Graphene nanosheets wrapped on SnO 2 -CuS nanoparticles as high- performance anode materials for lithium-ion batteries

Graphene nanosheets wrapped on SnO 2 -CuS nanoparticles as high- performance anode materials for lithium-ion batteries | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Graphene nanosheets wrapped on SnO 2 -CuS nanoparticles as high- performance anode materials for lithium-ion batteries Jianpeng Cheng, Deping Xiong, Wenqin Jiang, Wenbin Ye, Peng Song, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4570587/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract The synthesis of the ternary composite nanomaterial, SnO 2 -CuS-Graphene, involved a combination of hydrothermal and ball-milling techniques. Within the composite structure, the SnO2-CuS composite nanomaterials are evenly adhered to the Graphene, effectively shortening the diffusion pathways for electrons and Li + . This results in reduced volume fluctuations of the electrode during cycling, ultimately amplifying the conductivity of the hybrid material and offering plentiful active sites for lithium absorption. As a result, the SnO 2 -CuS-Graphene composite nanomaterial demonstrates exceptional electrochemical performance, achieving an impressive reversible capacity of 1106.7 mAh g − 1 after 200 cycles at 0.2 A g − 1 and maintaining a high reversible capacity of 991 mAh g –1 after 1000 cycles at 1.0 A g − 1 . These results underscore its remarkable cycling stability and substantial reversible capacity. SnO2 Anode CuS Graphene Lithium-ion batteries Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 1. Introduction As technology continues to advance, electronic devices such as smartphones, tablets, laptops, and the widespread adoption of new energy electric vehicles in urban transportation have become ubiquitous [1, 2]. It is widely recognized that battery longevity has consistently served as a pivotal selling point for these products. Therefore, investigating the stability and long-term usage capability of lithium-ion batteries is of significant research importance [3]. Rechargeable LIBs are fundamentally comprised of four essential components: two electrodes, a separator, and an electrolyte. During the charging phase, Li + liberated from the cathode migrate towards the anode, and during discharge, these Li + traverse from the anode to the cathode. Concurrently, the electrons discharged by lithium atoms at the anode traverse an external circuit to reach the cathode, where chemical reactions supply the electrical power [4, 5]. The pursuit of advanced anode materials with high capacity is a pivotal stride in the advancement of energy storage devices. Nevertheless, the current landscape is dominated by graphite, which boasts a mere theoretical capacity of 372 mAh g − 1 , constraining the evolution of LIBs [6]. Consequently, the imperative challenge is to identify a novel anode material characterized by a higher theoretical capacity. In many research endeavours, tin dioxide (SnO 2 ) has emerged as a promising contender. Not only does it exhibit great attributes, such as the theoretical capacity reaching up to 1494 mAh g − 1 and the lithium alloying potential of approximately 1.0 V, but it also received positive reviews for its environmental compatibility [7, 8]. The electrochemical processes of SnO 2 with Li + can be delineated through two principal equations: SnO 2 + 4Li + + 4e − \(\to\) Sn + 2Li 2 O and Sn + xLi + + xe − \(\leftrightarrow\) Li x Sn (0 \(\le\) x \(\le\) 4.4). The initial process involves an irreversible conversion, yielding a capacity of 731 mAh g −1 , whereas the subsequent one manifests an alloying reaction, resulting in a capacity of 763 mAh g − 1 [9, 10]. However, it is worth noting that this alloying reaction accompany a substantial volumetric change exceeding 200%. As a result, significant internal stress, material decomposition, and electrical contact loss are caused in the electrode material. Finally, the capacity of the lithium battery during the long cycle shows a rapid decrease [11]. The implementation of SnO2-based anode materials as an anode material is challenging due to the major limitations associated with it. In order to tackle the challenges outlined above and elevate the electrochemical