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Article

Advanced Electrochemical Performance of NiWO4/Graphene Oxide as Cathode Material for Zinc Ion Battery

by
Likai Deng
and
Shifa Wang
*
School of Electronic and Information Engineering, Chongqing Three Gorges University, Chongqing 404000, China
*
Author to whom correspondence should be addressed.
Energies 2025, 18(8), 2023; https://doi.org/10.3390/en18082023
Submission received: 18 March 2025 / Revised: 6 April 2025 / Accepted: 10 April 2025 / Published: 15 April 2025
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Abstract

:
The NiWO4 powder was prepared by combining the hydrothermal method with calcination. Several studies have demonstrated that the NiWO4/graphene oxide composite can enhance the electrochemical performance of the NiWO4 material. However, no studies have investigated the use of NiWO4/graphene oxide composite material as the cathode material in zinc-ion batteries. The successful preparation of the NiWO4/graphene oxide composite material is verified by various characterization techniques. The NiWO4/graphene oxide composite, which is meant to be a cathode material, is fabricated into electrode sheets and incorporated into CR2025 coin cells for electrochemical assessment. The experimental results indicate that the material exhibits a high charge–discharge specific capacity with high rates. At a current density of 0.1 A g−1, it has a specific capacity of 490.2 mA h g−1. Even after 2000 charge–discharge cycles at a current density of 1 A g−1, the capacity remains constant at 75.2%. Through calculations, it is found that the charge storage is mainly contributed to by pseudocapacitance.

1. Introduction

Energy is a crucial factor in the development of contemporary society. The use of fossil fuels can lead to energy shortages and environmental pollution. As a result, humans have been actively developing sustainable resources along with high-efficiency energy conversion and energy storage technologies [1,2]. Subsequently, an efficient energy storage system featuring high electrochemical performances, best safety characteristics, a long service life, and fast charging capabilities is the key technology for the rational utilization of intermittent renewable resources such as wind and solar energy [3,4]. Various metal ions have been explored as the charge carriers for batteries in the present time. Among these, lithium-ion batteries have achieved commercialization due to their ability to operate at high voltages and possess high energy densities [5,6,7].
However, lithium-ion batteries have issues such as poor safety performance, electrolyte pollution, and requirements for a special preparation environment. Recently, zinc-ion batteries have been widely regarded as alternatives to lithium-ion batteries due to the fact that zinc-ion batteries feature a low redox potential (−0.76 V) compared to conventional hydrogen electrodes, inexpensive materials, abundant supply, non-toxicity, and enhanced safety [8]. Nevertheless, the application of the positive electrodes of zinc-ion batteries is often restricted by their low capacity and poor stability. Developing high-performance cathode materials is crucial and essential for achieving both superior energy density and extended cycle stability in next-generation aqueous zinc-ion battery systems [9].
Graphene oxide (GO) serves as a versatile electrode matrix due to its intrinsic electrochemical properties, functioning as a conductive scaffold that enhances charge transfer kinetics and electronic conductivity when composited with transition metal oxides or other active materials [10]. It has been shown that the combination of NiWO4 and graphene oxide can improve the electrochemical performance of NiWO4. Xu et al. [11] prepared NiWO4/GO nanocomposites via the solvothermal method and exhibited a high specific capacitance of 1031.3 F g−1 at a current density of 0.5 A g−1. The capacitive performance of the NiWO4/GO electrode was significantly enhanced due to the NiWO4 nanoparticles and reduced graphene oxide work synergistically to provide conductive channels and active sites. Kumar et al. [12] prepared a reduced graphene–nickel tungstate (RGO/NiWO4) nanocomposite via the hydrothermal method and employed it as the negative electrode for lithium-ion batteries. Compared with NiWO4 nanoparticles, the RGO/NiWO4 nanocomposite exhibits better electrochemical performance and cycle stability. Xing et al. [13] prepared RGO/NiWO4 composites via the hydrothermal method by incorporating reduced graphene oxide (RGO) into NiWO4. Cyclic voltammetry and the constant-current charge–discharge method were employed to investigate the supercapacitor properties of the composites. Surprisingly, the specific capacitance of the RGO/NiWO4 composite is twice that of NiWO4, and its stability is better than that of NiWO4. The above results indicate that the composite has potential applications in electrochemistry and as a cathode material for lithium-ion batteries.
As a highly conductive current collector, carbon cloth significantly enhances charge transfer kinetics in battery systems. Wu et al. [14] developed a hierarchically structured cathode material through a rapid hydrothermal synthesis using ZIF-67-derived carbon frameworks as sacrificial templates. The resulting MnO2 nanosheet-assembled hollow polyhedrons anchored on carbon cloth (MnO2/CC) demonstrated superior zinc-ion storage capabilities, delivering a reversible capacity of 263.9 mAh g−1 at 1.0 A g−1 after 300 cycles, far exceeding those of the commercial MnO2 electrode. Therefore, the NiWO4/graphene oxide composite, when coated on carbon cloth as the negative electrode material for aqueous zinc-ion batteries, demonstrates potential for enhancing battery performance. However, this research strategy has not been reported in the literature.
In this paper, the NiWO4 powder synthesized via a sequential hydrothermal method and high-temperature calcination are ball-milled with graphene oxide to form a hybrid composite. Systematic evaluation is conducted on the electrochemical performance of the NiWO4/GO composite as a cathode material for aqueous zinc-ion batteries after being deposited onto a carbon cloth current collector. The composite demonstrates a high specific capacity of 490.2 mAh g−1 at 0.1 A g−1. The electrode demonstrates exceptional cycling stability, maintaining 75.2% capacity retention over 2000 cycles at 1 A g−1. This work offers new insights into the role of scheelite materials in high-energy-density batteries.

