An all-printed 3D-Zn/Fe3O4 paper battery
Graphical abstract
Introduction
Systems integrating both electronic and fluidic components have recently emerged as new and powerful platforms for the generation of new functional devices [1]. Originally, these electronic components were fabricated using complex, time-consuming and expensive processes like photolithography [2], vacuum deposition [3], and electroplating [4]. However, screen printed technology has recently been shown as a cost effective alternative technique [5,6]. Historically, fluidic structures were traditionally constructed using glass and polymeric materials such as poly(dimethylsiloxane) (PDMS). Recently, thermoplastic laminated materials [7,8] have been introduced to overcome hurdles presented by fabricating structures from PDMS.
There is great interest within the scientific community to simplify the fabrication procedures of microfluidic devices (MDs) and respective fluidic components and to reduce the costs of their production [9,10]. Presently, a focus is on integrating electronic and fluidic components onto a single sheet of paper [11]. There are a number of reasons paper is an excellent substrate for MDs. Paper is thin, available in a variety of thicknesses, is lightweight, compatible with biological samples, available in many forms with diversity of properties, and can be easily incinerated after use. Paper-based systems can be easily and inexpensively patterned using rapid prototyping techniques, thereby, minimizing the design complexity of the devices [12]. Furthermore, devices fabricated on paper allow for the storage of reactants, offer the possibility to enable their scalability, can be stored, and environmentally friendly [13]. Hence, paper-based systems are the ideal substrate for use in emergency medical situations where immediate results are warranted and in resource-limited settings where instrumentation may not be available [14].
Electrofluidic systems constructed from paper have been used as healthcare diagnostics [15], energy storage devices [16,17], environment monitors [18], displays [19], flexible electronics [20], and printed batteries [21]. All-printed batteries on paper displaying electrofluidic components have been shown to be low cost, flexible, easy to produce and integrated with electronic devices. [[22], [23], [24]]. Currently, the most mature battery system is the Li-ion primary (non-rechargeable) battery, due to its high specific energy density, high efficiency, and long shelf-life [25,26]. Researchers are now focused on alternative materials other than lithium that display similar performance. Different anodic materials have been proposed [27,28] with zinc being one of the most promising [29,30]. Transition metal oxides, such as iron oxide (Fe3O4), have also been widely investigated as a potential electrode material for batteries due to its good redox stability [31].
Therefore, zinc and iron oxide materials, as part of a printed battery are a natural combination given their individual advantages. Frequently, wax printing is utilized along with active materials in printed batteries to pattern hydrophobic areas onto paper. These wax barriers are usually used to direct the flow of fluids by capillary wicking. [32]. Non-printed components (e.g. current collectors as electrodes) could also be utilized. The most convenient and efficient method to realize wax patterning [33] on paper is by direct printing using a wax printer. Wax is also inexpensive and environmentally friendly [34,35]. Heating of deposited wax on paper permeates through the depth of the paper producing a viable barrier causing fluids to spread laterally across the cellulose matrix [36]. In addition, applying folding (or origami) techniques yield compact and stackable 3D battery structures from 2D sheets through multiple available degrees of folding along predefined creases [37]. This allows for more versatile device structures, functions, and even the possibility of integration into ubiquitous objects such as wallpapers, newspapers, and wrapping papers [4,38]
Herein, we describe a novel 3D origami-battery fabricated from Whatman 1 paper created using printed wax and active electrocatalytic materials for the electrodes. The 3D-battery consisted of two screen-printed Zn/Fe3O4 batteries in series activated by KOH. The triangle shaped batteries resembled the core of the fabricated 3D-device that is self-powered with water. These results demonstrate the potential of 3D origami-based structures constructed from paper and their coupling to Zn/Fe3O4 in the construction of batteries as an alternative low-cost energy source to power portable devices.
