Research Papers

Multilayer Nickel–Copper Anode for Direct Glucose Fuel Cell

[+] Author and Article Information
Antonina Maizelis

Department of Technical Electrochemistry,
National Technical University “Kharkiv Polytechnic Institute”,
Kyrpychova Street 2, Kharkiv 61002, Ukraine
e-mail: a.maizelis@gmail.com

Manuscript Received September 23, 2018; final manuscript received February 23, 2019; published online March 12, 2019. Assoc. Editor: Dirk Henkensmeier.

J. Electrochem. En. Conv. Stor. 16(4), 041003 (Mar 12, 2019) (7 pages) Paper No: JEECS-18-1101; doi: 10.1115/1.4042986 History: Received September 23, 2018; Accepted February 23, 2019

Multilayer nickel–copper coatings consisting of layers of nickel–copper alloy and a mixture of metals with hydroxides were obtained by electrodeposition from polyligand pyrophosphate–ammonia electrolyte by the two-pulse potentiostatic method. A comparison between two different electrodes with the same real surface area is presented. The equality of the surface area of electrodes deposited from the electrolyte containing different copper and nickel ions’ concentration ratio was achieved by deposition of different numbers of layers. It is shown that the increase in the copper content in electrolyte leads to an increase in the copper ions’ content in the coating and the electrode surface develops more intensively. Freshly deposited coatings have approximately the same catalytic activity in the glucose oxidation reaction in the alkaline solution. But a multilayer coating with a higher copper content is more corrosion resistant and more stable in long-term electrolysis.