capabilities of SnO 2 -based anodes, scientists have invented various methodologies, which include nanostructuring [12, 13], morphology manipulation [14], and combinations with carbon-based materials or other compounds, such as metal oxides and metal sulfides [15, 16]. Among these strategies, the most successful method is the fusion of nanostructured SnO2 particles with a carbon-rich matrix, proving to be an optimal solution for mitigating volumetric expansion. On the one hand, the miniature SnO 2 particles at the nanoscale provide a more extensive interface for interaction with the electrolyte. This results in a decrease in the Li + transport distances and an increase in the quantity of active sites within the electrode material a decrease [17, 18]. On the other hand, the carbon-rich matrix functions adeptly as a buffer against volumetric expansion and an exceptionally efficient electron conductor [19]. Notably, Graphene has exhibited remarkable efficacy in curbing lithium dendrite growth and expediting swift charge transport by minimizing lithium diffusion lengths. There are reports of notable improvements in electrochemical performance when electroactive materials are anchored, encapsulated, or enveloped by Graphene [20]. Consequently, SnO 2 -Graphene composite materials have emerged as a viable solution. They effectively counteract material volumetric fluctuations, enhance conductivity, and sustain exceptional stability during the charging and discharging. This leads to the attainment of high capacity and an extended cycling lifespan. When Graphene serves as an anode, it typically demonstrates a high specific capacity during the initial lithiation stage, but it struggles to fully release this capacity during subsequent delithiation processes [21]. This indicates that a significant portion of Li + are irreversibly consumed rather than being stored reversibly, resulting in a diminished Coulombic efficiency for the battery. Recent studies have shown that transition metals can effectively prevent the aggregation of tin (Sn) in reversible conversion reactions and create an abundance of oxygen vacancies, leading to a high reversible capacity. This phenomenon arises because the transformation reaction of transition metals with Li 2 O requires a lower energy barrier than the conversion of Sn to SnO 2 through the Sn/Li 2 O pathway [22]. Transition metal sulfides have garnered significant attention due to their impressive specific capacity. Replacing oxygen with sulfur, a less electronegative element, has enhanced performance compared to transition metal oxides [23]. Additionally, copper (Cu) nanoparticles exhibit excellent electron conductivity, offering multiple pathways for electron flow and improving charge transfer kinetics. This, in turn, promotes the presence of more active reaction sites within SnO 2 [24]. As a result, CuS has become a subject of extensive research and interest, owing to its cost-effectiveness, minimal environmental impact, prolonged and stable discharge voltage plateau, and high conductivity (10 − 3 S cm − 1 ) [25–27]. Moreover, the potential of CuS exceeds that of lithium precipitation, discouraging the growth of lithium dendrites, enhancing the safety of CuS in practical applications. Consequently, it is feasible to introduce doping with high theoretical capacity materials like SnO 2 and CuS, uniformly dispersing them on Graphene, to create a novel ternary anode material known as SnO 2 -CuS-Graphene (SCG). This material maintains exceptional cycling stability, achieves reversible capacity, and boasts an extended cycling lifespan, all while upholding excellent initial coulombic efficiency (ICE). Thus, by integrating the advantages of the strategies as mentioned above, this work adopted hydrothermal and ball-milling techniques to synthesize SCG composite nanomaterials. In the initial phase of ball milling, SnO 2 and CuS were thoroughly blended, and in the subsequent milling phase, they were uniformly anchored onto a few-layer Graphene. In this unique structural configuration, CuS assumed a dual role: inhibiting the coarsening of Sn and aiding in the reduction of Li2O. This led to an increased reversible capacity and improved ICE. The anchoring of SnO 2 -CuS nanoparticles onto