2. Experimental

2.1. Preparation of NiWO4

NiSO4·6H2O (≥98%), Na2WO4·4H2O (≥98%), and ZnSO4 (≥98%) were obtained from Kemiou Chem. Ltd., Tianjin, China, and used without further purification. The graphene oxide and acetylene black were obtained from Shanghai MeBao Ltd., Shanghai, China. N-Methylpyrrolidone (NMP) and polyvinylidene difluoride (PVDF) were purchased from Sinopharm Chemical Reagent Corp, Shanghai, China.

2.2. Preparation of NiWO4/Graphene Oxide

The NiWO4 powders were prepared by combining the hydrothermal method and high-temperature calcination. First, 0.1257 g of NiSO4·6H2O (≥98%) and 0.6597 g of Na2WO4·4H2O (≥98%) were dissolved in 60 mL of deionized water while stirring for 1 h. After complete dissolution, the mixture was poured into a polytetrafluoroethylene-lined vessel and transferred to an autoclave for hydrothermal treatment at 120 °C for 12 h. The obtained samples were washed repeatedly and dried for 8 h. Subsequently, the precursor was transferred to a tube furnace for calcination at 900 °C for 5 h, and pure NiWO4 monomers were obtained. Pure NiWO4 powders were ball-milled with graphene oxide for 8 h to obtain NiWO4/graphene oxide composite materials.

2.3. Preparation of Zn//NiWO4/Graphene Oxide Button Batteries

The Zn//NiWO4/graphene oxide batteries were fabricated using zinc foil (100 μm thick) as the anode and a CR2025 standard button-battery case. For the fabrication of the cathode, NiWO4/graphene oxide, acetylene black, and polyvinylidene difluoride (PVDF) were mixed at a weight ratio of 70:20:10, and then dispersed in N-Methylpyrrolidone (NMP) [15]. The resulting paste-like mixture was then applied to a carbon cloth (with a loading of 1.0–1.5 mg) using a coating mold (100 mm thick) and dried at 60 °C for 12 h. All the prepared electrodes were cut into circles with a diameter of 14 mm. A Zn//NiWO4/graphene oxide button battery with a glass-fiber GF/C diaphragm was assembled using 2.0 mol/L ZnSO4 as the electrolyte. Figure 1 shows the preparation flowchart of the Zn//NiWO4/graphene oxide button battery. After assembly, the Zn//NiWO4/graphene oxide battery was left to stand for 4 h before electrochemical testing.

2.4. Electrochemical Experiments

All tests were conducted at room temperature, with the test voltage ranging from 1.0 to 1.8 V. Both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests were performed on an electrochemical workstation (CHI 660E was purchased from CH Instruments, Inc. Shanghai, China). The cyclic performance test and the charge–discharge cycle tests of the battery were performed using the LANHE system (LANHE, CT3001A, was purchased from LANHE. Wuhan, China).

