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Article

Synthesis and Characterization of Coconut-Derived Graphene Nano Sheet (GNS) and Its Properties in Nickel/GNS and Zinc/GNS Hybrid Electrodes

by
Kerista Tarigan
1,2,
Rikson Siburian
2,3,*,
Isa Anshori
4,5,
Nuni Widiarti
6,
Yatimah Binti Alias
7,8,
Boon Tong Goh
9,
Jingfeng Huang
10,
Fathan Bahfie
11,
Yosia Gopas Oetama Manik
2,3,
Ronn Goei
10 and
Alfred Iing Yoong Tok
10
1
Department of Physics, Faculty of Mathematics and Natural Sciences, Universitas Sumatera Utara, Medan 20155, Indonesia
2
Carbon and Frankincense Research Center, Universitas Sumatera Utara, Medan 20155, Indonesia
3
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Sumatera Utara, Medan 20155, Indonesia
4
Lab on Chip Laboratory, Department of Biomedical Engineering, Bandung Institute of Technology, Bandung 40116, Indonesia
5
Research Center for Nanoscience and Nanotechnology (RCNN), Bandung Institute of Technology, Bandung 40132, Indonesia
6
Chemistry Department, Faculty of Mathematics and Natural Sciences, Universitas Negeri Semarang, Semarang 50229, Indonesia
7
Department of Chemistry, Faculty of Science, Universiti Malaya, Kuala Lumpur 50603, Malaysia
8
Centre for Ionic Liquids (UMCiL), University of Malaya, Kuala Lumpur 50603, Malaysia
9
Low Dimensional Materials Research Centre, Department of Physics, Faculty of Science, University of Malaya, Kuala Lumpur 50603, Malaysia
10
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
11
Research Center of Mining Technology—National Research and Innovation Agency of Indonesia, Jl. Sutami Km 15, Tanjung Bintang, South Lampung, Lampung 35361, Indonesia
 
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Author to whom correspondence should be addressed.
Processes 2024, 12(9), 1943; https://doi.org/10.3390/pr12091943
Submission received: 1 August 2024 / Revised: 4 September 2024 / Accepted: 6 September 2024 / Published: 10 September 2024
(This article belongs to the Special Issue High-Efficiency Nanomaterials Synthesis and Applications)
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Abstract

:
This study introduces a sustainable method of producing a graphene nano sheet (GNS) from coconut shells and investigates its application in GNS, Ni/GNS, and Zn/GNS electrodes for advanced energy storage devices. The GNS was synthesized in a scalable manner using a pyrolysis and impregnation technique, with its successful synthesis verified by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and electrical conductivity measurement characterizations. The study highlights the enhanced performance of Zn/GNS electrodes, which outperform both pure GNS and Ni/GNS variants. This superior performance is attributed to the smaller particle size of Zn (mean = 2.356 µm) compared to Ni (mean = 3.09 µm) and Zn’s more favourable electron configuration for electron transfer. These findings demonstrate the potential of bio-derived GNS composites as efficient, high-performance electrodes, paving the way for more sustainable and cost-effective energy storage solutions.

