Screen-printed nickel hydroxide electrodes: Semiconducting, electrocatalytic, and electrochromic properties

https://doi.org/10.1016/j.jelechem.2022.117052Get rights and content

Highlights

  • The development of a nickel hydroxide-based ink is described.

  • Screen-printed Nickel hydroxide electrodes feature several important properties.

  • Screen-printed Nickel hydroxide electrodes show fast electron transfer.

  • Screen-printed nickel hydroxide electrodes can be used for the enzyme-less detection of glucose.

  • The nickel hydroxide electrodes’ bandgap has been determined by diffuse reflectance.

Abstract

This work presents a methodology to develop functional metal-oxide based inks for screen-printing. Nickel hydroxide has been grown by co-precipitation on the surface of conducting microparticles using different particle to nickel salt ratios. The resulting particles formed the basis of screen-printing inks, used to print electrodes and test structures. The work describes the characterization of the materials through the different stages of development using a range of techniques including SEM, TEM, electrochemical and spectroscopic techniques. The screen printed electrodes have demonstrated their ability to oxidise water at 0.7–0.8 V vs Ag, making them suitable for electrolyzers. Also, glucose can be directly oxidised at these electrodes below 0.6 V vs Ag, with a detection limit around 65 µM, also pointing to enzyme-less biosensing applications. The electrodes also display electrochromism, with charge efficiencies in the range of 50 cm2 C−1. Last, the electrodes present an optical bandgap in the range 4.06–4.15 eV, determined by diffuse reflectance spectroscopy. The approach presented here is extensive to other metal oxides, which opens the range of possible screen-printed semiconductors and catalysts considerably.

Introduction

Metal oxides are used in many applications ranging from electrocatalysis, photochemistry, batteries, sensing and electronics. However, functional screen-printed metal oxide structures are difficult to achieve due to their high electrical resistance. Consequently, metal oxides are typically used in the form of thin films [1] or as nanomaterials modifying an underlying conducting substrate [2]. Printing techniques are attractive deposition strategies due to their flexibility and lower cost compared to thin-film processes, which has led to the growth of the industry known as printed electronics [3]. Among the many printing techniques available [4], screen-printing is widely adopted due to its robustness, affordability, ease of implementation, and high throughput. However, in contrast to other printing techniques such as gravure, pad printing, and ink-jet printing [5], screen-printed layers are typically several microns thick, preventing the screen-printing of metal oxide-based devices. To the best of the authors’ knowledge, currently there are no screen-printing metal oxide-based inks in the market. Although it is possible to formulate screen-printing inks based on metal oxide particles alone, the resulting structures are so highly resistive that their range of applications would be extremely narrow. Attempts to overcome this limitation involve the combination of the metal oxide with different conducting materials, among which carbon nanomaterials are the most common [6], [7]. Carbon nanomaterials are black, which precludes the observation of color changes, and highly conducting, which prevents, among other things, the construction of working p-n junctions [8] and Schottky contacts [9]. Moreover, Nickel oxide pastes also containing other oxides, such as iron-cobalt oxide [10] or manganese oxide [11], to enhance its electrocatalytic properties for sensing, have been described.

This work demonstrates the formulation of metal-oxide screen printing inks that enable the production of fully functional structures displaying, among others, semiconducting and electrochromic properties. Fig. 1 provides a conceptual representation of how the proposed material works. Metal oxide nanostructures grown on the surface of antimony-tin-oxide conducting microparticles are formulated into an ink, and screen-printed. The figure represents how thickness and density of the metal oxide layer on the conducting particles affect functionality of printed structures.

An optimum thickness allows fast and efficient electron transfer and ion exchange required by electrochemical processes. On the other hand, too thin coatings also provide limited functionality. This work shows the development of optimum Nickel hydroxide, Ni(OH)2, coatings, based on a methodology that can be extended to other oxides. Ni(OH)2 has been chosen for its versatility and usefulness in a wide range of applications. Nickel oxide, NiO, and Ni(OH)2 are used mainly in batteries [12] but also in photovoltaics [13], water splitting [8], electrochromics [14], and electrocatalysis [15]. In fact, NiO/Ni(OH)2 cathodes featured in the first rechargeable Ni-Cd battery, invented by Jungner in 1899 [16]. Since then, thanks to its energy density and long-term stability, NiO and Ni(OH)2 can be found in battery electrodes from Ni-MH batteries to present-day lithium ion batteries. In addition to batteries, NiO and Ni(OH)2 are used in other energy storage and generation devices, such as supercapacitors [17] and photovoltaic systems [18]. NiO has been used as a highly efficient blocking layer in p-type dye sensitized solar cells, DSSC [19], as well as in inverted Perovskite Solar Cells, where it acts as hole selective layer leading to record power conversion efficiencies [20]. Besides, nickel abundant availability, its oxides are relatively non-toxic, making it interesting from a cost-effective and eco-friendly viewpoint.