3. Results and Discussions

3.1. Phase Structure and FTIR Analysis

The phase structures of the NiWO4 and NiWO4/graphene oxide were investigated via X-ray powder diffraction (XRD). As shown in Figure 2a, the NiWO4 is in accordance with the standard card JCPDS No. 15-0755 [16], indicating that the NiWO4 was successfully synthesized by combining the hydrothermal method and high-temperature calcination [17]. After the addition of graphene, the diffraction peaks in XRD pattern showed no significant changes because of the low composite ratio, resulting in the failure of graphene oxide to form a distinct phase. There is a minor peak around 2θ = 28°, which corresponds to the characteristic peak of graphene oxide reported in the previous literature, demonstrating the successful complexation of graphene oxide [16]. It can work well with JCPDS No. 65-6212 [18].
To further explore the phase purity of the NiWO4 and NiWO4/graphene oxide, the FTIR spectra of the samples were measured using FTIR spectroscopy (FTIR-650 was purchased from TIANJIN GANGDONG SCI.&TECH. Co., Ltd., Tianjin, China), as shown in Figure 2b. The characteristic peaks of all samples at 3403 cm−1 are associated with the stretching vibration of adsorbed O–H water [19,20,21,22]. For both NiWO4 and NiWO4/graphene oxide, the peak at 1633 cm−1 is related to the H–O–H bending vibration of water [23]. In the 400–1000 cm−1 region, there are several peaks that can be attributed to the vibrations of metal–oxygen [24]. The characteristic peaks at 574 and 503 cm−1 belong to the O–W–O bending vibration and Ni–O stretching vibration, respectively [25]. The characteristic peak at 808 cm−1 corresponds to the bending vibration of the O–W–O bond [26].
The elemental composition, valence state, and charge state of the NiWO4/graphene oxide were investigated using X-ray photoelectron spectroscopy (XPS). XPS full-scan spectra as well as high-resolution XPS spectra of Ni 2p, W 4f, C 1s, and O 1s were acquired. Figure 3 presents the XPS full-scan spectra of the NiWO4/graphene oxide. It can be inferred that there are no other impurity elements in NiWO4/graphene oxide due to the fact that NiWO4/graphene oxide contains only Ni, W, O, and C elements.
In Figure 4a, the high-resolution Ni 2p spectrum of the NiWO4/graphene oxide can be fitted to eight peaks with spin-orbit splitting of Ni 2p3/2 and Ni 2p1/2. In the figure, the binding energies of Ni 2p3/2 and Ni 2p1/2 is 854.31 and 872.92 eV, respectively. The Ni 2p3/2 has satellite peaks at 857.18, 861.23, and 863.97 eV. Similarly, Ni 2p1/2 has satellite peaks at 876.43, 879.36, and 881.58 eV [27,28]. In Figure 4b, for the high-resolution W 4f spectrum of the NiWO4/graphene oxide, four peaks can be observed. The peaks at 35.4 and 34.8 eV correspond to the W 4f7/2. In addition, the peaks at 37.5 and 36.9 eV can be ascribed to the W 4f5/2. Among these, 34.8 and 36.9 eV belong to W5+, and 35.4 and 37.5 eV belong to W6+ [29,30]. In Figure 4c, the high-resolution O 1s spectrum of the NiWO4/graphene oxide can be divided into three peaks at 531.84, 530.90, and 529.65 eV, which, respectively, belong to the adsorbed oxygen, defect oxygen, and lattice oxygen of NiWO4. In Figure 4d, the high-resolution C 1s spectrum of the NiWO4/graphene oxide can be divided into three peaks, which, respectively, belong to the C–C, C = O, and C–O [13].