1. Introduction

Chemical potential energy is converted into electrical energy through the transfer of electrons between the cathode and the anode in batteries [1,2]. High-quality batteries are characterized by their energy density [3,4], power density [5,6], stability [7,8], low internal resistance [9,10], and cost-effectiveness [11]. Typically, carbon materials are employed as the anode in primary batteries, while carbon–metal alloys serve as the cathode [12,13]. The choice of materials used in battery production significantly affects the overall quality and cost of the batteries [14,15,16]. Therefore, exploring new alternative materials for mass-producing electrode material is essential [17,18].
Graphene has captured considerable attention in the field of electrochemical energy storage systems due to its remarkable properties [19,20]. As a single-layer carbon with a 2D lattice structure, graphene exhibits an array of remarkable characteristics, including its unique 2D carbon structure [21,22,23], sp2 hybridization [24,25], exceptional strength [26,27], a notably large surface area of 2600 m2g−1 [28,29], high electrical conductivity reaching up to 1250 Scm−1 [30,31,32], and impressive thermal conductivity ranging from 4840 to 5300 Wm−1K−1 [33,34]. Recent advancements have shown that tuning electronic properties through novel synthesis methods can significantly enhance material performance. For instance, Khan et al. demonstrated how the in situ solution synthesis of SnSe2/rGO nanocomposites improved thermoelectric performance by tuning electronic properties, highlighting the potential for integrating graphene with other nanomaterials to achieve superior functional characteristics [35]. Similarly, Liyanage et al. synthesized graphene oxide from sonicated graphite flakes, revealing valuable insights into the Hall effect measurements of these materials, which are critical for understanding and optimizing their electronic transport properties in energy storage applications [36]. These studies underscore the importance of continued innovation in graphene synthesis and modification to fully harness its potential in high-performance electrochemical systems.
Graphene is produced by the exfoliation of graphite. Many techniques of exfoliation are developed, such as scotch tape, electrochemical, chemical, liquid phase exfoliation, and ball milling [37]. These techniques have advantages and disadvantages. Meanwhile, the best quality graphene is produced by the Chemical Vapour Deposition (CVD) method, in which chemical gases or vapours (Hydrocarbon gas) react on the substrate surface to deposit coatings or nanostructures. This method can produce large-area graphene with good control over layer thickness instead. The process requires specialized equipment and high temperatures, and transferring graphene from the substrate to another surface can be challenging; however, the raw material used is graphite. According to our previous research, biomass has the potential raw material to produce graphene nanosheets via the pyrolysis technique [38]. This material is used as a supercapacitor and conducting material [39,40].
The distinctive characteristics of graphene-based materials, such as pristine graphene, graphene oxide (GO), reduced graphene oxide (rGO), and functionalized graphene, make them fundamental to the progress of battery technology. Pristine graphene exhibits exceptional conductivity, reaching up to 1250 S/cm, but it does not possess functional groups that facilitate robust material interactions. Functional groups on graphene oxide (GO) improve composite stability, while reduced graphene oxide (rGO) strikes a balance between conductivity and functionality, hence enhancing battery capacity and stability. Unique functionalized graphene, tailored for certain uses, attains improved performance. In previous reports, GNS were synthesized via pyrolysis, which is a simple method [41]. This method successfully produces graphene-derived biomass characterized by Raman, showing D, G, and 2D peaks. Moreover, XPS indicates the presence of Csp2 bonding intensity in GNS, with a broad XRD peak at 2θ = 23.7°, indicating that the produced graphene is layered [38].
An illustrative example that underscores the immense potential of graphene as an energy storage material is Li/graphene, exhibiting an impressive high capacity of 744 mAh/g [42,43]. This compelling result underscores the prospect of graphene as a highly efficient energy storage material, particularly for lithium and sodium ions in battery applications. The incorporation of graphene in electrochemical energy storage systems opens up exciting avenues for improving battery performance and meeting the increasing needs for cutting-edge energy storage solutions. The remarkable properties of graphene pave the way for advancements in battery technology, fostering the development of more sustainable and high-performance energy storage devices.
The development of batteries faces significant challenges, primarily the high cost and non-recyclability of lithium after use. Additionally, the energy density and capacity of conventional primary batteries remain relatively low [44]. Prolonged usage can lead to weak interactions between the electrodes, resulting in reduced electron transport [45,46] and potential loss of electrical contact [47,48]. To address these issues, incorporating graphene as electrode materials offers a promising solution. This research aims to demonstrate how graphene can enhance energy storage capacity, consequently increasing the specific energy and energy capacity of batteries [46,49].
In previous studies, graphene has been successfully utilized as a battery cathode, yielding positive results in enhancing energy storage capabilities [42,50]. Notably, the addition of graphene to battery anode materials enhances electron conductivity, thereby improving the anode’s power supply capacity. Furthermore, the introduction of Ni and Zn metals further boosts the anode’s activity while enhancing the electrical interaction quality of the graphene layer [51,52].
Researchers have proposed modifying carbon materials, particularly with the use of Nickel and Zinc [53,54,55], and employing these modified materials as electrode supports in primary battery cells. By leveraging the unique properties of graphene and its potential interactions with metal dopants, this approach holds great promise for advancing battery technology and addressing the limitations of traditional primary batteries. The exploration of modified carbon materials as an electrode support may pave the way for more efficient and high-performance primary battery systems.

2. Methodology

2.1. Chemical Reagents

Coconut shell from North Sumatera Province (Indonesia) was used as a raw material to produce the GNS powder. Distilled water, aluminium foil, activated carbon, nickel chloride (NiCl2 99 wt. %), zinc chloride (ZnCl2 99 wt. %), and ethanol (C2H5OH 96%) were purchased from E-Merck and used without any further purification.

2.2. GNS Production

The process began by cutting coconut shell charcoal into chips, and 15 g of these chips were subjected to heating at 600 °C for 1 h in an inert nitrogen atmosphere. After the heating process, a 150-mesh screen was employed to achieve a uniform shape and size of the GNS. The resulting material was then washed with distilled water and subsequently dried at 70 °C to obtain the final GNS product [38,56].

2.3. Preparation of Ni/GNS and Zn/GNS

To prepare Ni/graphene in a 1:1 ratio, 1 g of NiCl2 was first dissolved in 100 mL of absolute ethanol, and separately, 1 g of graphene was dispersed in another 100 mL of absolute ethanol. Both solutions were stirred individually for an hour at 500 rpm at room temperature. After this, the NiCl2/ethanol solution was combined with the graphene/ethanol solution, and the resulting mixture was further agitated for 2 h using an ultrasonic bath. The resulting solution was filtered and subsequently dried at 100 °C for 12 h to obtain the final Ni/GNS sample. Similarly, the Zn/GNS sample was prepared using the same method [56,57,58] shown in Figure 1.
In the first step (as shown in Figure 2), we produced Ni and Zn ions, which are deposited on the GNS surface. At this step, Ni and Zn precursors (NiCl2 and ZnCl2) were dissolved in ethanol solvent. Ni and Zn precursors with an oxidation state interact with ethanol, producing Ni and Zn ions. Then, Ni and Zn ions were deposited on the GNS surface, producing Ni and Zn ions/GNS. Ethanol may act as a reduction agent in the reduction process of Ni and Zn precursors. In the second step, the Ni or Zn metal ions are attached to GNS surfaces via chemical interaction between Ni or Zn on GNS, producing Ni or Zn metals where they are well deposited on GNS. That is possible because GNS may donate electrons to convert Ni and Zn ions to Ni and Zn metal clusters. In the last step, Zn metal clusters will be distributed (migrated) on the surface of GNS to form Zn/GNS (Zn metals deposited on GNS) on the same condition that Ni metal cluster will also be distributed (migrated) on the surface of GNS to form Ni/GNS (Ni metals deposited on GNS).