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Brouzgou, A., and Tsiakaras, P., 2015, “Electrocatalysts for Glucose Electrooxidation Reaction: A Review,” Top. Catal., 58(18–20), pp. 1311–1327. [CrossRef]
Gao, M., Liu, X., Irfan, M., Shi, J., Wang, X., and Zhang, P., 2018, “Nickle-Cobalt Composite Catalyst-Modified Activated Carbon Anode for Direct Glucose Alkaline Fuel Cell,” J. Electroanal. Chem., 43(3), pp. 1805–1815.
Niitsu, K., Ando, T., Kobayashi, A., and Nakazato, K., 2016, “Enhancement in Open-Circuit Voltage of Implantable CMOS-Compatible Glucose Fuel Cell by Improving the Anodic Catalyst,” Jpn. J. Appl. Phys., 56(1S), 01AH04. [CrossRef]
Spets, J. P., Lampinen, M. J., Kiros, Y., Rantanen, J., and Anttila, T., 2012, “Direct Glucose Fuel Cell With the Anion Exchange Membrane in the Near-Neutral-State Electrolyte,” Int. J. Electrochem. Sci., 7, pp. 11696–11705.
Apblett, C. A., Ingersoll, D., Sarangapani, S., Kelly, M., and Atanassov, P., 2010, “Direct Glucose Fuel Cell: Noble Metal Catalyst Anode Polymer Electrolyte Membrane Fuel Cell With Glucose Fuel,” J. Electrochem. Soc., 157(1), pp. B86–B89. [CrossRef]
Wojnicki, M., Luty-Błocho, M., Dobosz, I., Grzonka, J., Pacławski, K., Kurzydłowski, K. J., and Paclawski, K., 2013, “Electro-Oxidation of Glucose in Alkaline Media on Graphene Sheets Decorated With Gold Nanoparticles,” Mater. Sci. Appl., 4(02), pp. 162–169.
Yang, Z., Miao, Y., Wang, T., Liang, X., Xiao, M., Li, W., and Yang, Y., 2014, “The Self-Adsorption of Ni Ultrathin Layer on Glassy Carbon Surface and Their Electrocatalysis Toward Glucose,” J. Electrochem. Soc., 161(6), pp. H375–H378. [CrossRef]
Sincheskul, A., Pancheva, H., Loboichenko, V., Avina, S., Khrystych, O., and Pilipenko, A., 2017, “Design of the Modified Oxide-Nickel Electrode With Improved Electrical Characteristics,” East.-Eur. J. Enterp. Technol., 5(6(89)), pp. 23–28. [CrossRef]
Pospelov, A. P., Pilipenko, A. I., Kamarchuk, G. V., Fisun, V. V., Yanson, I. K., and Faulques, E., 2015, “A New Method for Controlling the Quantized Growth of Dendritic Nanoscale Point Contacts Via Switchover and Shell Effects,” J. Phys. Chem. C, 119(1), pp. 632–6399. [CrossRef]
Shtefan, V. V., and Smirnova, A. Y., 2015, “Synthesis of Ce-, Zr-, and Cu-Containing Oxide Coatings on Titanium Using Microarc Oxidation,” Russ. J. Electrochem., 51, pp. 1168–1175. [CrossRef]
Yang, Y. L., Liu, X. H., Hao, M. Q., and Zhang, P. P., 2015, “Performance of a Low-Cost Direct Glucose Fuel Cell With an Anion-Exchange Membrane,” Int. J. Hydrogen Energy, 40(34), pp. 10979–10984. [CrossRef]
Miao, F., Tao, B., and Chu, J., 2013, “Nonenzymatic Alkaline Direct Glucose Fuel Cell With a Silicon Microchannel Plate Supported Electrocatalytic Electrode,” J. Fuel Cell Sci. Technol., 10(4), 041003. [CrossRef]
Oncescu, V., and Erickson, D., 2013, “High Volumetric Power Density, Non-Enzymatic, Glucose Fuel Cells,” Sci. Rep., 3, 1226. [CrossRef] [PubMed]
Chen, J., Zheng, H., Kang, J., Yang, F., Cao, Y., and Xiang, M., 2017, “An Alkaline Direct Oxidation Glucose Fuel Cell Using Three-Dimensional Structural Au/Ni-Foam as Catalytic Electrodes,” RSC Adv., 7(5), pp. 3035–3042. [CrossRef]
Torto, N., Ruzgas, T., and Gorton, L., 1999, “Electrochemical Oxidation of Mono-and Disaccharides at Fresh as Well as Oxidized Copper Electrodes in Alkaline Media,” J. Electroanal. Chem., 464(2), pp. 252–258. [CrossRef]