3.2. Microstructural Analysis

Microstructure characterizations of NiWO4 and NiWO4/graphene oxide were performed by SEM and TEM. It can be seen from Figure 5a that the particles of the NiWO4 are approximately spherical, and they are well defined. The particles have high dispersion, and the fine particles are not fully grown grains. Figure 5b shows the SEM image of the NiWO4/graphene oxide composite material. A small number of graphene oxide particles were attached to the surface of NiWO4. Further detailed characterization needs to be performed by TEM.
Figure 5c shows the EDS spectrum of the NiWO4/graphene oxide. Elements Ni, W, O, C, and Cu were present in the EDS spectrum, and the presence of Cu was caused by the use of copper mesh in the test, so the NiWO4/graphene oxide did not contain other impurity elements. The results were consistent with those of XRD, FTIR, and XPS analysis. No other impurities were found in the NiWO4/graphene oxide. Figure 5d shows a TEM photograph of the NiWO4/graphene oxide. The fine particles covered the larger particles, which was consistent with the SEM results. Whether large particles or fine particles, particles are closely linked to each other. Figure 5e shows an HRTEM photograph of the NiWO4/graphene oxide. It can be seen from the figure that the interplanar spacing of the NiWO4 is about 0.29 nm, corresponding to its (111) crystal face. Figure 5f–j displays the BF-TEM image and corresponding element mapping images of the NiWO4/graphene oxide. The results further confirmed that graphene oxide was uniformly dispersed on the surface of NiWO4, which was consistent with SEM observation.

3.3. Electrochemical Testing

Figure 6a presents the galvanostatic charge–discharge (GCD) profiles of Zn//NiWO4/graphene oxide within the voltage range of 1.0–1.8 V. From the graph, it can be seen that as the current density increases, the specific discharge capacity of the samples decreases. Rate discharge experiments were conducted at current densities of 0.1, 0.2, 0.5, 1.0, 2.0, 3.0, and 0.1 A g−1. Evidently, at a current density of 0.1 A g−1, the sample exhibits a voltage plateau region between 1.58 and 1.60 V, as well as two voltage plateau regions between 1.36 and 1.4 V. The cyclic voltammetry (CV) results shown in Figure 7b are consistent with the results reported in the literature [31]. It is worth noting that the large oxidation area of charge distribution at a current density of 0.1 A g−1 can be ascribed to the hydrogen evolution reaction and the deposition of free Ni3+ in the electrolyte [32].
As depicted in Figure 6b, the rate charge–discharge performance of the Zn//NiWO4/graphene oxide battery was investigated at current densities of 0.1, 0.2, 0.5, 1.0, 2.0, 3.0, and 0.1 A g−1. For each current density, five cycles were carried out. Evidently, when the current density is 0.1 A g−1, the specific capacity of the Zn//NiWO4/graphene oxide battery increases with cycling due to the Zn2+ ions diffusing into the NiWO4 structure and accumulating during cycling [33,34]. In the first cycle, the discharge specific capacity can reach a maximum of 490.3 mAh g−1. This result validates the activation process taking place in the NiWO4/graphene oxide cathode of scheelite, which enhances its capacitive properties during charge–discharge cycling [35,36]. Furthermore, when the current density returns to 0.1 A g−1, the discharge capacity of Zn//NiWO4/graphene oxide can be restored to 391.0 mAh g−1 (79.7% of the initial discharge capacity at 0.1 A g−1), indicating good rate capability, even though there is a capacity decrease of nearly 80% due to the change in current density during the cycle (from 0.1 to 3.0 A g−1).
As presented in Figure 6c, after 100 cycles, the discharge capacity of the Zn//NiWO4/graphene oxide battery remains relatively high (119.4 mAh g−1 at 1.0 A g−1). These are the current density curves of the NiWO4/graphene oxide during the charge–discharge experiments at a current density of 0.1 A g−1 over 100 charge–discharge cycles. The densely packed microsphere structure formed after ball milling is beneficial for Zn2+ intercalation during the discharge process, thus enhancing the capacitance performance [37,38].
Figure 6d presents the electrochemical impedance spectra of the NiWO4/graphene oxide during the 1st charge–discharge cycle and after the 100th charge–discharge cycle. As can be observed, as the battery experiences multiple charge–discharge cycles, its internal resistance gradually increases. This increase in internal resistance is also the cause of the capacity decline [39].