2.4. Characterizations

In this study, we conducted an analysis of GNS, Ni/GNS, and Zn/GNS using EDX and XRD techniques. Before doping with metals, the GNS was characterized using a Renishaw inVia™ confocal Raman microscope, and the electrochemical performance was evaluated using autolab PGSTAT 30 potensiostat/galvanostat in a three-electrode setup. The electrochemical cell included a modified glassy carbon electrode (GCE) with a diameter of 3 mm as the working electrode, an Ag/AgCl electrode as the reference electrode, and a platinum rod as the counter electrode. GCE was polished with alumina powder and thoroughly rinsed with distilled water prior to use. To prepare a homogenized suspension, 1 mg/mL of the synthesized GNS was dispersed in distilled water using ultrasonication for 30 min. Then, 5 μL of this suspension was applied onto the GCE surface and left to air-dry at room temperature, forming the GNS-modified GCE (GNS/GCE).
EDX analysis was carried out using an EM 30 COXEM equipped with an accelerating voltage of 20 kV. The XRD analysis uses a beam size of 10 mm × 10 mm, with Cu/Kα monochromatic graphite radiation (λ = 1.5406) at 40 kV and 100 mA. The range of 2θ was set from 10° to 90° in 2.0° steps. The X-ray patterns was obtained using a SWXD Diffractometer from Rigaku Corporation (Singapore), operating at 18 kW. The data obtained were processed using D/MAX-2000/PC version 3.0.0.0. Additionally, a conductometer was used to evaluate the electrical conductivity of the GNS, Ni/GNS, and Zn/GNS samples.
These analytical techniques allowed us to characterize the structural and electrical properties of the different materials and provide valuable insights into their potential as electrode materials for primary batteries.