Section snippets
Equipment and chemicals
Zinc (Zn, <10 μm, ≥98%) and Iron(II,III) oxide (Fe3O4, 50–100 nm, 97%), potassium hydroxide (KOH), ethanol and acetone were purchased from Sigma-Aldrich. Graphite (LOCTITE EDAG 423SS) ink and silver ink (LOCTITE EDAG 725 A) were obtained from Henkel Electronic Materials LLC (Salisbury, NC). The electrodes of the battery were constructed from Whatman® cellulose chromatography paper (grade 1 Chr, 180 μm thick). Laminated adhesives sheets, for performing the individual electrochemical experiments
Ink characterization
The appropriate electrode thickness for the catalytic inks in the 3D-battery was first established. Here, a plain Ag/paper electrode (corresponds to the handmade working electrode) was tested by CV and the signal compared to the same electrode modified with different amounts of carbon ink. The aim of this study was to determine which carbon thickness provided full coverage of the Ag from electrode. Fig. 5(a) shows the response of the silver layer directly exposed to the electrolyte. Two
Conclusions
We have described an all-printed 3D-Zn/Fe3O4 origami-battery. The primary alkaline paper-based battery is simple, low cost, lightweight, and easy to fabricate from Whatman 1 paper. The battery was created using printed wax and screen-printed active electrocatalytic materials for the electrodes. The 3D battery was self-powered with water and could be used as a portable energy device for powering small electronic systems. In water, a maximum current and power of 7 mA and 3 mW, respectively, was
Financial & competing interests disclosure
The authors have no relevant affiliations or financial involvement with an organization or entity with a financial interest in or financial conflict with the subject matter or materials discussed in the manuscript. This includes employment, consultancies, honoraria, stock ownership or options, expert testimony, grants or patents received or pending, or royalties. No writing assistance was utilized in the production of this manuscript.
Acknowledgements
The authors gratefully acknowledge financial support for this research by grants from the National Science Foundation (DMR-1523588, HRD-1547723, EEC-0812348, IIA-1448166,) and the W. M. Keck Foundation. We also thank Maya Horii for assistance in fabrication of some of the battery components.
Maria Jose Gonzalez-Guerrero received her PhD in materials science from the University Autonomous of Barcelona (2015). She started working as a research associate at California State University, Los Angeles in 2016. She is currently working on microfluidic-based batteries and sensors.
References (47)
- et al.
Diagnostics for the developing world: microfluidic paper-based analytical devices
Anal. Chem.
(2010) - et al.
Paper based diagnostics for personalized health care: emerging technologies and commercial aspects
Biosens. Bioelectron.
(2017) - et al.
Development of a paper-based, inexpensive, and disposable electrochemical sensing platform for nitrite detection
Electrochem. commun.
(2017) - et al.
Miniaturized Al/AgO coin shape and self-powered battery featuring painted paper electrodes for portable applications
Sens. Actuators B Chem.
(2018) - et al.
Observation of electrochemical reactions at Zn Electrodes in Zn-Air secondary batteries
Electrochim. Acta
(2016) - et al.
Fe3O4–Carbon black nanocomposite as a highly efficient counter electrode material for dye-sensitized solar cell
Ceram. Int.
(2016) - et al.
Fabrication techniques for microfluidic paper-based analytical devices and their applications for biological testing: a review
Biosens. Bioelectron.
(2016) - et al.
Recent developments, characteristics and potential applications of screen-printed electrodes in pharmaceutical and biological analysis
Talanta
(2016) - et al.
Facile synthesis of hierarchically structured Fe3O4/carbon micro-flowers and their application to lithium-ion battery anodes
J. Power Sources
(2011) - et al.
Integrating electronics and microfluidics on paper
Adv. Mater.
(2016)
Printing methods and materials for large-area electronic devices
Proc. IEEE
The path to ubiquitous and low-cost organic electronic appliances on plastic
Nature
Stepping toward self‐powered papertronics: integrating biobatteries into a single sheet of paper
Adv. Mater. Technol.
Foldable printed circuit boards on paper substrates
Adv. Funct. Mater.
Paper electronics
Adv. Mater.
Membraneless glucose/O2 microfluidic enzymatic biofuel cell using pyrolyzed photoresist film electrodes
Lab Chip
Chip in a lab: microfluidics for next generation life science research
Biomicrofluidics
An open software platform for the automated design of paper-based microfluidic devices
Sci. Rep.
Rapid Development of Paper-Based Fluidic Diagnostic Devices
Paper prototyping: the fast and easy way to design and refine user interfaces
IEEE Trans. Prof. Commun.
Paper-based electrodes for flexible energy storage devices
Adv. Sci.
An optimized microfluidic paper-based NiOOH/Zn alkaline battery
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Maria Jose Gonzalez-Guerrero received her PhD in materials science from the University Autonomous of Barcelona (2015). She started working as a research associate at California State University, Los Angeles in 2016. She is currently working on microfluidic-based batteries and sensors.
Frank A. Gomez received his PhD from the University of California, Los Angeles in 1991. He is presently a professor of chemistry at California State University, Los Angeles. His current research interests include developing new microfluidic platforms (paper and thread in particular) for point-of-care (POC) diagnostic devices and sensors, fuel cells and batteries.