Graphene effectively curbed material aggregation, minimized volume fluctuations, and bolstered structural stability. Consequently, when assessing the SCG composite nanomaterials, highly favourable results were obtained. The SCG samples exhibited outstanding cycling stability, retaining a capacity of 1106.7 mAh g − 1 after 200 cycles at a current density of 0.2 A g − 1 and maintaining 991 mAh g − 1 even after 1000 cycles at 1.0 A g − 1 . Furthermore, they displayed exceptional stability in ten-cycle tests conducted at varying current densities. Given its outstanding cycling stability and reversible capacity, the SnO2-CuS-Graphene composite nanomaterial emerges as an up-and-coming candidate for future generations of lithium-ion batteries as an anode material. 2. Results and discussion The procedure for synthesizing SCG composite nanomaterials is delineated in Fig. 1 A. Initially, nanostructured SnO 2 material was produced using a hydrothermal technique, employing Na 2 SnO 3 ·3H 2 O and urea as source materials. Subsequently, the hydrothermally derived nanostructured SnO 2 material was blended with CuS, and the resulting mixture underwent planetary ball milling for 15 hours to yield SnO 2 -CuS composite nanomaterials. The final phase entailed the incorporation of the few-layer Graphene into the composite SnO 2 -CuS, followed by an additional 5 hours of ball milling, to from the SCG composite nanomaterial. After adding Graphene for further ball milling, the size of the composite material will be further reduced, and SnO 2 -CuS composite nanomaterials will be uniformly embedded in Graphene. In this distinctive structural configuration, Graphene played a pivotal role in impeding the migration of SnO 2 and CuS particles between individual grains throughout charge and discharge processes. X-ray diffraction (XRD), is a widely recognized technique, which is elucidating the crystalline structure of composite materials [28]. Consequently, a comparative analysis of the XRD patterns was conducted for SCG, SG, and SnO 2 . As depicted in Fig. 1 B, owing to the well-defined crystallinity of these samples, distinct diffraction peaks were discerned at 26.6°, 33.8°, and 51.7°, which correspond to the (1 1 0), (1 0 1), and (2 1 1) crystal planes of SnO 2 [29]. Additionally, SCG and SG exhibited prominent and sharp diffraction peaks at 26.7° due to the superimposition of Graphene and SnO 2 . It is noteworthy that the SCG spectrum did not reveal any prominent CuS diffraction peaks, which is likely attributed to the relatively low CuS content within the SCG composite material. Raman spectroscopy is the most widely utilized technique for characterizing carbon hybridization and identifying impurity characteristics. It is pivotal in evaluating the impact of doping modifications on hybrid carbon anode materials. As illustrated in Fig. 1 C, the Raman spectra exhibit two distinct peaks, notably the D peak at 1345 cm − 1 and the G peak at 1698 cm − 1 . The ratio of I(D) representing disordered carbon and I(G) meaning graphite carbon serves as an indicator of the disordered carbon content within the composite material. After investigation, it was found that SCG had a higher I(D)/I(G) ratio, and proved the enhancement in electronic conductivity, which was attributed to the introduction of CuS inducing more outstanding defects within the Graphene matrix. Furthermore, to ascertain the Graphene content in the SCG composite material. As depicted in Fig. 1 D, thermal gravimetric analysis (TGA) was performed. A slight drop due to the evaporation of water vapour was observed before 150 degrees, and there was a substantial 29.1% reduction in curve magnitude during the heating process from 150 to 750 degrees, primarily attributable to carbon oxidation. Therefore, it can be concluded that the proportion of Graphene is 29.1% XPS was employed for a comprehensive analysis of the elemental composition and chemical states within the composite materials. As illustrated in Fig. 2 A, it can be confirmed that the SCG composite material consists of four elements: Sn, O, Cu, and C. This observation indirectly validates the successful amalgamation of SnO 2 , CuS, and Graphene through the ball-milling technique. Additionally, Fig. 2 B provides high-resolution