3.4. Battery Performance

Figure 7a presents the long-term cycling performance of the NiWO4/graphene oxide at a high current density of 1 A g−1. After 2000 cycles, it maintains a reversible discharge capacity of 85.1 mAh g−1 (75.2% of the value in the first cycle). Moreover, the coulombic efficiency remains at 100% throughout the cycling process, indicating excellent reversibility. The high-rate electrochemical performance of the NiWO4/graphene oxide is mainly ascribed to the synergistic effect between the ultrathin nanoparticles and the graphene oxide matrix [40]. Table 1 shows the battery performance in this work compared to some previous studies [15,31,41,42,43,44,45,46,47]. It can be seen that this work has a higher point capacity at a low current of 0.1 A g−1, and this research has a longer life and a higher capacity retention rate at a high current of 1 A g−1. Consequently, the NiWO4/graphene oxide proposed in this study can be regarded as a promising cathode material for zinc ion batteries.
As depicted in Figure 7b, the electrochemical characteristics of the Zn//NiWO4/graphene oxide battery were further investigated through cyclic voltammetry (CV) tests. These tests were conducted at different scan rates ranging from 0.1 to 1 mV s−1 within a potential voltage range of 1.0–1.8 V. Evidently, as the scan rate increases, the current density signals of both the anodic peak and the cathodic peak increase, which indicates the characteristics of polarization and ion diffusion processes [48].
The charge storage mechanism can be evaluated by using the peak current generated under different scan rates based on power law relationships. This can be represented by the following Equations (1) and (2) [49].
i = a ν b
log ( i ) = b log ( ν ) + log ( a )
where i represents the redox peak current, v denotes the scan rate, and the values of a and b are variable parameters. Fundamentally, when the value of the b parameter approaches 0.5, the diffusion mechanism predominantly governs the electrochemical behavior. The b value of 1 indicates pseudocapacitive characteristics [50]. Figure 7c presents the plot of log(i) versus log(v). The b values at oxidation–reduction peak 1 and peak 2 were calculated to be 0.82 and 0.84, respectively. These values indicate the characteristics of synergistic diffusion and capacitive control. The capacitance and diffusion controlled contribution mechanisms of the Zn//NiWO4/graphene oxide batteries can be quantified using the expression in Equation (3) [51].
i = k 1 ν + k 2 ν 0.5
where k1 and k2 are the constants. k1 represents the capacitive contribution, while k2v0.5 represents the diffusion controlled contribution. The values of k1 and k2 can be calculated by plotting the relationship between i/v0.5 and v0.5.
Figure 7d depicts a graph presenting the proportion of capacitive contribution and diffusion contribution. The contribution rate of capacitance gradually rises, while the contribution rate of diffusion decreases correspondingly [52]. When the scan rate ranges from 0.1 mV s−1 to 1.0 mV s−1, the percentage contribution of capacitive behavior increases from 55% to 80%, indicating that the capacitive behavior makes a greater contribution at higher scan rates. For the NiWO4/graphene oxide, although the entire electrode reaction process is still dominated by the diffusion of zinc ions, the capacitive process involves the double-electric layer due to the characteristics of nanoparticles. Therefore, these results clearly demonstrate a favorable dominant capacitive-controlled contribution for Zn2+ ion intercalation/deintercalation in NiWO4/graphene oxide. This includes maintaining an appropriate contribution ratio between diffusion and pseudocapacitive behavior, which endows the Zn//NiWO4/graphene oxide battery with sufficient rate performance.