3. Results and Discussion

3.1. GNS Characterization and Electrochemical Performance

The GNS was synthesized from coconut shell, a byproduct with abundant carbon elements. The reported method in Section 2 successfully transforms biomass into GNS. The material was characterized via Raman spectroscopy and compared with commercial graphene. Through Raman Scattering, shifts in energy provides details about the system’s vibrational modes and provides data regarding the number of layers, charge doping, stress, and strain conditions.
As seen in Figure 3, the obtained graphene has three major peaks: D, G, and 2D bands at ±1350 cm−1, ±1580 cm−1, and ±2790 cm−1 [60], respectively. The peaks show slight differences in peak width. The full-width half maximum (FWHM) of the peaks were calculated using the Lorentzian fitting shown in Table 1.
From Table 1, the GNS synthesized has a broader peak than the commercial graphene. The feedstock contains various organic functional groups, such as carbonyl, ether, and amine. The pyrolysis process at 600 °C may have introduced defects in the GNS structure. The D peak indicates defects in the crystal lattice leading to a disruption of the hexagonal carbon structure’s symmetry [61]. The G peak signifies the presence of well-organized graphitic carbons, and the 2D peak usually combines with G peaks, indicating the graphitic sp2 [62,63]. The ratio ID/IG of the GNS synthesized is 0.622 compared to the commercial graphene, which is 0.136. The ID/IG commercial graphene is lower than the GNS synthesized, indicating a high degree of graphitization and a lower value of defects. Defects can have an important role in defining the mechanical and electrochemical properties of electrode materials [64]. The previous results reported Reduce Graphene Oxide (RGO) from coconut husk via electrochemical techniques has an ID/IG of 0.90 and an I2D/IG of 0.84 [56]. Thereby, our technique is more environmentally friendly, cheaper, and capable of scaling. To evaluate the electrochemical properties of the GNS material, Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) were used, as shown in Figure 4.
We used a neutral electrolyte of 0.1 M KCl for initial electrochemical studies to investigate the general redox behaviour and electrode stability in a common and mild electrolyte environment. This approach is consistent with previous studies that utilize KCl due to its inert nature and ability to provide a stable ionic background in electrochemical measurements [65]. The use of 1 M KOH, an alkaline electrolyte, was chosen to further explore the electrochemical performance under conditions more representative of practical applications, particularly in alkaline batteries where such environments are prevalent. The specific concentrations were selected based on established practices in electrochemical testing to ensure compatibility with the electrodes. The GNS has an oxidation–reduction pair [Fe(CN)3−]/[Fe(CN)4−]. The electrochemical behaviour of the GNS-modified GCE was compared to glassy carbon electrode (GCE). Both curves cover a range of potentials from −0.6 to 1.0 volts compared to Ag/AgCl as seen in Figure 4a. The current density of Bare GCE and GNS/GCE were 1.0562 mA/cm2 and 1.0111 mA/cm2. The data show that the Bare GCE performs better than the GNS/GCE. However, when examining Figure 4c, the broader CV curves of the GNS/GCE suggest improved electrochemical properties such as increased surface area and enhanced conductivity. To substantiate this observation, we conducted capacitance calculations on Figure 4c, we use (Equation (1)):
Cp = A/(2mk (V2 − V1))
which represents a relationship where Cp is the capacitance measured in farads (F/g), A is the area (cm2), m is the mass (g), k is the scan rate (V/s), and V2 − V1 represents the voltage (V) difference between two points, with V2 and V1 being the second and first voltages, respectively. As shown in Figure 4c, the cycling of modified electrodes in 1 M KOH scan rate at 50 mV/s increases the capacitance for Bare GCE (50.4 F/g) and GNS/GCE (98.8 F/g). In Figure 4a, the bare glassy carbon electrode (Bare GCE) exhibits clearer redox peaks compared to GNS/GCE, indicating that in a neutral electrolyte, the unmodified GCE has more efficient electron transfer kinetics due to lower electron transfer resistance. Conversely, in Figure 4c, the GNS/GCE shows broader CV curves and higher capacitance in an alkaline medium. This is attributed to the increased surface area and conductivity provided by GNS, which enhances the interaction between the electrode and ions in the solution. According to the double-layer capacitor theory, increased active surface area and conductivity directly boost charge storage capacity and electron transfer rate, especially in more demanding alkaline conditions [66]. These differences suggest that GNS modification is more beneficial under complex electrochemical conditions, such as in alkaline media, where capacitance and electron transfer kinetics are crucial.
Based on Figure 4b, EIS graph shows the Nyquist plot, which illustrates the impedance characteristics of the electrode system. The plot provides insights into the charge transfer resistance, double layer capacitance, and Warburg impedance, reflecting the electrochemical behaviour of the modified electrode compared to the bare electrode. The charge transfer resistance (Rct) values for the Bare GCE and GNS/GCE are 0.30 kΩ and 0.88 kΩ, respectively. Rct is associated with the rate of the redox reaction occurring at the surface of the electrode. The circuit’s parameterization is as follows: The solution resistance, denoted as Rs, is associated with the beginning Z’ of the Nyquist curve. The charge transfer resistance, denoted as Rct, is associated with the Nyquist semicircle. The constant phase element of ion transfer in the composite electrode is denoted as W. Q is the measure of the capacitance of the electrochemical double layer (EDL) at the interface between the electrode and reaction solution. The technical characteristics of the electrode materials are presented in Table 2.
A lower Rct value signifies a more rapid electron transfer rate, implying that the unmodified GCE exhibited greater electrochemical activity compared to the GCE treated with GNS. However, the observed rise in Rct following the GNS synthesized change implies that this alteration potentially introduced an impediment to the flow of electrons. The reason for this may be attributed to the inherent physical characteristics of the carbon material, including its porosity, surface area, and functional and chemical composition [67]. The enhanced efficiency of the GNS/GCE in terms of current density and peak precision highlights its potential for utilization in sensors, energy storage, or other technologies that make use of electrochemical features.