XPS spectra for SCG, SG, and SnO 2 . Two prominent peaks at 495.9 eV and 487.3 eV correspond to Sn3d 3/2 and Sn3d 5/2 , respectively, confirming the presence of Sn 4+ in the SCG [30]. What catches the eye is that, compared to SG and SnO 2 materials, both Sn3d peaks of the SCG composite nanomaterial shift towards higher binding energies. This indicates an augmented electron density surrounding SnO 2 and strengthened electron interaction between SnO 2 and CuS. These improvements amplify electrochemical performance and foster structural stability during lithium alloying and dealloying processes [31]. Subsequently, Fig. 2 C presents high-resolution XPS spectra of Cu2p, where peaks at 952.3 eV and 935.0 eV correspond to the binding energies of Cu2p 1/2 and Cu2p 3/2 . The high-resolution XPS spectrum of C1s in Fig. 2 D reveals two clear peaks at 284.7 eV and 286.5 eV, which are associated with C-C and C-O bonds, respectively. Hence, it is observed that SnO 2 particles, CuS particles, and Graphene are well integrated in the microstructural characterization. In this work, scanning electron microscopy (SEM) was employed to observe the morphological attributes of the SCG composite nanomaterial. As portrayed in Fig. 3A, Graphene facilitates the aggregation of numerous nanoparticles, demonstrating that the incorporation of graphene effectively integrates these three materials. The amplified SEM depiction in Fig. 3B unveils a substantial accumulation of layer-stacked Graphene within the SCG composite nanomaterial, accompanied by the attachment of SnO 2 and CuS materials. The high-resolution SEM illustration in Fig. 3C demonstrates the uniform arrangement of layered Graphene in the SCG mixture, signifying the incorporation of SnO 2 within CuS nanoparticles, with Graphene enveloping the entire structure consistently, culminating in the formation of the SCG composite nanomaterial. To investigate the kinetics of lithium insertion/extraction in the electrode material, the obtained SCG electrode was subjected to initial three cycles of cyclic voltammetry (CV) in a potential range of 0.01-3.0 V at a scan rate of 0.1 mV s − 1 , as depicted in Fig. 4 A [32]. In the first cathodic cycle of the SCG sample, a prominent reduction peak near 0.82 V is visible. However, this same peak is absent in the second and third cycles, where a significant decline occurs, attributed to electrolyte decomposition and the formation of the solid electrolyte interface (SEI) film [33]. The cathodic and anodic peaks at 0.01 V and 0.1 V are linked to the lithium extraction and insertion into Graphene, respectively [34]. Furthermore, a conspicuous peak around 0.55 V corresponds to an alloying reaction, represented as Sn + xLi + + xe − \(\to\) Li x Sn (0 \(\le\) x \(\le\) 4.4), whereas the oxidation peaks near 0.49 V are associated with the dealloying of Li x Sn. Subsequent oxidation peaks around 1.28 V and 1.89 V indicate the oxidation of Sn to SnO and SnO 2 [35–37]. Moreover, the minor reduction peaks near 0.18 V and 1.23 V correspond to the reduction of CuS and SnO 2 with Li + , as described by CuS + 2Li + + 2e − → Cu + LiS and SnO 2 + 4Li + + 4e − → Sn + 2Li 2 O [38, 39]. In summary, after three cycles, the second and third scan curves largely overlap, indicating the formation of a well-functioning SEI layer and ensuring cycling stability [40]. Figure 4 B-D exhibits the initial three charge-discharge profiles for SCG, SnO 2 -Graphene (SG), and SnO 2 materials. Initially, in the discharge curve of the first cycle, a conspicuous plateau emerges near 0.85 V, stemming from the formation of the SEI film. Subsequently, the plateaus appearing around 0.55 V correspond to the alloying of Li x Sn. Thereafter, upon examining the charging curve, the stable potential plateau around 0.5 V is attributed to dealloying reactions. Additionally, the oxidation of Sn to SnO x is reflected by the elongated plateau between 1.23 V and 1.88 V. Remarkably, these results closely align with the oxidation-reduction peaks observed in the CV as mentioned above analysis. Furthermore, the achieved ICE for the prepared SCG sample reaches 53.9%, whereas SG and SnO 2 materials exhibit lower ICE values of only 47.5% and 20.2%, respectively. The significant irreversible capacity loss