O2 biofuel cell

O2 biofuel cell

Journal of Power Sources 360 (2017) 516e519 Contents lists available at ScienceDirect Journal of Power Sources journal homepage: www.elsevier.com/lo...

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Journal of Power Sources 360 (2017) 516e519

Contents lists available at ScienceDirect

Journal of Power Sources journal homepage: www.elsevier.com/locate/jpowsour

Short communication

A screen-printed circular-type paper-based glucose/O2 biofuel cell Isao Shitanda a, b, *, Saki Nohara a, 1, Yoshinao Hoshi a, b, Masayuki Itagaki a, b, Seiya Tsujimura b, c, 1 a

Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641, Yamazaki, Noda, Chiba 278-8510, Japan Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba 278-8510, Japan c Division of Material Science, Faculty of Pure and Applied Science, University of Tsukuba, 1-1-1, Tennodai, Tsukuba, Ibaraki 305-5358, Japan b

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 A circular-type paper-based fuel cell (PBFC), powered by glucose, is proposed.  An array-structure realizes the open circuit voltage of 2.65 V.  The PBFC exhibits a remarkable power output of 350 mW.  The PBFC is capable of illuminating an LED directly.

a r t i c l e i n f o

a b s t r a c t

Article history: Received 13 March 2017 Received in revised form 20 May 2017 Accepted 14 June 2017

The printable paper-based enzymatic biofuel cell (PBFC) to directly power small devices is an important objective for realizing cost-effective and disposable energy harvesting devices. In the present study, a screen-printed circular-type PBFC, composed of a series of 5 individual cells, was constructed. The PBFC exhibited the open circuit potential of 2.65 V and maximum power of 350 mW at 1.55 V, which were sufficient to illuminate an LED without requiring a booster circuit. The output voltage of this PBFC can also be easily adjusted as required. © 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Paper-based biofuel cell Glucose Screen-printing Array

1. Introduction There is an urgent need to develop new printable, flexible, and lightweight power sources with excellent safety for small electrical devices, such as wearable devices and sensor tags to realize smart community. Paper-based enzymatic biofuel cells (PBFCs) are attracting increasing attention as an energy harvesting device,

* Corresponding author. Department of Pure and Applied Chemistry, Faculty of Science and Technology, Tokyo University of Science, 2641, Yamazaki, Noda, Chiba 278-8510, Japan. E-mail address: [email protected] (I. Shitanda). 1 S. N. and S. T. contributed equally to this work.

since enzymatic biofuel cells can generate electricity from safe biological resources such as sugars [1e12]. In addition, paper is the ideal substrate in such cells because it is (i) printable, (ii) combustible, (iii) flexible, lightweight and thin, and (v) disposable and biocompatible. Although great progress has been made in the study of PBFC, several challenges still need to be addressed before it can use used in practical applications. One of the challenges involves the generation of sufficient voltage to power electronic devices. Normally, a primary or secondary dry battery (e.g. alkaline battery and lithium ion battery) with a voltage higher than 1.5 V is used to power electrical devices. In comparison, the maximum output voltages of previously reported PBFCs are usually 0.5e0.7 V [1e12], which are

http://dx.doi.org/10.1016/j.jpowsour.2017.06.043 0378-7753/© 2017 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

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lower than that required for most electrical devices such as sensor tags. Thus, most PBFCs require a DC/DC boost converter for powering even low-power electronic devices. For example, the minimum required voltages of blue light-emitting diodes and Bluetooth Low Energy devices are about 2.5 and 2.4 V, respectively [13]. The individual elements of biofuel cells, such as the anode, cathode, and paper, can be stacked in series to increase the effective output voltage, although several separate parts need to be stacked to form an array-type biofuel cell prior to use [9,14]. Recently, we introduced a printable origami PBFC, which was constructed as an array of two individual cells on one sheet of paper by screen-printing [15]. This printable origami PBFC, whose output voltage could be

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modulated by paper folding, exhibited an open-circuit voltage of almost 1 V. However, suitable array structures of printable PBFC with an output voltage of more than 1.5 V have not been reported. In the present study, we demonstrated a circular-type PBFC by combining a series of 5 individual cells to directly power lowpower electronics. Printable array-type PBFC could be low-cost and disposable, since this technique allows for mass production with high reproducibility. This circular-type PBFC exhibited an open circuit potential of 2.65 V, and to our best knowledge it is the first report of printable circular-type PBFC. This concept for PBFC is highly useful for developing high-power, low-cost, and flexible energy harvesting devices.