3.2. Ni or Zn Decorated on GNS Study

Ni and Zn were selected as the focus of this study for several reasons. Firstly, Ni and Zn share some similarities with Li in terms of their properties, making them suitable candidates for comparison. Additionally, both metals possess a high charge storage capacity, which sets them apart from other metals and enhances their potential as electrode materials. Moreover, their reactivity is lower than that of Li, making them more stable for battery applications. Combining Ni and Zn with GNS has the potential to create a synergistic effect, further boosting the activity of the composite material. Another advantage of using Ni and Zn is their ease of deposition onto GNS, which is more straightforward compared to Li. This results in lower processing and material costs, making them attractive choices for battery electrode materials.
To confirm the presence of Ni and Zn on the GNS material, X-ray diffraction (XRD) was employed. The XRD analysis allowed the demonstration of the successful deposition of Ni and Zn on the GNS surface, as shown in Figure 5. This verification further supported the potential of GNS-based composites for energy storage applications.
As seen in Figure 5, the enhanced pyrolysis method utilized in this study successfully produced GNS. The presence of weak GNS layers is indicated by the prominent peak observed at 2θ = 23.83°, corresponding to a d-spacing of 3.35 Å. This finding is consistent with previously reported results [68,69,70], further validating the successful formation of the GNS using the scalable pyrolysis method in our study.
Figure 5 illustrates the XRD diffraction patterns of the GNS, Ni/GNS, and Zn/GNS. In the case of Ni/GNS, three prominent peaks have been identified as C (002) at 2θ = 24.97°, 2θ = 44.5°, and 2θ = 78°. These peaks indicate the successful deposition of Ni metal on the surface of the GNS, as they correspond to the crystallographic planes of Ni (111) 2θ = 44.5° and Ni (220) 2θ = 78° [71,72]. Furthermore, the C (002) peak at 2θ = 25.21° in Zn/GNS confirms the presence of the GNS. Additionally, the appearance of peaks at 2θ = 44.5° suggests that Ni metal has also been effectively deposited on the GNS surface in Zn/GNS, with these peaks corresponding to the crystallographic planes of Zn (101) 2θ = 36.2°, Zn (110) 2θ = 43.4°, Zn (102) = 54.3°, and Zn (110) = 71° [73,74].
The XRD analysis presented strong evidence for the successful deposition of Ni and Zn metals onto the GNS material, confirming the synthesis of Ni/GNS and Zn/GNS composites. The presence of these composites holds significant potential for improving the performance of primary battery electrodes and advancing energy storage technology. To further demonstrate the successful doping of Ni and Zn atoms onto the GNS lattice, EDX analysis was conducted. The EDX data and weight composition information of Ni/GNS, Zn/GNS, and GNS are shown in Figure 6, Figure 7, Figure 8, and Table 3, respectively.
This additional analysis provides further validation of the successful incorporation of Ni and Zn atoms into the GNS structure. The combination of XRD and EDX data enhances our understanding of the compositional distribution of the composites, supporting their potential application as electrode materials in primary batteries.
In Figure 6, the EDX shows that the GNS primarily consists of carbon (C) elements, accounting for 90.72 wt. % of its composition. Additionally, oxygen (O) elements make up the remaining 9.28 wt. %. This result indicates that the majority of the GNS’s composition comprises carbon, which is consistent with its characteristics as a GNS material. The presence of oxygen likely arises from surface functional groups or oxygen-containing compounds that may be naturally present in the precursor. A previous report on the synthesis of a GNS from graphite revealed the presence of carbon and oxygen element characteristic peaks at 0.15 and 0.25 keV, similar to our product [75]. Another report on carbon derivated, such as CNT, conducted by Allaedini et al., revealed the presence of carbon element peak at 0.5 keV [76]. which shifting compared to GNS. However, to characterize the structure, one needs to collaborate with other instruments, such as Raman spectroscopy, shown in Figure 3, and XRD, shown in Figure 5.
The EDX measurements provide conclusive evidence of the presence of Nickel and Zinc atoms on the GNS material. This finding aligns with the weight percentage data of Nickel and Zinc in the Ni/GNS and Zn/GNS composites, respectively (Table 3). According to the data, Nickel and Zinc atoms are successfully deposited onto the GNS, with weight percentages of 0.213 wt. % and 2.95 wt. %, respectively (Table 3). The EDX data displayed in Figure 6 and Figure 7. further support these findings, corroborating the successful incorporation of Nickel and Zinc onto the GNS surface. The majority of the GNS’s composition consists of carbon, constituting 90.88 wt. %, which is in line with its characteristic as a single-layer carbon material.
In Figure 9 the mean size of metals doped in GNS via single metal selection was obtained under SEM. The mean particle sizes of Ni/GNS and Zn/GNS were 3.09 µm and 2.356 µm. Figure 10 presents the morphology of Ni/GNS, Zn/GNS, and GNS. The GNS exhibits a characteristic wrinkled surface and thin sheet-like structure Figure 9a. In the case of Ni/GNS (Figure 10b) and Zn/GNS (Figure 10c), small white spots can be observed on the GNS surfaces, indicating a well-distributed presence of Ni and Zn particles on the GNS material.
The distinct morphological features observed in Figure 10, along with the electrical conductivity data, shed light on the structural and electrical characteristics of the composite materials. These findings contribute to a comprehensive understanding of the potential applications and performance of Ni/GNS and Zn/GNS in electrochemical energy storage systems.
Siburian et al. reported that GNS reduced the metal sizes of metals Fe and Pt [57,59]. We suggest two crucial parameters for the decreased size of Ni or Zn particles on GNS. The initial factor pertains to the impact of auxiliary substances, specifically GNS. The GNS possesses exceptional characteristics, namely C-sp2 hybridization, π-bonding, and a substantial surface area. The GNS possesses a clearly defined thin and flat surface. It is reasonable to anticipate that the chemical interaction and reduced size on GNS would enhance the catalytic activity of Ni or Zn. This phenomenon is made possible by the presence of Ni or Zn atoms that are bonded to the surface of the GNS. The occurrence is likely due to an interaction between Nickel (Ni) or Zinc (Zn) and GNS. The evidence is substantiated by the SEM and EDX results presented in Figure 7, Figure 8, and Table 3. The data validate that the Ni or Zn atoms were uniformly dispersed and firmly adhered to the GNS surface, resulting from the chemical bonding between the metals and GNS. Ultimately, we present the schematic representation of diminished metal particles deposited on a GNS substrate, as depicted in Figure 11.

