Self-healable wire-shaped supercapacitors with two twisted NiCo<sub>2</sub>O<sub>4</sub> coated polyvinyl alcohol hydrogel fibers

Rui Jia; La Li; Yuanfei Ai; Hui Du; Xiaodong Zhang; Zhaojun Chen; Guozhen Shen

doi:10.1007/s40843-017-9177-5

SCIENCE CHINA Materials

Download PDF

SCIENCE CHINA Materials, Volume 61, Issue 2: 254-262(2018) https://doi.org/10.1007/s40843-017-9177-5

Self-healable wire-shaped supercapacitors with two twisted NiCo₂O₄ coated polyvinyl alcohol hydrogel fibers

Rui Jia^1,2,?, La Li^2,?, Yuanfei Ai², Hui Du¹, Xiaodong Zhang¹, Zhaojun Chen^1,*, Guozhen Shen^2,3,*

More info

ReceivedNov 8, 2017
AcceptedDec 8, 2017
PublishedJan 12, 2018

Previous Table of Contents Next

Rating

Abstract

Wire-shaped supercapacitors (SCs) possessing light-weight, good flexibility and weavability have caught much attention, but it is still a challenge to extend the lifespan of the devices with gradual aging due to the rough usage or external factors. Herein, we report a new stretchable and self-healable wire-shaped SC. In the typical process, two polyvinyl alcohol/potassium hydroxide (PVA/KOH) hydrogel wrapped with urchin-like NiCo₂O₄ nanomaterials were twisted together to form a complete SC devices. It is noted that the as-prepared PVA hydrogel can be easily stretched up to 300% with small tensile stress of 12.51?kPa, superior to nearly 350?kPa at 300% strain of the polyurethane. Moreover, the wire-like SCs exhibit excellent electrochemical performance with areal capacitance of 3.88?mF?cm^?2 at the current density of 0.053?mA?cm^?2, good cycling stability maintaining 88.23% after 1000 charge/discharge cycles, and 82.19% capacitance retention even after four damaging/healing cycles. These results indicate that wire-shaped SCs with two twisted NiCo₂O₄ coated polyvinyl alcohol hydrogel fibers is a promising structure for achieving the goal of high stability and long-life time. This work may provide a new solution for new generation of self-healable and wearable electronic devices.

Funded by

Beijing Natural Science Foundation(4162062)

CAS(QYZDY-SSW-JSC004)

and the Key Research Program of Frontiers Sciences

the National Natural Science Foundation of China(61625404)

Acknowledgment

This work was supported by the National Natural Science Foundation of China (61625404 and 61504136), Beijing Natural Science Foundation (4162062), and the Key Research Program of Frontiers Sciences, CAS (QYZDY-SSW-JSC004).

Interest statement

The authors declare no conflict of interest.

Contributions statement

Jia R and Li L contributed equally to this work. The paper was written through contributions of all authors. All authors have given approval to the final version of the paper.

Author information

Rui Jia received her BE degree from Huaqiao University in 2015. Now she is a master student at the College of Chemistry and Chemical Engineering, Qingdao University. Her research interest focuses on flexible supercapacitors.

La Li received her BSc degree from Jilin University in 2013. She is a PhD candidate at the College of Physics, Jilin University, China. Her research interests mainly focus on flexible micro-supercapacitors and self-powered integrated devices.

Zhaojun Chen received his BE degree and MSc degree from Qingdao University in 2000 and 2005, respectively, and received his PhD degree from China University of Petroleum in 2015. He is currently an Associate Professor at Qingdao University. His current research focuses on the design and synthesis of novel nanostructure materials for applications in supercapacitors, biomedical materials and catalysts.

Guozhen Shen received his BSc degree in 1999 from Anhui Normal University and PhD degree in 2003 from the University of Science and Technology of China. From 2004 to 2009, he conducted his research in Hanyang University (Korea), National Institute for Materials Science (Japan), University of Southern California (USA) and Huazhong University of Science and technology. He joined the Institute of Semiconductors, Chinese Academy of Sciences as a professor in 2013. His current research focuses on flexible electronics and printable electronics, including transistors, photodetectors, sensors and flexible energy-storage devices.