can be attributed to electrolyte decomposition and the formation of the SEI film [41]. Significantly, among the three electrodes, the SCG composite nanomaterial demonstrates superior ICE and higher reversible capacity. This superiority can be attributed to the CuS nanoparticles in the SCG composite nanomaterial, which facilitate the reoxidation of Sn to SnO 2 , thereby enhancing the reversibility of the conversion reaction and achieving a higher ICE [42]. Figure 5 A presents the cyclic performance of SCG composite nanomaterials, SG synthesized materials, and SnO 2 materials at a current density of 0.2 A g − 1 . The SCG composite nanomaterials exhibit a remarkable reversible capacity of 1106.7 mAh g − 1 after 200 cycles. Notably, Coulombic efficiency of SCG increases from 53.9% in the initial cycle to an impressive 97.92% after five cycles, maintaining above 98% in subsequent cycles. In contrast, SG materials, cycled at 0.2 A g − 1 , display a gradual decline in reversible capacity after 43 cycles, ultimately reaching a final reversible capacity of only 594.1 mAh g − 1 . Similarly, for SnO 2 materials, the reversible capacity gradually diminishes from the initial 577.5 mAh g − 1 to 197.1 mAh g − 1 after 200 cycles at the same current density of 0.2 A g − 1 . Moreover, SCG exhibits a progressive increase in reversible capacity after 100 cycles, reaching a stable plateau. This behaviour may be attributed to the rise in the number of dynamic sites for Li + storage within the SCG composite nanomaterial [43]. In summary, SCG not only surpasses SG and SnO 2 in terms of reversible capacity but also demonstrates superior cycling stability. To delve further into the electrochemical performance of SCG, its cyclic behaviour at a higher current density of 1.0 A g − 1 is displayed in Fig. 5 C. As observed, after 200 cycles, the reversible capacity of SCG stabilizes, possibly due to the beneficial confinement effect of CuS, which effectively mitigates the localization of Li x Sn precipitates and amorphous Li 2 O [44, 45]. Impressively, even after 1000 cycles, the capacity remains high at 991 mAh g − 1 , accompanied by a Coulombic efficiency of 99.47%. Based on these results, it can be concluded that SCG composite nanomaterials exhibit exceptional reversible capacity and remarkable long-term cycling stability, potentially attributable to several factors: (1) CuS nanoparticles play a significant role in inhibiting the coarsening of Sn, effectively preventing the aggregation of SnO 2 particles. (2) The inclusion of Graphene in SnO 2 -CuS composites contributes to the establishment of maintaining a stable structure throughout the conversion reaction. For a more comprehensive assessment of the performance with SCG composite nanomaterial, a comparative study was conducted with SG and SnO 2 materials. Each material underwent ten cycles of cycling at current densities of 0.2 A g − 1 , 0.5 A g − 1 , 1.0 A g − 1 , and 2.0 A g − 1 , followed by a return to a current density of 0.2 A g − 1 to evaluate its rate capability. As illustrated in Fig. 5 B, SCG consistently delivered high-rate capacities of 1147.5, 1058.3, 976.1, 858.6, and 1145.9 mAh g − 1 at these current densities. Importantly, it demonstrated exceptional stability throughout ten cycles at each current density. In contrast, SG (921.6, 743.5, 609.3, 521.5, and 768.4 mAh g − 1 ) and pure SnO 2 (382.8, 161.5, 2.1, 4.6, and 223.5 mAh g − 1 ) materials exhibited lower rate capacities at the corresponding current densities. Furthermore, SG and pure SnO 2 materials displayed diminished stability during the ten-cycle tests at various current densities compared to SCG. These results from the evaluation of both cycling and rate performance consistently reinforce the superior performance of the SCG composite nanomaterial. Its distinctive structure, where each component is synergistic, contributes significantly to its exceptional performance. Subsequently, the electrode process kinetics of the SCG composite material were probed using electrochemical impedance spectroscopy (EIS) measurements. In Fig. 6 A, the Nyquist plot exhibits a distinct dual-component structure: a high-frequency semicircle denoting charge transfer resistance (R ct ) and a low-frequency linear segment