3.5. Battery Cycle Stability

To further understand the cycle stability of the Zn//NiWO4/graphene oxide button batteries, XPS was used to observe the compositional changes of each element in NiWO4/graphene oxide after the 1st and 100th discharge cycles. The binding energy comparison tables are given in Table 2, Table 3, Table 4, Table 5 and Table 6. Figure 3 shows the XPS full-scan spectra of the NiWO4/graphene oxide. In the initial state, no Zn signal was detected in the Zn 2p region. Conversely, under full charge–discharge conditions, two peaks at 1022.21 and 1045.37 eV can be clearly observed in Figure 8a. This indicates that the Zn2+ has been inserted into the lattice of the NiWO4/graphene oxide. After 100 cycles, the observed change is that the intensity of the characteristic peak is slightly reduced, and no other significant changes are found. This confirms the occurrence of the Zn2+ insertion into NiWO4 during the cycling process [53].
As presented in Figure 8b, for the original NiWO4/graphene oxide electrode, the peaks of Ni 2p3/2 and Ni 2p1/2 are at 855.51 and 873.22 eV, respectively. The Ni 2p3/2 has satellite peaks at 858.58, 861.90, and 865.67 eV, while the Ni 2p1/2 has satellite peaks at 876.13, 878.56, and 880.88 eV. When the battery was charged and discharged, new strong peaks at 552.22 and 573.71 eV corresponding to the Ni2+ were observed. This indicates that the Ni2+/Ni3+ redox reaction provided capacity during the cycling process [54]. The Ni 2p spectrum reveals that there are obvious changes in the peak intensity of each characteristic of Ni 2p1/2 in the first cycle and Ni 2p1/2 after 100 cycles. Moreover, there is also a bias shift in the potential. The intensity of the peaks is slightly enhanced, which is associated with the partial oxidation of Ni2+ [55]. In the discharge state, the shift of the binding energy of Ni 2p3/2 to a lower level and the weakening of the peak strength of Ni2+ indicate that the concentration of the Ni2+ gradually decreases due to its interaction with Zn2+[56].
As shown in Figure 8c, after charging and discharging, an increase in W5+ and W6+ ratios and distances is shown. Figure 8c presents the W 4f spectrum of the Zn//NiWO4/graphene oxide. The main peak of W 4f7/2 is at 34.81 eV, and its satellite peak is at 35.34 eV. The main peak of W 4f5/2 is at 36.93 eV, and its satellite peak at 35.34 eV is also observed. Among these, 34.81 and 37.52 eV belong to W5+, and 35.34 and 37.52 eV belong to W6+. As depicted in Figure 8c, after charge–discharge cycles, an increase in the ratios and amounts of W5+ and W6+ is observed.
Figure 8d presents the high-resolution XPS spectrum of O 1s. In the original NiWO4/graphene oxide electrode, three peaks can be detected at 532.94, 531.80, and 530.15 eV, corresponding to adsorbed oxygen, defect oxygen, and lattice oxygen of NiWO4, respectively [57]. As shown in Figure 8d, the ratios and intensities of the three peaks of the battery change significantly.
Figure 9a presents the C 1s spectrum after the first cycle, while Figure 9b shows the C 1s spectrum after the 100th cycle. There are more characteristic peaks of O=C–O in the sample compared to the NiWO4/graphene oxide composite. This might be attributed to the insertion of the Zn2+ into the carbon structure when the electrode material participates in the redox reaction [13,58]. Furthermore, the XPS spectra of C 1s in the electrode material did not exhibit significant changes after the 1st and 100th charge–discharge cycles. This indicates that carbon shows good stability during the experiment.
Overall, after charge–discharge processes, Zn2+ is successfully inserted into the negative electrode. Compared with the raw materials, the valence state and charge of the electrons change after charge–discharge, yet no other impurities are generated, and the material demonstrates stable performance. This is also the reason why the battery can maintain a high capacity even after 2000 charge–discharge cycles.

4. Applications

Figure 10 shows two assembled button batteries connected in series to light the red, blue, and green light belts (3 V) in daylight and dark environments, respectively. Firstly, the assembled button battery is charged when the voltage is charged to 1.8 V. Secondly, two charged button batteries are connected in series (2–3.6 V), then the discharge voltage range reaches the voltage range for charging the 3 V lamp belt. Finally, when the light belt is not connected, it cannot light up due to lack of power. When connected, the light belt is successfully lit. It can be clearly seen that the previously unconnected lamp is successfully illuminated, with the small lights of different colors remaining stable, and these small lights can maintain their brightness for a long time.

5. Conclusions

In summary, a convenient method for synthesizing a NiWO4/graphene oxide composite material as a cathode for zinc batteries via the hydrothermal method has been proposed. The zinc button battery with a cathode of the NiWO4/graphene oxide coated on carbon cloth exhibits a maximum discharge capacity of 490.3 mAh g−1 at a current density of 0.1 A g−1 within the voltage range of 1.0–1.8 V. The Zn//NiWO4/graphene oxide battery can deliver remarkable energy density values ranging from 490.3 mAh g−1 to 97.6 mAh g−1 at different current densities. At a current density of 1 A g−1, the Zn//NiWO4/graphene oxide battery maintains a cycling stability of 75.2% after 2000 cycles. The XPS results confirmed the structural dynamic evolution in NiWO4/graphene oxide. During the first 100 cycles, the transformation of Ni2+/Ni3+and W5+/W6+ enhanced the insertion of Zn2+ ions into the nickel/tungsten oxides. This study will contribute to the understanding of the NiWO4/graphene oxide cathode material for aqueous zinc batteries and lay the foundation for the progress of zinc batteries in the field of battery technologies.