Supplement

Supporting data are available in the online version of the paper.

References

[1] Liu N, Ma W, Tao J, et al. Cable-type supercapacitors of three-dimensional cotton thread based multi-grade nanostructures for wearable energy storage. Adv Mater, 2013, 25: 4925-4931 CrossRef PubMed Google Scholar

[2] Shim BS, Chen W, Doty C, et al. Smart electronic yarns and wearable fabrics for human biomonitoring made by carbon nanotube coating with polyelectrolytes. Nano Lett, 2008, 8: 4151-4157 CrossRef PubMed ADS Google Scholar

[3] Zhong J, Zhang Y, Zhong Q, et al. Fiber-based generator for wearable electronics and mobile medication. ACS Nano, 2014, 8: 6273-6280 CrossRef PubMed Google Scholar

[4] Xie K, Wei B. Materials and structures for stretchable energy storage and conversion devices. Adv Mater, 2014, 26: 3592-3617 CrossRef PubMed Google Scholar

[5] Xu Y, Lin Z, Huang X, et al. Flexible solid-state supercapacitors based on three-dimensional graphene hydrogel films. ACS Nano, 2013, 7: 4042-4049 CrossRef PubMed Google Scholar

[6] Tao J, Liu N, Ma W, et al. Solid-state high performance flexible supercapacitors based on polypyrrole-MnO₂-carbon fiber hybrid structure. Sci Rep, 2013, 3: 2286 CrossRef PubMed ADS Google Scholar

[7] Jiang K, Wang J, Li Q, et al. Superaligned carbon nanotube arrays, films, and yarns: a road to applications. Adv Mater, 2011, 23: 1154-1161 CrossRef Google Scholar

[8] Deng F, Lu W, Zhao H, et al. The properties of dry-spun carbon nanotube fibers and their interfacial shear strength in an epoxy composite. Carbon, 2011, 49: 1752-1757 CrossRef Google Scholar

[9] Peng H, Jain M, Peterson DE, et al. Composite carbon nanotube/silica fibers with improved mechanical strengths and electrical conductivities. Small, 2008, 4: 1964-1967 CrossRef PubMed Google Scholar

[10] Wang Q, Wang X, Xu J, et al. Flexible coaxial-type fiber supercapacitor based on NiCo₂O₄ nanosheets electrodes. Nano Energ, 2014, 8: 44-51 CrossRef Google Scholar

[11] Kou L, Huang T, Zheng B, et al. Coaxial wet-spun yarn supercapacitors for high-energy density and safe wearable electronics. Nat Commun, 2014, 5: 3754 CrossRef PubMed ADS Google Scholar

[12] Zhang D, Miao M, Niu H, et al. Core-spun carbon nanotube yarn supercapacitors for wearable electronic textiles. ACS Nano, 2014, 8: 4571-4579 CrossRef PubMed Google Scholar

[13] Jian M, Wang C, Wang Q, et al. Advanced carbon materials for flexible and wearable sensors. Sci China Mater, 2017, 60: 1026-1062 CrossRef Google Scholar

[14] Raymundo-Pi?ero E, Cadek M, Wachtler M, et al. Carbon nanotubes as nanotexturing agents for high power supercapacitors based on seaweed carbons. ChemSusChem, 2011, 4: 943-949 CrossRef PubMed Google Scholar

[15] Wang X, Lu X, Liu B, et al. Flexible energy-storage devices: design consideration and recent progress. Adv Mater, 2014, 26: 4763-4782 CrossRef PubMed Google Scholar

[16] Huang L, Yi N, Wu Y, et al. Multichannel and repeatable self-healing of mechanical enhanced graphene-thermoplastic polyurethane composites. Adv Mater, 2013, 25: 2224-2228 CrossRef PubMed Google Scholar