Ni(OH)2 is a semiconductor with a wide band-gap, around 3.7–4.1 eV [21], leading to very low conductivities, between around 10−5 Ω−1 cm−1 and down to 10−9 Ω −1 cm−1 for different hydroxides [22]. Ni(OH)2 and NiO are either used in the form of very thin layers, a few nm thick, or as nanoparticles. Such thin layers may be produced by chemical vapour deposition, CVD, and physical vapour deposition methods [14], [23], [24], [25]. Electrodeposition of Ni(OH)2 on porous Ni electrodes has also been reported in the production of supercapacitors with specific capacities over 3000F g−1 at voltages between 0.05 and 0.45 V [26]. The latter work reports Ni(OH)2 deposits in the range of 10 nm, which increases the specific surface area but also facilitates the current exchange between the electrolyte and the underlying Ni collector (electrode).

On the other hand, nanoparticles are used to modify electrodes either through direct deposition on an electrode surface [27], or mixed with conducting materials from which electrodes are subsequently produced [28]. Nickel oxide species have also been synthesised in the presence of carbon nanotubes [29] and other nanomaterials [30], [31], [32]. To be deposited on an electrode or combined with a resin binder into a paste [33].

Moreover, the electrocatalytic properties of NiO and Ni(OH)2 are of great interest beyond energy storage and generation. Nickel hydroxide favours the oxidation of water at lower potentials than other electrode materials, which makes it very useful for the construction of electrolysers for the production of hydrogen gas [15], [34]. By decreasing the oxygen evolution potential, nickel hydroxide anodes also reduce the energy needed to produce hydrogen gas at the cell cathode. This electrocatalytic activity has also been exploited to oxidise small molecules such as glycine [32], methanol [35] and, more importantly, glucose [36], Despite relatively poor selectivity, NiO/Ni(OH)2 modified electrodes are currently being studied for the development of enzyme-less glucose sensors in the hope that they will last longer than their enzyme-based biosensing counterparts.

In this work we present the synthesis and formulation into screen-printing inks of nickel hydroxide-modified conducting particles that enable the production of highly functional electrodes. A comprehensive characterization of the main properties of this new material is presented. To the best of our knowledge, this is the first report of a screen-printed electrochromic Ni-based paste.

Section snippets

Materials.

NiCl2·6H2O and NaOH were purchased from Sigma-Aldrich (ES) and used as received. KOH 0.1 M, pH = 13, were used as background electrolyte, unless otherwise stated. All solutions were prepared with deionized water of resistivity not<18 MΩ cm. Nitrocellulose Walsroder A400 (Dow Chemicals, DE), Zelec 1610-S SiO2/ATO (Milliken, BE). Nitrocellulose is preferred to other cellulosic materials, such as ethylcelluose, because it improves wettability and thus it facilitates electrochemical processes in

Phase identification

The diffraction data recorded for the synthesized Ni(OH)2 phase are presented in Fig. 2a. All the diffraction peaks have been assigned to the β–Ni(OH)2 phase and the diffraction data have been indexed based on a hexagonal structure [space group: P-3 m1] with cell parameters: a = b = 3.079(2) Å and c = 4.688(8) Å. No mixtures were observed with the α–Ni(OH)2 phase that are usually found in this type of compound [44]. Although the peak located at 33.29° matches the position of one of the maxima

Conclusions

To the best of our knowledge, this is the first report of an electrochromic, screen-printable nickel hydroxide paste. Moreover, the material described may also find application in energy storage and electrocatalysis. Ni(OH)2 has been grown by co-precipitation on the surface of conducting particles. Morphologic study by SEM and TEM images have allowed us to determine that these Ni(OH)2 deposits differ in structure and thickness, depending on the synthesis conditions. Providing a larger surface

CRediT authorship contribution statement

Alaine Sánchez: Investigation, Formal analysis, Visualization, Writing – original draft. Ahmed Esmail Shalan: Investigation. Maibelín Rosales: Investigation, Formal analysis, Visualization, Writing – original draft. Idoia Ruiz de Larramendi: Resources, Writing – review & editing. Francisco Javier del Campo: Conceptualization, Methodology, Supervision, Writing – original draft, Funding acquisition.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

Project number PID2020-113154RB-C22 from the Spanish Ministry of Science and Innovation is gratefully acknowledged. The authors are grateful for the technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF). Jon Velasco's help during the revision of this manuscript is also gratefully acknowledged.

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