Inkjet-Printed Electrodes on A4 Paper Substrates for Low-Cost, Disposable, and Flexible Asymmetric Supercapacitors.

Printed electronics is widely gaining much attention for compact and high-performance energy-storage devices because of the advancement of flexible electronics. The development of a low-cost current collector, selection, and utilization of the proper material deposition tool and improvement of the device energy density are major challenges for the existing flexible supercapacitors. In this paper, we have reported an inkjet-printed solid-state asymmetric supercapacitor on commercial A4 paper using a low-cost desktop printer (EPSON L130). The physical properties of all inks have been carefully optimized so that the developed inks are within the printable range, i.e., Fromm number of 4 < Z < 14 for all inks. The paper substrate is made conducting (sheet resistance ∼ 1.6 Ω/sq) by printing 40 layers of conducting graphene oxide (GO) ink on its surface. The developed conducting patterns on paper are further printed with a GO-MnO2 nanocomposite ink to make a positive electrode, and another such structure is printed with activated carbon ink to form a negative electrode. A combination of both of these electrodes is outlaid by fabricating an asymmetric supercapacitor. The assembled asymmetric supercapacitor with poly(vinyl alcohol) (PVA)-LiCl gel electrolyte shows a stable potential window of 0-2.0 V and exhibits outstanding flexibility, good cyclic stability, high rate capability, and high energy density. The fabricated paper-substrate-based flexible asymmetric supercapacitor also displays an excellent electrochemical performances, e.g., a maximum areal capacitance of 1.586 F/cm2 (1023 F/g) at a current density of 4 mA/cm2, highest energy density of 22 mWh/cm3 at a power density of 0.099 W/cm3, a capacity retention of 89.6% even after 9000 charge-discharge cycles, and a low charge-transfer resistance of 2.3 Ω. So, utilization of inkjet printing for the development of paper-based flexible electronics has a strong potential for embedding into the next generation low-cost, compact, and wearable energy-storage devices and other printed electronic applications.

[1]  J. E. Fromm,et al.  Numerical calculation of the fluid dynamics of drop-on-demand jets , 1984 .

[2]  Yang Li,et al.  Nanoporous Ni(OH)2 thin film on 3D Ultrathin-graphite foam for asymmetric supercapacitor. , 2013, ACS nano.

[3]  Xu Xiao,et al.  Paper-based supercapacitors for self-powered nanosystems. , 2012, Angewandte Chemie.

[4]  L. Lan,et al.  All Inkjet-Printed Metal-Oxide Thin-Film Transistor Array with Good Stability and Uniformity Using Surface-Energy Patterns. , 2017, ACS applied materials & interfaces.

[5]  N. Munichandraiah,et al.  Synthesis and Characterization of Nano- MnO2 for Electrochemical Supercapacitor Studies , 2008 .

[6]  Sang-Young Lee,et al.  All-inkjet-printed, solid-state flexible supercapacitors on paper , 2016 .

[7]  Joo-Yun Jung,et al.  Ferroelectric Zinc Oxide Nanowire Embedded Flexible Sensor for Motion and Temperature Sensing. , 2017, ACS applied materials & interfaces.

[8]  C. Zhi,et al.  Enhanced tolerance to stretch-induced performance degradation of stretchable MnO2-based supercapacitors. , 2015, ACS applied materials & interfaces.

[9]  Matiar M. R. Howlader,et al.  Inkjet Printing of a Highly Loaded Palladium Ink for Integrated, Low‐Cost pH Sensors , 2016 .

[10]  Yong Ding,et al.  Hydrogenated ZnO core-shell nanocables for flexible supercapacitors and self-powered systems. , 2013, ACS nano.

[11]  Xue-Feng Lu,et al.  Asymmetric Paper Supercapacitor Based on Amorphous Porous Mn3O4 Negative Electrode and Ni(OH)2 Positive Electrode: A Novel and High-Performance Flexible Electrochemical Energy Storage Device. , 2015, ACS applied materials & interfaces.

[12]  K. Liang,et al.  Paper-Based Inkjet-Printed Flexible Electronic Circuits. , 2016, ACS applied materials & interfaces.

[13]  P. Hu,et al.  Self-assembly of ultrathin MnO2/graphene with three-dimension hierarchical structure by ultrasonic-assisted co-precipitation method , 2016 .

[14]  Qiuquan Guo,et al.  Fabrication of flexible copper-based electronics with high-resolution and high-conductivity on paper via inkjet printing , 2014 .

[15]  G. Jabbour,et al.  Inkjet Printing—Process and Its Applications , 2010, Advanced materials.

[16]  Weijie Liu,et al.  Inkjet printing of conductive patterns and supercapacitors using a multi-walled carbon nanotube/Ag nanoparticle based ink , 2015 .

[17]  Candace K. Chan,et al.  Printable thin film supercapacitors using single-walled carbon nanotubes. , 2009, Nano letters.

[18]  Mathieu Toupin,et al.  Charge Storage Mechanism of MnO2 Electrode Used in Aqueous Electrochemical Capacitor , 2004 .

[19]  Jooho Moon,et al.  Influence of fluid physical properties on ink-jet printability. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[20]  Weijie Liu,et al.  Fully screen printed highly conductive electrodes on various flexible substrates for asymmetric supercapacitors , 2015 .

[21]  MinHo Yang,et al.  Coaxial RuO₂-ITO nanopillars for transparent supercapacitor application. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[22]  W. S. Hummers,et al.  Preparation of Graphitic Oxide , 1958 .

[23]  F. Wei,et al.  Fast and reversible surface redox reaction of graphene–MnO2 composites as supercapacitor electrodes , 2010 .

[24]  Sungho Jeong,et al.  Subdermal Flexible Solar Cell Arrays for Powering Medical Electronic Implants , 2016, Advanced healthcare materials.

