Graphene oxide synthesized from zinc-carbon battery waste using a new oxidation process assisted sonication: Electrochemical properties

https://doi.org/10.1016/j.matchemphys.2021.125308Get rights and content

Highlights

  • Sonication-assisted oxidation and exfoliation process was recycled for graphene oxide (SGO) production.

  • ∙The carbon powder of (ZnC) batteries rods and its graphene oxide (SGO) were characterized.

  • ∙The energy and reaction time along with explosion problems were avoided by the proposed approach.

  • ∙Electrochemical performances of SGO were investigated and compared to the Hummers graphene oxide (HGO).

Abstract

The purpose of this paper is to fabricate graphene oxide (GO) from carbon rods of spent (ZnC) batteries using a new optimized approach in electrochemical applications. The proposed method-based sonication for the recycling of carbon rods was adopted as a fast and economical process via a less aggressive pathway. The energy reaction time and explosion problems were avoided by the proposed protocol. The waste graphite powder (carbon rods) and the powder produced by the developed method-based sonication (SGO) were characterized by UV–Visible, XRD, FTIR and SEM. The electrochemical performance of the prepared SGO was evaluated by cyclic voltammetry (CV) and current-voltage (I–V) techniques. The results revealed that SGO has a higher electrocatalytic property compared to the graphene oxide by the standard Hummers method (HGO).

Introduction

Zinc-carbon (ZnC) batteries are used as an important source of energy for operating various electrical devices and appliances, such as remote controls, radio receivers, flashlights, toys and electronic calculators …; however, for non-rechargeable batteries, their application is limited to a single-use. The battery waste does not naturally degrade and it contains heavy metals such as mercury, lead, and zinc, which may be potentially hazardous for human health and the environment [[1], [2], [3], [4], [5], [6]]. The dumping and burying of used batteries in landfills do not represent a solution to the possible risk of waste materials (gases or liquids) leakage into the environment [[7], [8], [9]]. Therefore, the recycling of the used batteries by an environmentally friendly technology, e.g. hydrometallurgy [10], solvent extraction [[11], [12], [13]], chemical precipitation [14,15], electrochemistry [16], calcinations [17], and mechanochemistry [18] is required. The graphite component in the form of a rod (cathode) from a ZnC battery was used as a precursor for producing GO materials [19,20].

Graphene is a planar two-dimensional sheet of atomically thin carbon atoms, forming a hexagonal lattice structure of sp2 hybridization [21]. It has some unique physical and chemical properties, such as a large specific surface area, high-speed electron mobility, excellent electric and thermal conductivity, employed frequently in different research applications and new industrial fields [22,23].

In particular, graphene oxide is a carbonaceous-based amorphous compound with a two-dimensional (2D) structure, covalently bonded to oxygen and hydrogen atoms [24]. It was discovered accidently by Brodie. Normally, graphene is hydrophobic because of the aromatic domains, but at high oxygen-containing functional groups, it becomes a more hydrophilic material (graphene oxide), making it easily dispersed in the solvents. Recently, GO has attracted considerable attention of scientists and researchers increasingly in fields such as physics, chemistry, biology and material sciences, because of being an important building block via many promising routes towards the large-scale production of graphene and other related materials [25]. Currently, the main approaches to the synthesis of GO were the methods of Brodie (1859, fuming HNO3 and KClO3 as the intercalant and oxidant) [26], Staudenmayer (1898, H2SO4 and HNO3 in conjunction with an oxidant of KClO3) [27] and Hammers (1958, H2SO4, NaNO3 and KMnO4) [28], where the latter method is preferred for GO synthesis.