[17] Hager MD, Greil P, Leyens C, et al. Self-healing materials. Adv Mater, 2010, 22: 5424-5430 CrossRef PubMed Google Scholar

[18] Huang Y, Zhu M, Huang Y, et al. Multifunctional energy storage and conversion devices. Adv Mater, 2016, 28: 8344-8364 CrossRef PubMed Google Scholar

[19] Sun H, You X, Jiang Y, et al. Self-healable electrically conducting wires for wearable microelectronics. Angew Chem Int Ed, 2014, 53: 9526-9531 CrossRef PubMed Google Scholar

[20] Xue Q, Sun J, Huang Y, et al. Recent progress on flexible and wearable supercapacitors. Small, 2017, 13: 1701827 CrossRef PubMed Google Scholar

[21] Huang Y, Zhong M, Shi F, et al. An intrinsically stretchable and compressible supercapacitor containing a polyacrylamide hydrogel electrolyte. Angew Chem Int Ed, 2017, 56: 9141-9145 CrossRef PubMed Google Scholar

[22] Wang S, Liu N, Su J, et al. Highly stretchable and self-healable supercapacitor with reduced graphene oxide based fiber springs. ACS Nano, 2017, 11: 2066-2074 CrossRef Google Scholar

[23] Wang H, Zhu B, Jiang W, et al. A mechanically and electrically self-healing supercapacitor. Adv Mater, 2014, 26: 3638-3643 CrossRef PubMed Google Scholar

[24] Wang K, Zhang X, Li C, et al. Chemically crosslinked hydrogel film leads to integrated flexible supercapacitors with superior performance. Adv Mater, 2015, 27: 7451-7457 CrossRef PubMed Google Scholar

[25] Wang DW, Li F, Liu M, et al. 3D aperiodic hierarchical porous graphitic carbon material for high-rate electrochemical capacitive energy storage. Angew Chem Int Ed, 2008, 47: 373-376 CrossRef PubMed Google Scholar

[26] Yuan C, Zhang X, Su L, et al. Facile synthesis and self-assembly of hierarchical porous NiO nano/micro spherical superstructures for high performance supercapacitors. J Mater Chem, 2009, 19: 5772-5777 CrossRef Google Scholar

[27] Wu T, Li J, Hou L, et al. Uniform urchin-like nickel cobaltite microspherical superstructures constructed by one-dimension nanowires and their application for electrochemical capacitors. Electrochim Acta, 2012, 81: 172-178 CrossRef Google Scholar

[28] Li L, Lou Z, Han W, et al. Flexible in-plane microsupercapacitors with electrospun NiFe₂O₄ nanofibers for portable sensing applications. Nanoscale, 2016, 8: 14986-14991 CrossRef PubMed Google Scholar

[29] Wu H, Jiang K, Gu S, et al. Two-dimensional Ni(OH)₂ nanoplates for flexible on-chip microsupercapacitors. Nano Res, 2015, 8: 3544-3552 CrossRef Google Scholar

[30] Ai Y, Lou Z, Li L, et al. Meters-long flexible CoNiO₂-nanowires@carbon-fibers based wire-supercapacitors for wearable electronics. Adv Mater Technol, 2016, 1: 1600142 CrossRef Google Scholar

[31] Wang Z, Tao F, Pan Q. A self-healable polyvinyl alcohol-based hydrogel electrolyte for smart electrochemical capacitors. J Mater Chem A, 2016, 4: 17732-17739 CrossRef Google Scholar

[32] Sun K, Ran F, Zhao G, et al. High energy density of quasi-solid-state supercapacitor based on redox-mediated gel polymer electrolyte. RSC Adv, 2016, 6: 55225-55232 CrossRef Google Scholar

[33] Huang Y, Huang Y, Zhu M, et al. Magnetic-assisted, self-healable, yarn-based supercapacitor. ACS Nano, 2015, 9: 6242-6251 CrossRef Google Scholar