Zhang, X., Luo, J., Tang, P., Morante, J. R., Arbiol, J., Xu, C., Li, Q., and Fransaer, J., 2018, “Ultrasensitive Binder-Free Glucose Sensors Based on the Pyrolysis of In Situ Grown Cu MOF,” Sens. Actuators B, 254, pp. 272–281. [CrossRef]
D’Eramo, F., Marioli, J. M., Arévalo, A. A., and Sereno, L. E., 1999, “HPLC Analysis of Carbohydrates With Electrochemical Detection at a Poly-1-Naphthylamine/Copper Modified Electrode,” Electroanalysis, 11(7), pp. 481–486. [CrossRef]
Kang, X., Mai, Z., Zou, X., Cai, P., and Mo, J., 2007, “A Sensitive Nonenzymatic Glucose Sensor in Alkaline Media With a Copper Nanocluster/Multiwall Carbon Nanotube-Modified Glassy Carbon Electrode,” Anal. Biochem., 363(1), pp. 143–150. [CrossRef] [PubMed]
Huang, Y., Zhang, H., Xu, X., Zhou, J., Lu, F., Zhang, Z., Hu, Z., and Luo, J., 2018, “Fast Synthesis of Porous Copper Nanoclusters for Fluorescence Detection of Iron Ions in Water Samples,” Spectrochim. Acta Part A, 202, pp. 65–69. [CrossRef]
Ahmad, R., Tripathy, N., Ahn, M. S., Bhat, K. S., Mahmoudi, T., Wang, Y., Yoo, J. Y., Kwon, D. W., Yang, H. Y., and Hahn, Y. B., 2017, “Highly Efficient Non-Enzymatic Glucose Sensor Based on CuO Modified Vertically-Grown ZnO Nanorods on Electrode,” Sci. Rep., 7(1), 5715. [CrossRef] [PubMed]
Raziq, A., Tariq, M., Hussain, R., Mahmood, M. H., Ullah, I., Khan, J., and Muhammad, M., 2018, “Highly Sensitive, Non-Enzymatic and Precious Metal Free Electrochemical Glucose Sensor Based on Ni–Cu/TiO2 Modified Glassy Carbon Electrode,” J. Serb. Chem. Soc., 83(6), pp. 733–744. [CrossRef]
Danaee, I., Jafarian, M., Forouzandeh, F., Gobal, F., and Mahjani, M. G., 2008, “Kinetic Interpretation of a Negative Time Constant Impedance of Glucose Electrooxidation,” J. Phys. Chem. B, 112, pp. 15933–15940. [CrossRef] [PubMed]
Qiu, R., Zhang, X. L., Qiao, R., Li, Y., Kim, Y. I., and Kang, Y. S., 2007, “CuNi Dendritic Material: Synthesis, Mechanism Discussion, and Application as Glucose Sensor,” Chem. Mater., 19(17), pp. 4174–4180. [CrossRef]
Yeo, I. H., and Johnson, D. C., 2001, “Electrochemical Response of Small Organic Molecules at Nickel–Copper Alloy Electrodes,” J. Electroanal. Chem., 495(2), pp. 110–119. [CrossRef]
Wolfart, F., Maciel, A., Nagata, N., and Vidotti, M., 2013, “Electrocatalytical Properties Presented by Cu/Ni Alloy Modified Electrodes Toward the Oxidation of Glucose,” J. Solid State Electrochem., 17(5), pp. 1333–1338. [CrossRef]
Jafarian, M., Forouzandeh, F., Danaee, I., Gobal, F., and Mahjani, M. G., 2009, “Electrocatalytic Oxidation of Glucose on Ni and NiCu Alloy Modified Glassy Carbon Electrode,” J. Solid State Electrochem., 13(8), pp. 1171–1179. [CrossRef]
An, L., Zhao, T. S., Zeng, L., and Yan, X. H., 2014, “Performance of an Alkaline Direct Ethanol Fuel Cell With Hydrogen Peroxide as Oxidant,” Int. J. Hydrogen Energy, 39(5), pp. 2320–2324. [CrossRef]
Yan, X. H., Zhao, T. S., An, L., Zhao, G., and Shi, L., 2016, “A Direct Methanol–Hydrogen Peroxide Fuel Cell With a Prussian Blue Cathode,” Int. J. Hydrogen Energy, 41(9), pp. 5135–5140. [CrossRef]
Yamada, Y., Yoneda, M., and Fukuzumi, S., 2015, “High and Robust Performance of H2O2 Fuel Cells in the Presence of Scandium Ion,” Energy Environ. Sci., 8(6), pp. 1698–1701. [CrossRef]
Miglbauer, E., Wójcik, P. J., and Głowacki, E. D., 2018, “Single-Compartment Hydrogen Peroxide Fuel Cells With Poly (3, 4-Ethylenedioxythiophene) Cathodes,” Chem. Commun., 54(84), pp. 11873–11876. [CrossRef]