The oxidation process of graphite was recently modified by Tour's group by excluding NaNO3. The amount of KMnO4 was increased and the reaction was performed in a 9:1 ratio mixture of H2SO4/H3PO4, resulting in improved efficiency and yield of the oxidation process [[29]a), [29]. Nishina et al. also excluded the sodium nitrate by minimizing the hazardous reagent of the reaction and been provided a continuous flow system for large-scale synthesis of GO [[29]b), [29]]. Xing et al. reduced the quantity of KMnO4 using K2FeO4 to enhance the oxidation reaction to proceed at room temperature [30]. The percentage of oxygen present in GO was controlled by varying the ratio of oxidant (KMnO4) to graphite [31,32]. The Low oxygen content of 18 wt% was obtained, when the ratio of graphite to KMnO4 varied from 3 to 0.25 (w/w) [33]. Realizing the reaction only in the presence of sulphuric acid/potassium persulfate followed by hydrolysis under controlled temperatures yields a lower degree of structural defects (1–4%) in the obtained carbon framework [34,35]. It must be noted that the degree of oxidation of GO also depends on the graphite nature and source. Few researchers attempted to valorise the waste zinc-carbon battery's graphite into graphene oxide, since the commercial dry battery is a popular choice, we intended to prepare low-cost graphene in protonic acids with oxidizing agents assisted sonication. After graphite being separated, washed and crushed, it's treated with acid (HCl, H3PO4,H2SO4, …) for impurities removal, then the recovered product is generally oxidized to graphene oxide by the hummer's method [36]. Shi et al. reported that the flake size of graphite also plays a pronounced role in simplifying the purification process of GO with better yields. Phosphoric acid can expand the interlayer distance of graphite reaching ∼7.3 Å, with an appreciable intercalation efficiency, as recently reported by Kovtyukhova et al. [[37], [37](a)]. The purification strategy of GO by gravity settling in sulphuric and phosphoric acids as intercalants was reported by Lochab et al. [[37], [37](b)].

The problems of explosion (ClO2), acid fog, toxic gases release (NO2 and N2O4), prolonged reaction time, tedious purification (sifting, filtration, centrifugation, decantation, multiple washings), occasional use of organic solvents (ethanol, ether) and the generation of large wastewater amounts (Na+, NO3) are mostly observed in these synthetic protocols. In addition, the reaction control requests energy and time. Thereby demanding the need for easier synthetic protocol. Nonetheless, a synthetic route that eliminates the usage of sodium nitrate and minimizes the energy and reaction time may be advantageous. As the known threat of pollution by different sources such as organic compounds (pesticides, dyes, drugs …) and heavy metals [38], graphene has been used for their detection due to its high sensitivity and potential reactive surface [39,40].

The purpose of this work is to develop a cost-effective and simple synthesis process, which includes ultrasonication based on standard Hummer's reagents to fabricate graphene oxide (SGO) from carbon rods of ZnC primary batteries, in order to minimize the energy and reaction through some simplified steps with common instruments. The produced SGO by the novel method, as well as its characterizations were discussed and assessed compared to bare graphite rod (ZnC battery), where the cost was estimated accordingly. The electrochemical behavior of SGO and HGO was studied by cyclic voltammetry (CV) and current-voltage (I–V) methods and was compared to the raw graphite for the redox kinetic behavior of Ferri/ferrocyanide by the modification of carbon paste electrode. The synthesis approach by modifying some key parameters was adopted to produce an interesting electrocatalyst that demonstrated high performances as a carbon paste electrode modifier.

Section snippets

Materials and methods

Sodium nitrate (NaNO3 ≥99.0%), potassium permanganate (KMnO4 ≥99.0%), sulphuric acid (H2SO4 95.098.0%), hydrogen peroxide [H2O2 30% (w/v)] and hydrochloric acid (HCl 37%), were purchased from Sigma Aldrich, USA, and used as such.

The UV spectra were registered using (Shimadzu spectrophotometer, model biochrom) single monochromator instrument in the wavelength range 220620 nm. X-ray diffraction studies of the (ZnC) carbon battery rod and its graphene oxide (SGO) were carried out using a

Characterization of the prepared graphene oxide (GO)

The preparation of graphite oxide GO from the carbon rods of the (ZnC) batteries was confirmed by the UV–Visible spectroscopy (Fig. 2A). The SGO exhibited at 243 nm and 314 nm the bands typical of graphene oxide, which are attributed to π–π* transitions of aromatic C–C and C–O bonds, respectively; which is not the case for HGO that exhibited only a band at 296 nm [43]. The band gap between the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO), was estimated from the

Conclusion

In summary, a novel optimized method-based sonication to produce graphene oxide (GO) from carbon powder ((ZnC) battery's carbon rod) was presented, founded on recycling the carbon material in batteries. In addition, it is fast and economical via a less aggressive approach to open new trails based on the properties and materials degree of oxidation. The energy reaction time and explosion problems were avoided by the proposed method.

The graphite rods of the (ZnC) batteries and the graphene oxide

CRediT authorship contribution statement

A. Loudiki: Conceptualization, Methodology, Supervision, Visualization, Writing – original draft, Writing – review & editing. M. Matrouf: Conceptualization, Methodology, Supervision, Visualization, Writing – original draft, Writing – review & editing. M. Azriouil: Conceptualization, Methodology. F. Laghrib: Methodology, Writing – original draft. A. Farahi: Writing – original draft, Supervision. M. Bakasse: Conceptualization, Writing – review & editing. S. Lahrich: Conceptualization,

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.

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