability) reported thus far.50,51 Additionally, textilecapacitors showed an outstanding stability up to 10,000 cycles of charge/discharge (Figure S18). The capacitance of PANI/CNT/textile-capacitor gradually increased up to 5,000 cycles primarily due to the electrochemical activation of PANI and the improvement in the wetting of gel electrolyte at textile surfaces.

Figure 4d is a schematic illustration of the omnidirectional stretchability of our PANI/CNT/textile-capacitor. Discharge profiles in the galvanostatic measurements show no distinct modification under the omnidirectional stretching up to 50 % (Figure 4e). Energy capacity retained 95 % of original capacitance (Figure 4f) and moreover, maintained 93 % of capacitance after 2,000 cycles of stretching (Figure 4g). While the electrochemical activity of energy textile is dominated by CNT and PANI layers, their effective surface area and electrical conductivity are well-preserved under the severe deformation of textile. We also evaluated our textile-capacitors under bending and twisting deformations. The capacitors retained their original CV curves under harsh bending up to 0.1 cm bending radius and 90° twisting condition (Figure S19). Even under a dynamic strain operation, the electrochemical performance was wellmaintained with stable CV curves (Movie S1). Ragone plot in Figure 4h compares the areal (red circles) and gravimetric (blue circle) power and energy densities of PANI/CNT/textile-capacitor with other uniaxial or biaxial stretchable electrochemical capacitors reported thus far.13,17,18,52-57 The maximal areal and gravimetric energy densities of the as-prepared device are 36.7 μWh cm-2 and 18.7 Wh kg-1 with high power densities of 0.11 mW cm-2 and 58.3 W kg-1, respectively. The outstanding energy storage/supply capability retained 95 % of original energy and power densities under 50 %-omnidirectional stretching (star). As a demonstration of device application, 12 ACS Paragon Plus Environment

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three 25 cm2 PANI/CNT/textile-capacitors with PVA/LiCl gel electrolyte were serially connected to light up a red light-emitting diode (LED) (Figure S20). By virtue of high energy capacity of our devices, the LED lighting prolonged over 1 hour with a single full charge. The sustainability of LED lighting was also tested under repeated omnidirectional stretching/releasing. Interestingly, LED maintained its original brightness without any noticeable flickering or diminishing of intensity under the dynamic deformation cycles, as shown in Figure 4i (Movie S2). The energy textile capacitors could also be integrated into our daily clothes as wearable power sources compatible to human elbow joint motion for lighting LED (Movie S3 and S4).

CONCLUSION Electrochemically active hybrid textile structure is introduced for the high performance wearable energy storage adaptable to the complex omnidirectional deformation at human joints. The platform presented here relies on three key design features for truly wearable power devices: (1) providing omnidirectional deformability with elastic and woven substrate structure, (2) retaining electrical activity for energy delivery under repeated mechanical deformation with robust interfacial treatment with CNT/conductive polymer layer and (3) facilitating active redox behavior for high energy storage with in-situ polymerized conductive polymers. Significantly, intimate conformal interfacial growth of conductive polymers effectively strengthen the physical junctions among one-dimensional CNT strands such that electrical conductive pathway through CNT network structure is well-sustained even under complex large deformation modes and provides highly stable electrical and electrochemical performances. This rational material design and integration concept represents a typical instance generally applicable to many different 13 ACS Paragon Plus Environment


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wearable devices other than energy storage. We also propose a methodology for the quantitative evaluation of omnidirectional stretchability for functional materials and devices, while imposing well-defined deformation analogous to human joint motion. Overall, this study defines the importance of deformability towards arbitrary direction for the practical utilization of wearable materials and devices, and suggests a viable way to cloth-integrated electronics.


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Figure 1. Omnidirectional deformable energy textile preparation. (a) Synthetic procedure for PANI/CNT/textile composite structure. (b-d) SEM images of CNT/textile composites. (e-g) SEM images of PANI/CNT/textile composites. Scale bars are 2 μm in b, e, 200 nm in c, f, 10 μm in d, g.



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Y

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Tensile strain (%) Figure 2. Electrical stability of PANI/CNT/textile and CNT/textile under diverse mechanical deformation modes. (a, b) Variation of electrical resistance for PANI/CNT/textile and CNT/textile under bending and twisting conditions; Insets are optical images for bending and twisting test. (c) Variation of electrical resistance for PANI/CNT/textile and CNT/textile under tensile stretching. X, Y and XY indicate stretching direction as indicated in d. (d) SEM images of textiles (black edge, top-left) under 100 % stretching toward ii) X-, iii) Y-, and iv) XY- direction; Insets are high magnification SEM images showing the corresponding angle changes between neighboring yarns. Scale bars are 500 nm.


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Pressure

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Figure 3. Quantitative evaluation of omnidirectional deformability. (a) Schematic illustration of quantitative evaluation method for omnidirectional stretchability (top) and real experimental setup (bottom). (b) SEM images of textiles under omnidirectional stretching; Insets are high magnified SEM images showing the corresponding angle changes between neighboring yarns. Scale bars are 500 nm. (c) Variation of electrical resistance of PANI/CNT/textile and CNT/textile under omnidirectional tensile loading. (d) Cycle stability of PANI/CNT/textile (closed symbols) and CNT/textile (open symbols) with repeated 20 % omnidirectional stretching.



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102 101

Figure 4. Electrochemical capacitors made from PANI/CNT/textile and CNT/textile. (a) Device configuration of electrochemical capacitors assembled from textile electrodes and phosphoric acid/PVA gel electrolyte. (b) Cyclic voltammograms of textile-based electrochemical capacitors at various scan rates. (c) Areal specific capacitance vs. current density. (d) Schematic illustration of evaluation method for omnidirectional stretchability of electrochemical capacitors. (e) Galvanostatic charge/discharge curves under various omnidirectional stretching levels. (f) Capacitance retention under various omnidirectional stretching levels. (g) Cycle stability of 18 ACS Paragon Plus Environment

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PANI/CNT/textile capacitors under repeated 20 % omnidirectional stretching. (h) Ragone plot with previously reported stretchable electrochemical capacitors. (i) Red LED lightening powered by three PANI/CNT/textile electrochemical capacitors in a series under omnidirectional stretching with finger pressure.



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ASSOCIATED CONTENT Supporting Information Experimental procedures and Materials characterization, Figure S1-S20 Movie showing bending and twisting test Movie showing lighting LED powered by energy textiles under omnidirectional stretching Movie showing lighting LED powered by energy textiles under human elbow motion This material is available free of charge via the Internet at http://pubs.acs.org.

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

Author Contributions J. L. principally performed the experiments and leaded this project. S.O.K. supervised the entire project. S.O.K. and J.L. conceived the idea and designed the overall experiments. J. L., H. J. L., S. P. S. and S. H. K carried out the materials synthesis, characterizations and fabrication of textile-based capacitors. D.S.C., G.Y.L and K. E. L. performed X-ray photoelectron spectroscopy and Raman spectroscopy measurements, and analyzed the results. All authors cowrote the paper and participated in discussions.


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Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work was supported by the KOLON Corporation, Korea, through the KOLON-KAIST Lifestyle Innovation Center Project (LSI14-MAKSW0001), the Multi-Dimensional Directed Nanoscale Assembly Creative Research Initiative (CRI) Center (2015R1A3A2033061) and the Nano-Material Technology Development Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (2016M3A7B4905613).

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TOC figure

PANI/CNT/textile

Releasing

Stretching


Omnidirectional Deformable Energy Textile for Human Joint

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