Guo, F., Cheng, K., Ye, K., Wang, G., and Cao, D., 2016, “Preparation of Nickel-Cobalt Nanowire Arrays Anode Electro-Catalyst and Its Application in Direct Urea/Hydrogen Peroxide Fuel Cell,” Electrochim. Acta, 199, pp. 290–296. [CrossRef]
Yang, F., Cheng, K., Xiao, X., Yin, J., Wang, G., and Cao, D., 2014, “Nickel and Cobalt Electrodeposited on Carbon Fiber Cloth as the Anode of Direct Hydrogen Peroxide Fuel Cell,” J. Power Sources, 245, pp. 89–94. [CrossRef]
An, L., Zhao, T. S., and Zeng, L., 2013, “Agar Chemical Hydrogel Electrode Binder for Fuel-Electrolyte-Fed Fuel Cells,” Appl. Energy, 109, pp. 67–71. [CrossRef]
An, L., Zhao, T. S., Zhou, X. L., Wei, L., and Yan, X. H., 2012, “A High-Performance Ethanol–Hydrogen Peroxide Fuel Cell,” RSC Adv., 4(110), pp. 65031–65034. [CrossRef]
An, L., Zhao, T. S., Chen, R., and Wu, Q. X., 2011, “A Novel Direct Ethanol Fuel Cell With High Power Density,” J. Power Sources, 196(15), pp. 6219–6222. [CrossRef]
An, L., Zhao, T. S., and Xu, J. B., 2011, “A Bi-Functional Cathode Structure for Alkaline-Acid Direct Ethanol Fuel Cells,” Int. J. Hydrogen Energy, 36(20), pp. 13089–13095. [CrossRef]
An, L., and Zhao, T. S., 2011, “Performance of an Alkaline-Acid Direct Ethanol Fuel Cell,” Int. J. Hydrogen Energy, 36(16), pp. 9994–9999. [CrossRef]
Khadke, P. S., Sethuraman, P., Kandasamy, P., Parthasarathi, S., and Shukla, A. K., 2009, “A Self-Supported Direct Borohydride-Hydrogen Peroxide Fuel Cell System,” Energies, 2(2), pp. 190–201. [CrossRef]
Maizelis, A. A., Bairachniy, B. I., Trubnikova, L. V., and Savitsky, B. A., 2012, “The Effect of Architecture of the Cu/(Ni-Cu) Multilayer Coatings on Their Microhardness,” Funct. Mater., 19(2), pp. 238–244.
Maizelis, A., and Bairachny, B., “Voltammetric Analysis of Phase Composition of Zn-Ni Alloy Thin Films Electrodeposited From Weak Alkaline Polyligand Electrolyte,” J. Nano- Electron. Phys., 9(5), 05010.
Maizelis, A., and Bairachniy, B., 2017, “Electrochemical Formation of Multilayer SnO2-SbxOy Coating in Complex Electrolyte,” Nanosc. Res. Lett., 12(1), p. 119. [CrossRef]
Maizelis, A., and Bairachniy, B., 2016, “Electrochemical Formation of Multilayer Metal and Metal Oxide Coatings in Complex Electrolytes,” International Conference on Nanotechnology and Nanomaterials, Springer, Cham, August, pp. 557–572.
Maizelis, A. A., 2017, “Voltammetric Analysis of Phase Composition of Zn-Ni Alloy Thin Films Electrodeposited Under Different Electrolyze Modes,” 2017 IEEE 7th International Conference Nanomaterials: Application Properties (NAP), 02NTF13.
Gira, M. J., Tkacz, K. P., and Hampton, J. R., 2016, “Physical and Electrochemical Area Determination of Electrodeposited Ni, Co, and NiCo Thin Films,” Nano Converg., 3(1), p. 6. [CrossRef] [PubMed]
Sattarahmady, N., and Heli, H., 2012, “A Non-Enzymatic Amperometric Sensor for Glucose Based on Cobalt Oxide Nanoparticles,” J. Exp. Nanosci., 7(5), pp. 529–546. [CrossRef]
Jafarian, M., Moghaddam, R. B., Mahjani, M. G., and Gobal, F., 2006, “Electro-Catalytic Oxidation of Methanol on a Ni–Cu Alloy in Alkaline Medium,” J. Appl. Electrochem., 36(8), pp. 913–918. [CrossRef]
Norouzi, B., and Norouzi, M., “Methanol Electrooxidation on Novel Modified Carbon Paste Electrodes With Supported Poly (Isonicotinic Acid)(Sodium Dodecyl Sulfate)/Ni-Co Electrocatalysts,” J. Solid State Electrochem., 16(9), pp. 3003–3010. [CrossRef]