3.3. Ni/GNS and Zn/GNS Electrode Performance

The analysis of the electrical conductivity of the GNS, Ni/GNS, Zn/GNS, commercial primary battery cathode, and commercial primary battery anode (Zn metal plate) were evaluated by a multimeter at room temperature, as shown in Table 4.
As seen in Table 4, the electrical conductivity data shows that Zn/GNS exhibits the highest electrical conductivity, while undoped GNS shows the lowest electrical conductivity. This difference in conductivity can be attributed to the nature of Ni metal as a metalloid, resulting in poorer electrical conductivity compared to Zn. The introduction of the metal dopant has been observed to increase the electrical conductivity of the GNS. This finding aligns with previously published research [51,77,78,79], which reported that metal–GNS alloys have a higher surface-to-volume ratio, enhancing the stability of electron mobility rates. Many factors influence the conductivity of the material, such as the presence of oxygen on graphene, it can increase the conductivity of carbon materials [80], especially graphene. The oxygen-containing groups contributing to improve the charge storage capability of Zn/graphene by enabling the additional reversible adsorption/desorption of ions, such as H+, in RGO sheets. This process disrupts the π cloud in the aromatic domain, leading to improved electrochemical kinetics and performance of Zn/GNS [81]. Moreover, the Raman characterization shown in Figure 3 revealed a significant D peak, indicating the presence of defects in the GNS crystal structure. These defects, including dislocations, atomic vacancies, and oxygen-containing functional groups, can significantly disrupt the sp2 conductive network in graphene, thereby reducing electron mobility and lowering the electrical conductivity of the material. It is important to note that metal doping (such as Ni and Zn) in the GNS can help fill vacancies and improve the structure of the material [82]. This metal doping can enhance the conductivity of the GNS by repairing the conduction pathways and reducing the resistance caused by structural defects. Our results show that while GNS has lower conductivity shown in Table 4, the conductivity increases after metal doping, consistent with this understanding. However, the commercial cathode has higher conductivity than a synthesized electrode due to the composite material being an active material and electrolyte, which increases the electricity performance [83].
The enhancement of electrical conductivity in metal-doped GNS materials is of significant interest, as it has potential implications for improving the performance of energy storage devices. The results from Table 4 contribute to a better understanding of the conductive properties of the composites and support their potential use in electrochemical energy storage systems.
To observe the performance of the composite, we compared it to electrodes that were separated from the primer commercial battery. The trend in electrical conductivity and power density vs. energy density in the GNS is shown in Figure 11 and Figure 12.
From Figure 13, the GNS demonstrates somewhat reduced electrical conductivity in comparison to conventional materials. Nevertheless, it possesses chemical inertness, hence preventing contamination that might potentially augment conductivity via electron sources. In addition, GNS exhibits remarkable stability since it maintains conductivity levels exceeding 1 volt. The power density versus energy density is tested to assess the performance of materials used as cathodes and anodes [84]. The conductivity number is in line with the power density vs. energy density, showing the commercial is more high and stable than GNS, modifying the GNS with metals may be expected to modify their performances, as shown in Figure 14.
As can be seen in Figure 11, Zn/GNS is lower than the commercial anode; however, Zn/GNS performs better than Ni/GNS. Focusing on the potential increases to 1.5 V, its specific capacity drops slightly due to GNS’s high surface area and exceptional conductivity, which may enhance the charge storage capability under higher potentials, leading to an increased specific capacity. Additionally, the GNS’s ability to maintain structural integrity under varying potential conditions could contribute to this phenomenon This could be due to some attributed factors, such as the first Ionic Size dopant, as seen in Figure 8. The particles of Zn are smaller than Ni; this size difference could potentially enable a more effective arrangement of ions and enhance the movement of electrons, resulting in improved conductivity [85]. Further, the position 2 theta peaks are different between the Zn- and Ni-doped GNS, as shown in Figure 5. Probably, the size among them is different. It may affect the electrical performances. A corresponding inverse correlation with the optical band gap [86] in line with the increasing band gap reduces the electrical conductivity due to a more significant band gap, indicating that fewer electrons may move into the conduction band. Second, the charge transfer, when metals like Zinc (Zn) or Nickel (Ni) are applied to carbon materials, has the ability to either provide or receive electrons, which in turn modifies the electronic configuration of the carbon and thus affects its conductivity. However, Zn, being a member of group II on the periodic table, typically donates two electrons to form Zn2⁺. Ni, as a transition metal, also commonly donates two electrons to form Ni2⁺, although the electron donation in transition metals can involve more complex interactions due to their partially filled d orbitals [87]. This electron donation process is relatively straightforward and efficient, enhancing Zn’s ability to participate in redox reactions within the electrode, thereby improving charge storage efficiency in the graphene nano sheet (GNS). In contrast, Nickel (Ni), although capable of donating two electrons to form Ni2⁺, is a transition metal with a partially filled d orbital, which introduces more complex and less efficient electron interactions. This complexity can reduce the effectiveness of interactions between Ni and GNS, leading to lower electrochemical performance. Therefore, the ease of electron donation and the stable interaction between Zn and GNS contribute to the superior performance of Zn/GNS compared to Ni/GNS.