[34] Wang Q, Wang X, Liu B, et al. NiCo₂O₄ nanowire arrays supported on Ni foam for high-performance flexible all-solid-state supercapacitors. J Mater Chem A, 2012, 1: 2468-2473 CrossRef Google Scholar

[35] Wang Q, Liu B, Wang X, et al. Morphology evolution of urchin-like NiCo₂O₄ nanostructures and their applications as psuedocapacitors and photoelectrochemical cells. J Mater Chem, 2012, 22: 21647-21653 CrossRef Google Scholar

[36] Bae J, Song MK, Park YJ, et al. Fiber supercapacitors made of nanowire-fiber hybrid structures for wearable/flexible energy storage. Angew Chem Int Ed, 2011, 50: 1683-1687 CrossRef PubMed Google Scholar

[37] Li L, Chen C, Xie J, et al. The preparation of carbon nanotube/MnO₂ composite fiber and its application to flexible micro-supercapacitor. J Nanomaterials, 2013, 2013: 1-5 CrossRef Google Scholar

[38] Ren J, Li L, Chen C, et al. Twisting carbon nanotube fibers for both wire-shaped micro-supercapacitor and micro-battery. Adv Mater, 2013, 25: 1155-1159 CrossRef PubMed Google Scholar

[39] Huang Y, Zhong M, Huang Y, et al. A self-healable and highly stretchable supercapacitor based on a dual crosslinked polyelectrolyte. Nat Commun, 2015, 6: 10310 CrossRef PubMed ADS Google Scholar

Click to view Download high-quality image

Figure 1
(a) Optical images of the stretchable PVA/KOH hydrogel: stretching from 1.5 to 6?cm by employing one-dimensional platform (left) and twisting on the thumb (upper right). (b) Illustration of the PVA/KOH hydrogel to support a 5?g mass: before damaging (left), after healing (right) and magnified image of the wound positions. (c) Schematic plot of the self-healing mechanism. (d) Tensile tests of the PVA/KOH hydrogel fiber after different damaging/healing cycles. (e) Tensile strengths and Young’s modulus of the PVA/KOH hydrogel fiber after different damaging/healing cycles.
Click to view Download high-quality image

Figure 2
(a, b) SEM images, (c, d) TEM images, (e) HRTEM image and (f) XRD pattern of the obtained urchin-like NiCo₂O₄ nanostructures.
Click to view Download high-quality image

Figure 3
Electrochemical performance of the fabricated wire-like SCs with urchin-like NiCo₂O₄ electrodes. (a) CV curves at different scan rates ranging from 0.1 to 3.0?V?s^?1. (b) GCD curves at different current densities from 0.053 to 0.319?mA?cm^?2 in the potential window of 0–0.8?V. (c) The areal capacitance with various currents. (d) The high-frequency region of Nyquist impedance plot. The inset displays the Nyquist impedance plot of the wire-like SCs. (e) Performance of capacitance stability of the NiCo₂O₄ SC with 1000 cycles. (f) Areal energy and power density of the wire-like SCs. The inset is schematic diagram of the wire-like SC.
Click to view Download high-quality image

Figure 4
The stretchable properties of the wire-like SC devices. (a, b) CV curves and GCD curves under stretching from 0 to 200%. (c) Variation of capacitance stability of the 100% stretching with 1000 cycles. The insets present the photographs of the device under pristine and stretching states. (d) The Nyquist impedance plots of the as-prepared SC with various stretch.
Click to view Download high-quality image

Figure 5
The self-healing properties of wire-like SC device at different cutting/self-healing cycles. (a) CV curves at the scan rate of 3.0?V?s^?1. (b) GCD curves at the current density of 0.106?mA?cm^?2. (c) Capacitance retention of the device after self-healing for 4 cycles. The insets show the photographs of the device under cutting and healing states. (d) The corresponding Nyquist impedance plots with different self-healing times.