Grahic Jump Location
Fig. 1

CVA on Pt in the pyrophosphate–ammonia electrolyte with different metal ion concentration ratios [Cu2+]:[Ni2+]: 1–1:5; 2–1:20. The potential scan rate is 50 mV s−1. The potential delay at −1.35 V was for 5 s. Inset: the chronopotentiogram of multilayer coatings formation.

Grahic Jump Location
Fig. 2

Anodic polarization curves of dissolution of sublayers of (1, 3) ML5 and (2, 4) ML20 coatings deposited on Pt (1, 2) at −1.175 V for 60 s and (3, 4) at −1.35 V for 4 s. Both coating deposition and dissolution were carried out in the electrolyte for coating deposition. The potential scan rate is 10 mV s−1.

Grahic Jump Location
Fig. 3

Chronoamperograms of (1) ML5 and (2) ML20 multilayer coatings formation on the copper substrate

Grahic Jump Location
Fig. 4

ALSV of electrodes with (2) ML20 and (1) ML5 multilayer coatings in the 3 mol l−1 KOH electrolyte. The potential scan rate is 50 mV s−1.

Grahic Jump Location
Fig. 5

CVA of electrodes with (a) ML20 and (b) ML5 multilayer coatings in the 3 mol l−1 KOH electrolyte. The potential scan rate is 50 mV s−1. The cycle number is mentioned in the figure.

Grahic Jump Location
Fig. 6

Morphology of the electrodes with (a) ML5 and (b) ML20 coatings

Grahic Jump Location
Fig. 7

Dependence of capacitive current Idl of electrodes with (1) ML5 and (2) ML20 coating in 3 mol l−1 KOH on scan rate at the potential of 0.0 V. Inset: cyclic voltammograms at various scan rates from 25 mV s−1 to 400 mV s−1 in the double-layer region.

Grahic Jump Location
Fig. 8

CVA of electrodes with (a) ML20 and (b) ML5 coating in 3 mol l−1 KOH and 1 mol l−1 Glc electrolyte. Potential scan rate (mV s−1) is as follows: 1–25.0; 2–34.0; 3–46.3; 4–63.0; 5–85.7; 6–116.7; 7–158.7; 8–216.0; 9–293.0; and 10–400.0.

Grahic Jump Location
Fig. 9

CVA of electrodes with (1, 2, 3—solid lines) as-deposited (1, 3) ML20 and (2) ML5 coating in (3, 3′) 3 mol l−1 KOH solution and (1, 2, 1′, 2′) 3 mol l−1 KOH, 1 mol l−1 Glc solution, and (1′, 2′, 3′—dashed lines) after 500 cycles. Potential scan rate is 50 mV s−1.

Grahic Jump Location
Fig. 10

(a) Corrosion diagrams of electrodes with (1) ML20 and (2) ML5 multilayer coating in 3 mol l−1 KOH, 0.5 mol l−1 Glc solution after exposure in the solution for 1 h, the potential scan rate is 1 mV s−1; (b) CVA of electrodes with (a) ML5 and (b) ML20 multilayer coating in 3 mol l−1 KOH electrolyte after the corrosion test. The potential scan rate is 50 mV s−1. The cycle number is mentioned in the figure.

Grahic Jump Location
Fig. 11

CVA of electrodes with (1, 1′) ML5 and (2) ML20 coating in (1′) 3 mol l−1 KOH and (1, 2) 3 mol l−1 KOH, 0.1 mol l−1 Glc. Potential scan rate is 10 mV s−1.

Grahic Jump Location
Fig. 12

(a) Chronoamperograms of electrodes with (1) ML5 and (2) ML20 multilayer coating at a potential of 0.33 V under periodic renewal of the solution of 3 mol l−1 KOH, 0.1 mol l−1 Glc and (b) CVA of electrodes with (a) ML20 and (b) ML5 multilayer coating in 3 mol l−1 KOH electrolyte after electrolysis at 0.33 V. The potential scan rate is 50 mV s−1. The cycle number is mentioned in the figure.



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