4. Conclusions

This study successfully synthesized and characterized a graphene nano sheet (GNS) from coconut shells and explored their application in Ni/GNS and Zn/GNS hybrid electrodes for energy storage. The following key conclusions are drawn:
(1)
Synthesis and Characterization: GNS was successfully produced using a scalable pyrolysis method, displaying high surface area and electrical conductivity, confirming the potential of biomass-derived materials.
(2)
Enhanced Performance of Zn/GNS: Zn/GNS showed superior electrical conductivity (340 µS/cm2) and electrochemical performance compared to Ni/GNS and undoped GNS, attributed to Zinc’s favourable electron transfer properties and smaller particle size.
(3)
Application in Energy Storage: Zn/GNS demonstrated potential as a high-performance electrode material for batteries, offering enhanced conductivity and stability, making it a promising candidate for sustainable energy storage solutions.
(4)
Environmental and Scalability Benefits: Utilizing coconut shells not only provides a cost-effective and scalable method for GNS production but also supports environmental sustainability by repurposing waste materials.
(5)
Future Research: Further optimization of GNS production and the exploration of additional applications, such as supercapacitors or sensors, are recommended to expand the utility of these composites.

Author Contributions

Conceptualization, K.T. and R.S.; methodology, R.S.; software, I.A.; validation, J.H.; formal analysis, F.B.; investigation, R.G.; resources, B.T.G.; data curation, N.W.; writing—original draft preparation, K.T.; writing—review and editing, R.S., Y.B.A. and A.I.Y.T.; visualization, R.G.; supervision, R.S.; project administration, Y.G.O.M.; funding acquisition, R.S. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by to the Rector of the University of Sumatera Utara and the DAPT-LPDP under the scheme “Riset Kolaborasi Indonesia, Universitas Sumatera Utara Tahun Anggaran 2024 SKEMA—C” (Nomor: 16773/UN5.1.R/PPM/2024).

Data Availability Statement

The original contributions presented in the study are included in the article, further inquiries can be directed to the corresponding author.

Acknowledgments

The authors express their gratitude to PT Dynatech International–Jakarta for providing support on SEM–EDX for this research.

Conflicts of Interest

The authors declare no conflicts of interest.