Fig. 1. (A) Fabrication process and (B) computer-aided design (CAD) data of the circular-type paper-based biofuel cell (PBFC) containing a series of five individual cells.

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2. Experimental Fig. 1A shows a schematic illustration of the circular-type PBFC connected in the 5-series combination, with the computer-aided design (CAD) data shown in Fig. 1B. A screen printer (LS-150TV, NEWLONG SEIMITSU KOGYO Co. Ltd. Japan) was used throughout to fabricate the circular-type PBFC, using a filter paper (Whatman No. 1002e110) as the substrate. Firstly, a conductive carbon layer was printed onto the paper using a commercial carbon ink (JELCOM CH-10, Jujo Chemicals, Japan). Then, the printed conductive carbon layer was cured at 60  C for 30 min. The formed carbon layer had 25 pores whose diameter was 0.5 mm. A silver layer was then deposited to connect the cells to each other, and to reduce the inner resistance of the conducting carbon layer. To protect the silver layer from corrosion in the test solution, it was coated with a resistive layer (DSR-330T12-11, Tamura Corp.). A water repellent (Fluorosurf FG3030C-30, FluoroTechnology Co. Ltd. Japan) was further coated over the resistive layer to increase the water repellency of this layer. A 100 mm2 porous carbon layer was then formed on top of the conductive carbon layer by screen-printing, then dried at 25  C for 1 h. We prepared a new porous carbon ink for the bioanode composed of 320 mg of Ketjen black (KB) and 80 mg of polyvinylidene difluoride (PVdF) binder (Kureha Corp.) in 5 mL of isophorone. The porous carbon ink was mixed by ultrasonic homogenization for 5 min, followed by planetary centrifugation at 2000 rpm (ARE-310, Thinky Co. Japan) for 3 min. The composition of the porous carbon ink for the biocathode was 300 mg of KB, 20 mg of carboxymethylcellulose (serogen WS-A, Dai-ichi Kogyo Seiyaku), and 40 mg of styrene butadiene rubber binder (BM-400B, Zeon Corp. Japan) dispersed in 2.5 mL of water. This porous carbon ink was also treated by ultrasonication for 3 min. For the preparation of the bioanode, the porous carbon layer surface was first treated by UV/ozone irradiation for 15 min. Then, 20 mL of glucose oxidase (GOx, 20 U mL 1, Wako) solution was prepared by dissolving GOx in phosphate buffer. The pH of the phosphate buffer solution was 7.0. The GOx solution and 18 mL saturated tetrathiafulvalene (TTF) solution in methanol were immobilized in the porous carbon layer by a casting method. In the case of the biocathode, 5 mL of bilirubin oxidase (BOD, Amano Enzyme) solution (1 U mL 1) containing 0.015% of Triton X-100 was dropped on the porous carbon layer, and pretreated by UV/ozone. One set of the sheets (see front side of Fig. 1A(d)) has three bioanode and two biocathode components, while the other set (back side) has two bioanode and three biocathode components. The non-printed sides of the two sets of sheets were stacked together using water-repellent, double-sided tape. The stacked sheets were then cut as shown in Fig. 1A(e) to prevent the cell from short-circuiting. Finally, the non-printed sides of two sets of sheets were stacked using water-repellent and double-sided tape (Fig. 1A(f)). The characteristics of the bioanode and biocathode were investigated independently using the three-electrode method according to reported procedure [7]. The electrochemical response of the 5-series PBFC was examined, and the output power and current were measured by casting a 1 M phosphate buffer solution containing glucose (1 mL) on each edge of the paper.