[25]  Jeffrey W. Long,et al.  To Be or Not To Be Pseudocapacitive , 2015 .

[26]  Peihua Huang,et al.  Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon. , 2010, Nature nanotechnology.

[27]  Y. Bando,et al.  Cable‐Type Supercapacitors of Three‐Dimensional Cotton Thread Based Multi‐Grade Nanostructures for Wearable Energy Storage , 2013, Advanced materials.

[28]  Y. Tong,et al.  Design and synthesis of MnO₂/Mn/MnO₂ sandwich-structured nanotube arrays with high supercapacitive performance for electrochemical energy storage. , 2012, Nano letters.

[29]  Siyuan Ma,et al.  Fabrication of Novel Transparent Touch Sensing Device via Drop-on-Demand Inkjet Printing Technique. , 2015, ACS applied materials & interfaces.

[30]  C. R. Raj,et al.  Facile shape-controlled growth of hierarchical mesoporous δ-MnO2 for the development of asymmetric supercapacitors , 2016 .

[31]  Wei Li,et al.  Layered-MnO₂ Nanosheet Grown on Nitrogen-Doped Graphene Template as a Composite Cathode for Flexible Solid-State Asymmetric Supercapacitor. , 2016, ACS applied materials & interfaces.

[32]  M. El‐Kady,et al.  Laser Scribing of High-Performance and Flexible Graphene-Based Electrochemical Capacitors , 2012, Science.

[33]  R. Sun,et al.  Flexible Asymmetrical Solid-State Supercapacitors Based on Laboratory Filter Paper. , 2016, ACS nano.

[34]  Zijian Zheng,et al.  Wearable energy-dense and power-dense supercapacitor yarns enabled by scalable graphene–metallic textile composite electrodes , 2015, Nature Communications.

[35]  Y. Tong,et al.  Flexible Cellulose Paper‐based Asymmetrical Thin Film Supercapacitors with High‐Performance for Electrochemical Energy Storage , 2014, Advanced Functional Materials.

[36]  Weilie Zhou,et al.  Three-Dimensional Cobalt Phosphide Nanowire Arrays as Negative Electrode Material for Flexible Solid-State Asymmetric Supercapacitors. , 2017, ACS applied materials & interfaces.

[37]  Yury Gogotsi,et al.  Materials science: Energy storage wrapped up , 2014, Nature.

[38]  Seung Hwan Ko,et al.  Ag/Au/Polypyrrole Core-shell Nanowire Network for Transparent, Stretchable and Flexible Supercapacitor in Wearable Energy Devices , 2017, Scientific Reports.

[39]  Eunsung Lee,et al.  Synthesis and characterization of manganese dioxide spontaneously coated on carbon nanotubes , 2007 .

[40]  James S. Daubert,et al.  Effect of Meso- and Micro-Porosity in Carbon Electrodes on Atomic Layer Deposition of Pseudocapacitive V2O5 for High Performance Supercapacitors , 2015 .

[41]  U. Schubert,et al.  Inkjet Printing of Narrow Conductive Tracks on Untreated Polymeric Substrates , 2008 .

[42]  S. Devaraj,et al.  Effect of Crystallographic Structure of MnO2 on Its Electrochemical Capacitance Properties , 2008 .

[43]  Andreas Ruediger,et al.  Fully inkjet printed flexible resistive memory , 2017 .

[44]  Zhixiang Wei,et al.  Combining Electrode Flexibility and Wave‐Like Device Architecture for Highly Flexible Li‐Ion Batteries , 2017 .

[45]  Xu Xiao,et al.  WO3−x/MoO3−x Core/Shell Nanowires on Carbon Fabric as an Anode for All‐Solid‐State Asymmetric Supercapacitors , 2012 .

[46]  Yu-Lun Chueh,et al.  Fiber-based all-solid-state flexible supercapacitors for self-powered systems. , 2012, ACS nano.

[47]  Zhenxing Zhang,et al.  Freestanding three-dimensional graphene/MnO2 composite networks as ultralight and flexible supercapacitor electrodes. , 2013, ACS nano.

[48]  Siegfried Bauer,et al.  Flexible electronics: Sophisticated skin. , 2013, Nature materials.

[49]  Wenqiang Wang,et al.  Enhancing the energy density of asymmetric stretchable supercapacitor based on wrinkled CNT@MnO2 cathode and CNT@polypyrrole anode. , 2015, ACS applied materials & interfaces.

[50]  Danick Briand,et al.  Inkjet printed SnO 2 gas sensor on plastic substrate , 2015 .

[51]  Y. Gogotsi,et al.  Materials for electrochemical capacitors. , 2008, Nature materials.

[52]  V. Srdić,et al.  Inkjet patterning of in situ sol–gel derived barium titanate thin films , 2016 .

[53]  W. Lu,et al.  Improved synthesis of graphene oxide. , 2010, ACS nano.

[54]  Zhirun Hu,et al.  Graphene Nanoflakes Printed Flexible Meandered-Line Dipole Antenna on Paper Substrate for Low-Cost RFID and Sensing Applications , 2016, IEEE Antennas and Wireless Propagation Letters.

[55]  Yihua Gao,et al.  Solid-State High Performance Flexible Supercapacitors Based on Polypyrrole-MnO2-Carbon Fiber Hybrid Structure , 2013, Scientific Reports.

[56]  Sarada P. Mishra,et al.  Asymmetric supercapacitor devices based on dendritic conducting polymer and activated carbon , 2017 .

[57]  Daisuke Yamamoto,et al.  Efficient Skin Temperature Sensor and Stable Gel‐Less Sticky ECG Sensor for a Wearable Flexible Healthcare Patch , 2017, Advanced healthcare materials.