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Processes 12 01943 g001
Figure 1. Schematic of Ni or Zn metals doping process on GNS.
Figure 1. Schematic of Ni or Zn metals doping process on GNS.
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Processes 12 01943 g002
Figure 2. Schematic forming Ni or Zn cluster process illustrates the step-by-step impregnation of Ni and Zn ions onto the GNS surface [59].
Figure 2. Schematic forming Ni or Zn cluster process illustrates the step-by-step impregnation of Ni and Zn ions onto the GNS surface [59].
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Processes 12 01943 g003
Figure 3. Raman spectra comparison between synthesized GNS derived from coconut shells and commercial graphene showing D, G, and 2D peaks. For GNS, the deconvoluted Raman peaks are shown using different coloured lines [D (red), G (green) and 2D (blue)].
Figure 3. Raman spectra comparison between synthesized GNS derived from coconut shells and commercial graphene showing D, G, and 2D peaks. For GNS, the deconvoluted Raman peaks are shown using different coloured lines [D (red), G (green) and 2D (blue)].
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Processes 12 01943 g004
Figure 4. (a) CV curves of Bare GCE and GNS/GCE recorded in 0.1 M KCl containing 5 mM [Fe(CN)6]3−/4− at 50 mV/s; (b) EIS result of Bare GCE, and GNS/GCE recorded in 0.1 M KCl containing 5 mM [Fe(CN)6]3−/4−; (c) CV curves Bare GCE, and GNS/GCE recorded in 1 M KOH at 50 mV/s.
Figure 4. (a) CV curves of Bare GCE and GNS/GCE recorded in 0.1 M KCl containing 5 mM [Fe(CN)6]3−/4− at 50 mV/s; (b) EIS result of Bare GCE, and GNS/GCE recorded in 0.1 M KCl containing 5 mM [Fe(CN)6]3−/4−; (c) CV curves Bare GCE, and GNS/GCE recorded in 1 M KOH at 50 mV/s.
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Figure 5. XRD patterns of GNS, Ni/GNS, and Zn/GNS composites. Displays characteristic peaks confirming Ni and Zn deposition on GNS.
Figure 5. XRD patterns of GNS, Ni/GNS, and Zn/GNS composites. Displays characteristic peaks confirming Ni and Zn deposition on GNS.
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Figure 6. Energy dispersive X-ray (EDX) spectra of GNS showing high carbon content (90.72 wt. %) with oxygen (9.28 wt. %), confirming successful GNS synthesis suitable for conductive applications EDX spectra of GNS with inset the elements mapping of GNS (a), C (b), and O (c).
Figure 6. Energy dispersive X-ray (EDX) spectra of GNS showing high carbon content (90.72 wt. %) with oxygen (9.28 wt. %), confirming successful GNS synthesis suitable for conductive applications EDX spectra of GNS with inset the elements mapping of GNS (a), C (b), and O (c).
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Figure 7. EDX spectra and elemental mapping of GNS showing predominant carbon and oxygen content, indicating surface functional groups affecting electrochemical properties Ni/GNS (a), C (b), O (c), and Ni (d).
Figure 7. EDX spectra and elemental mapping of GNS showing predominant carbon and oxygen content, indicating surface functional groups affecting electrochemical properties Ni/GNS (a), C (b), O (c), and Ni (d).
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Figure 8. EDX spectra of Zn/GNS, with inset the mapping element of Zn/GNS (a), carbon (b), oxygen (c), and Zinc elements (d) confirming successful Zn deposition on GNS.
Figure 8. EDX spectra of Zn/GNS, with inset the mapping element of Zn/GNS (a), carbon (b), oxygen (c), and Zinc elements (d) confirming successful Zn deposition on GNS.
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Figure 9. Particle size of Ni/GNS (a) and Zn/GNS (b) essential for enhanced conductivity and performance.
Figure 9. Particle size of Ni/GNS (a) and Zn/GNS (b) essential for enhanced conductivity and performance.
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Figure 10. SEM Image of GNS (a), Zn/GNS (b), and Ni/GNS (c).
Figure 10. SEM Image of GNS (a), Zn/GNS (b), and Ni/GNS (c).
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Figure 11. Electrical conductivity comparison between commercial cathode (a) and GNS (b).
Figure 11. Electrical conductivity comparison between commercial cathode (a) and GNS (b).
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Figure 12. Power density vs. energy density plots comparing the performance of commercial cathodes (a) and GNS (b).
Figure 12. Power density vs. energy density plots comparing the performance of commercial cathodes (a) and GNS (b).
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Figure 13. Electrical conductivity of commercial battery anode (a), Ni/GNS (b), and Zn/GNS (c).
Figure 13. Electrical conductivity of commercial battery anode (a), Ni/GNS (b), and Zn/GNS (c).
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Figure 14. Power density vs. energy density of commercial battery anode (a), Ni/GNS (b), and Zn/GNS (c).
Figure 14. Power density vs. energy density of commercial battery anode (a), Ni/GNS (b), and Zn/GNS (c).
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Table 1. FWHM number of GNS and commercial graphene.
Table 1. FWHM number of GNS and commercial graphene.
D FWHMG FWHM2D FWHM
GNS239.92 ± 2.6678.46 ± 0.85690.21 ± 6.23
Commercial graphene28.19 ± 10.2328.91 ± 0.8664.46 ± 2.17
Table 2. EIS results of fitted Nyquist plot.
Table 2. EIS results of fitted Nyquist plot.
Rs (Ω)Rct (Ω)Q (µMho)NW (mMho)
Bare GCE493.81297.091.030.860.0017
GNS/GCE136.488814.980.780.0016
Table 3. Comparison of elements of Ni/GNS, Zn/GNS, and GNS (EDX data).
Table 3. Comparison of elements of Ni/GNS, Zn/GNS, and GNS (EDX data).
ElementNi/GNSZn/GNSGNS
C89.54 (wt. %)71.29 (wt. %)90.72 (wt. %)
O10.25 (wt. %)25.75 (wt. %)9.28 (wt. %)
Ni0.21 (wt. %)--
Zn-2.95 (wt. %)-
Table 4. Electrical conductivity of GNS, Ni/GNS, and Zn/GNS.
Table 4. Electrical conductivity of GNS, Ni/GNS, and Zn/GNS.
SampleMeasurement of Conductivity (µS/cm2)
GNS227
Ni/GNS264
Zn/GNS340
Commercial primary battery anode 400
Commercial primary battery cathode580
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Tarigan, K.; Siburian, R.; Anshori, I.; Widiarti, N.; Alias, Y.B.; Goh, B.T.; Huang, J.; Bahfie, F.; Manik, Y.G.O.; Goei, R.; et al. Synthesis and Characterization of Coconut-Derived Graphene Nano Sheet (GNS) and Its Properties in Nickel/GNS and Zinc/GNS Hybrid Electrodes. Processes 2024, 12, 1943. https://doi.org/10.3390/pr12091943

AMA Style

Tarigan K, Siburian R, Anshori I, Widiarti N, Alias YB, Goh BT, Huang J, Bahfie F, Manik YGO, Goei R, et al. Synthesis and Characterization of Coconut-Derived Graphene Nano Sheet (GNS) and Its Properties in Nickel/GNS and Zinc/GNS Hybrid Electrodes. Processes. 2024; 12(9):1943. https://doi.org/10.3390/pr12091943

Chicago/Turabian Style

Tarigan, Kerista, Rikson Siburian, Isa Anshori, Nuni Widiarti, Yatimah Binti Alias, Boon Tong Goh, Jingfeng Huang, Fathan Bahfie, Yosia Gopas Oetama Manik, Ronn Goei, and et al. 2024. "Synthesis and Characterization of Coconut-Derived Graphene Nano Sheet (GNS) and Its Properties in Nickel/GNS and Zinc/GNS Hybrid Electrodes" Processes 12, no. 9: 1943. https://doi.org/10.3390/pr12091943

APA Style

Tarigan, K., Siburian, R., Anshori, I., Widiarti, N., Alias, Y. B., Goh, B. T., Huang, J., Bahfie, F., Manik, Y. G. O., Goei, R., & Tok, A. I. Y. (2024). Synthesis and Characterization of Coconut-Derived Graphene Nano Sheet (GNS) and Its Properties in Nickel/GNS and Zinc/GNS Hybrid Electrodes. Processes, 12(9), 1943. https://doi.org/10.3390/pr12091943

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