was clearly observed in the presence of glucose (red line). The density of the catalytic current was 3.4 mA cm 2 at 0.5 V. On the other hand, such a redox wave was not observed in the absence of glucose (blue line). The cyclic voltammograms of the biocathode were measured with and without BOD (Fig. 2b). A catalytic oxygen reduction current was not observed without the enzyme (blue line), but clearly observed in the presence of BOD (red line), revealing the direct catalytic reaction of BOD [7]. The catalytic current density at 0.3 V was 0.5 mA cm 2. Next, as preliminary work, we fabricated two single PBFCs and arranged them in a serial configuration as shown in Fig. S1, followed by performance evaluation. The power-potential curves of these PBFCs are shown in Fig. S2(a). The open circuit potential (OPC) of the single cell was 0.57 V, and is attributed to the difference between the onset potentials of the bioanode and biocathode. The OPC of the single cell was 0.57 V. The maximum power density of the fabricated single cell was 11.6 mW (46 mW cm 2) at 0.31 V, and that of the 2-series cell was 23.1 mW at 0.63 V. The OPC of the 2series cell was 1.04 V, which are about 2 times higher than that of the single cell. Finally, we measured the output powers by using a 1 M phosphate buffer solution (pH 7.0) containing 100 mM glucose. The current-potential and power-potential curves of the circular-type PBFC are shown in Fig. 3a. The electrolyte solution containing glucose flowed into the paper, passing through the pores of the conductive carbon layer to reach the porous carbon layer. The OPC

3. Results and discussion Firstly, we investigated the performance of the bioanode and biocathode by cyclic voltammograms measured independently using the three-electrode method [7]. During the measurements, the edges of bioanode and biocathode were immersed in the 1 M phosphate buffer solution containing the glucose. Fig. 2a shows the cyclic voltammograms of the bioanode with and without 100 mM glucose at 25  C. A catalytic current wave due to glucose oxidation

Fig. 2. Cyclic voltammograms of (a) bioanode, on which GOx and TTF were immobilized in 1 M phosphate buffer (pH 7.0) with (red line) and without (blue line) 100 mM glucose at 25  C. (b) The biocathode with (red line) and without (blue line) BOD at 25  C. The scan rate was 10 mV s 1. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

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Fig. 3b, the maximum power clearly changes with the glucose concentration between 1 and 100 mM. Thus, the present circulartype PBFC also has the potential as a self-powered biosensor, by monitoring the glucose concentration through its output power [9,10,16e18] and interfacing with low-power wireless transmission devices or smartphones, etc. Finally, Fig. 4 demonstrates that this PBFC could be used directly to power an LED, without the need for a booster circuit. In future work, we aim to improve the power of these PBFCs, evaluate their stabilities and responses to glucose, and fabricate self-powered biosensors. 4. Conclusions In summary, we have constructed a high-power PBFC with an array structure. This PBFC exhibits a remarkable power output of 350 mW, which is sufficient to power an LED without the need for a booster circuit. Such a PBFC is highly useful in the development of wearable, low-cost, and disposable biofuel cells. Acknowledgements This work was supported by JST A-STEP (AS272S004a). I.S. acknowledges financial support from the Hosokawa Powder Technology Foundation (14108) and the Iwatani Naoji Foundation. Appendix A. Supplementary data Fig. 3. (a) Current-potential and power-potential curves of the circular-type PBFC, measured at pH 7.0 and 25  C in a phosphate buffer containing 100 mM glucose. (b) Relation between glucose concentration and output power in the present PBFC.

Supplementary data related to this chapter can be found at http://dx.doi.org/10.1016/j.jpowsour.2017.06.043. References

Fig. 4. LED illumination test using the circular-type PBFC.

was found to be 2.65 V, which was almost five times higher than that of the single cell. The maximum current and output power were determined to be 305 mA (at 0 V) and 350 mW (at 1.55 V), respectively. The maximum output power density was 70 mW cm 2. From these results, we conclude that the voltage and output power of the cell can easily be adjusted as required without any power loss using the present procedure, by adjusting the number of individual electrode-containing sheets. Furthermore, we performed a trial evaluation of the relationship between glucose concentration and maximum power. As shown in

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