Author Contributions

Data curation, L.D.; writing—original draft preparation, L.D.; writing—review and editing, L.D.; supervision, S.W.; funding acquisition, S.W. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Talent Introduction Project (09924601), the Science and Technology Research Program of Chongqing Education Commission of China (KJQN202400601, KJQN202201204, KJQN202102903, and KJQN202202902), the National key research and development program (2021YFB3901405), Graduate Education Teaching Reform research project of Chongqing Three Gorges University (XYJG202304), Chongqing Graduate Education Teaching Reform Research Project (yjg243120), Chongqing Higher Education Teaching Reform Research Project (243215), and Key laboratory research platform of Chongqing Preschool Education College (2021KYPT-04).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

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

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. The preparation flowchart of the Zn//NiWO4/graphene oxide button battery.
Figure 1. The preparation flowchart of the Zn//NiWO4/graphene oxide button battery.
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Figure 2. (a) XRD patterns and (b) FTIR spectra of NiWO4 and NiWO4/graphene oxide.
Figure 2. (a) XRD patterns and (b) FTIR spectra of NiWO4 and NiWO4/graphene oxide.
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Figure 3. XPS full-scan spectra of the NiWO4/graphene oxide.
Figure 3. XPS full-scan spectra of the NiWO4/graphene oxide.
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Figure 4. High-resolution XPS spectra of the NiWO4/graphene oxide. (a) Ni 2p, (b) W 4f, (c) O 1s, (d) C 1s.
Figure 4. High-resolution XPS spectra of the NiWO4/graphene oxide. (a) Ni 2p, (b) W 4f, (c) O 1s, (d) C 1s.
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Figure 5. SEM images of (a) NiWO4 and (b) NiWO4/graphene oxide. (c) EDS spectrum, (d) TEM, (e) HRTEM, (f) BF-TEM, and (g–j) element-mapping images of the NiWO4/graphene oxide.
Figure 5. SEM images of (a) NiWO4 and (b) NiWO4/graphene oxide. (c) EDS spectrum, (d) TEM, (e) HRTEM, (f) BF-TEM, and (g–j) element-mapping images of the NiWO4/graphene oxide.
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Figure 6. Electrochemical properties of Zn//NiWO4/graphene oxide button battery. (a) GCD curves at different current densities. (b) Charge–discharge capacities at different current densities. (c) Charge/discharge curves at different cycles at 0.1 A g−1. (d) EIS curves at 1st and 100th cycles.
Figure 6. Electrochemical properties of Zn//NiWO4/graphene oxide button battery. (a) GCD curves at different current densities. (b) Charge–discharge capacities at different current densities. (c) Charge/discharge curves at different cycles at 0.1 A g−1. (d) EIS curves at 1st and 100th cycles.
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Figure 7. (a) The 2000-cycle charge–discharge experiment, (b) CV at scan rates ranging from 0.1 to 1 mV s−1, (c) log(i)–log(v), (d) the capacitive and diffusion contribution ratio at different scan rates of Zn//NiWO4/graphene oxide button battery at a current density of 1 A g−1.
Figure 7. (a) The 2000-cycle charge–discharge experiment, (b) CV at scan rates ranging from 0.1 to 1 mV s−1, (c) log(i)–log(v), (d) the capacitive and diffusion contribution ratio at different scan rates of Zn//NiWO4/graphene oxide button battery at a current density of 1 A g−1.
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Figure 8. The 1st and 100th cycles of the high-resolution XPS spectra with Zn/NiWO4/graphene oxide anode materials. (a) Zn 2p, (b) Ni 2p, (c) W 4f, and (d) O 1s.
Figure 8. The 1st and 100th cycles of the high-resolution XPS spectra with Zn/NiWO4/graphene oxide anode materials. (a) Zn 2p, (b) Ni 2p, (c) W 4f, and (d) O 1s.
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Figure 9. High-resolution C 1s XPS spectrum of (a) after the 1st charge–discharge cycle, and (b) after the 100th charge–discharge cycle.
Figure 9. High-resolution C 1s XPS spectrum of (a) after the 1st charge–discharge cycle, and (b) after the 100th charge–discharge cycle.
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Figure 10. The picture of a lighting strip lamp (3 V) powered by a Zn//NiWO4/graphene oxide button battery.
Figure 10. The picture of a lighting strip lamp (3 V) powered by a Zn//NiWO4/graphene oxide button battery.
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Table 1. The previous reports of electrochemical performance of zinc-ion batteries in comparison with Zn//NiWO4/graphene oxide battery.
Table 1. The previous reports of electrochemical performance of zinc-ion batteries in comparison with Zn//NiWO4/graphene oxide battery.
ElectrodeElectrolyteCurrent
(mA g−1)		Cycle
Number		Capacity
(mA h g−1)		Capacity
Retention		Voltage
(V)		Ref.
γ-MnO21 M ZnSO4 + 0.1 M MnSO4-40158.063.0%1.0–1.8[41]
Co-Mn3O42 M ZnSO4 + 0.2 M MnSO42000110081.172.5%0.2–2.2[42]
FeFe(CN)63 M ZnSO4 + 0.2 M MnSO44210112.070.0%0.8–1.8[43]
V2O53 M Zn(CF3SO3)2 10090292.025.0%0.2–1.6[44]
MnCo2O42 M ZnSO4 + 0.5 M MnSO4100100405.011.0%0.8–1.8[31]
MnO2/Carbon cloth1 M ZnSO4 + 0.1 M MnSO41003091.782.4%0.8–1.8[15]
Mn3O42 M ZnSO4 + 0.1 M MnSO4500300106.1-1.0–1.8[45]
ZnMn2O43 M Zn(CF3SO3)2500500150.098.0%1.0–2.0[46]
α-MnO21 M ZnSO4423014070.0%0.8–1.9[47]
NiWO4/graphene oxide2 M ZnSO4100100287.041.4%1.0–1.8This work
10002000113.475.2%
Table 2. Binding energies of Zn 2p for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
Table 2. Binding energies of Zn 2p for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
SampleZn
2p1/22p3/2
1st Cycle NiWO4/graphene oxide1045.551022.41
100th cycle
NiWO4/graphene oxide		1045.161022.06
Table 3. Binding energies of Ni 2p for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
Table 3. Binding energies of Ni 2p for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
SampleNiSatellite
2p3/22p1/2
1st cycle
NiWO4/graphene oxide		856.23873.05851.59854.02859.04862.01874.43876.46878.29880.89
100th cycle
NiWO4/graphene oxide		856.20873.65852.04854.22858.26862.22857.08876.46878.83881.49
Table 4. Binding energies of W 4f for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
Table 4. Binding energies of W 4f for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
SampleW
4f7/24f5/2
+5+6+5+6
1st cycle NiWO4/graphene oxide35.8235.4838.0037.57
100th cycle
NiWO4/graphene oxide		35.9535.3938.0537.52
Table 5. Binding energies of O 1s for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
Table 5. Binding energies of O 1s for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
SampleAdsorbed OxygenDefective OxygenLattice Oxygen
1st cycle NiWO4/graphene oxide533.76532.01529.98
100th cycle
NiWO4/graphene oxide		533.99532.01530.17
Table 6. Binding energies of C 1s for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
Table 6. Binding energies of C 1s for NiWO4/graphene oxide after the 1st cycle and 100th cycle.
SampleC-CC=CC-OO=C-O
1st cycle NiWO4/graphene oxide284.69286.27288.33290.62
100th cycle
NiWO4/graphene oxide		284.74286.25288.72290.63
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Deng, L.; Wang, S. Advanced Electrochemical Performance of NiWO4/Graphene Oxide as Cathode Material for Zinc Ion Battery. Energies 2025, 18, 2023. https://doi.org/10.3390/en18082023

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Deng L, Wang S. Advanced Electrochemical Performance of NiWO4/Graphene Oxide as Cathode Material for Zinc Ion Battery. Energies. 2025; 18(8):2023. https://doi.org/10.3390/en18082023

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Deng, Likai, and Shifa Wang. 2025. "Advanced Electrochemical Performance of NiWO4/Graphene Oxide as Cathode Material for Zinc Ion Battery" Energies 18, no. 8: 2023. https://doi.org/10.3390/en18082023

APA Style

Deng, L., & Wang, S. (2025). Advanced Electrochemical Performance of NiWO4/Graphene Oxide as Cathode Material for Zinc Ion Battery. Energies, 18(8), 2023. https://doi.org/10.3390/en18082023

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