representing impedance arising from diffusion processes, known as the Warburg component [46]. Notably, SCG displays the smallest semicircle compared to SG and pure SnO 2 , indicating superior electron transfer capability. Moreover, SCG exhibits the steepest slope in the linear portion, signifying a relatively rapid Li + diffusion rate [47]. These findings underscore the role of layered Graphene in enhancing electronic conductivity, while CuS effectively disrupts SnO 2 aggregation, serving as a bridge to reduce electron and Li + transport distances. Furthermore, EIS assessed the SCG composite material before and after 200 cycles. As depicted in Fig. 6 B, following 200 cycles at a rate of 0.2 A g − 1 , the semicircle diminishes in size, accompanied by an increased slope. The performance improvement is primarily ascribed to activating active materials, significantly impacting the insertion and extraction of Li + [48]. It is widely recognized that CV conducted at various current rates offers a more comprehensive insight into the electrochemical performance. Thus, in this work, performance evaluation of the SCG composite nanomaterial was carried out at elevated rates within the voltage range of 0.1 to 3.0 V and current rates ranging from 0.1 to 2.0 mV s − 1 . Figure 7 A illustrates that the CV curves obtained at these six different current rates closely resemble each other, with substantial overlap in the positions of oxidation-reduction peaks. This observation underscores the excellent reversibility and rate capability of the electrodes fabricated with SCG. Moreover, the entire charge storage process can be analyzed by separating it into diffusion-controlled processes and capacitive contributions. This analysis utilizes the 'b' values in the equation: I = aν b , where 'ν' and 'i' represent the scanning rate and peak current during the work [40]. Meanwhile, 0.5 represents the absolute diffusion control process, while 1.0 represents the entire capacitance contribution. Therefore, we computed the 'b' values for the fabricated electrodes using the formula mentioned above, as shown in Fig. 7 B. Clearly, the measured b values for the anode and cathode are 0.80 and 0.82, respectively, validating that the charge storage behaviour of the SCG electrode is governed by a combination of diffusion and capacitive contributions. Subsequently, the capacitive and diffusion-controlled contributions were quantified using the equation i(ν) = k 1 ν + k 2 ν 1/2 , where k 1 v represents the capacitive contribution, and k 2 ν describes the diffusion-controlled process [41, 49]. Additionally, in Fig. 7 C, at a scan rate of 2.0 mV s − 1, the shaded region highlights that capacitive contributions constitute 75.29%. Figure 7 D summarizes the capacitive contribution rates at different scan rates, namely 0.1 mV s − 1 , 0.2 mV s − 1 , 0.4 mV s − 1 , 0.7 mV s − 1 , and 1.0 mV s − 1 , which are 40.75%, 45.51%, 49.50%, 55.36%, and 62.33%, respectively. To assess the intricate morphological alterations following extensive charge-discharge cycles, scanning electron microscopy (SEM) was employed. As depicted in Fig. 8 A and Fig. 8 B, the structure of the SCG composite electrode underwent substantial restoration, exhibiting minimal aggregation, following 200 cycles at 0.2 A g − 1 . On the contrary, Fig. 8 C and Fig. 8 D reveal that after 200 cycles at 0.2A g − 1 , the SG composite electrode exhibits significant aggregation and slight surface cracks. However, as illustrated in Fig. 8 E and Fig. 8 F, significant gaps and substantial aggregation were evident in the SnO 2 composite electrode after 200 cycles at 0.2 A g − 1 . These findings underscore the stability of the SCG composite nanomaterial, likely attributed to the ability of CuS nanoparticles to curtail SnO 2 aggregation during the charge and discharge processes. Furthermore, the Graphene coating on SnO 2 -CuS nanoparticles contributes to accommodating volume changes during lithium insertion. 3. Conclusion In summary, the SCG composite nanomaterial was synthesized through hydrothermal processing and surface ball milling, ensuring the homogeneous dispersion of SnO 2 and CuS nanoparticles on the Graphene matrix. Within this composite architecture, several vital attributes contribute to its remarkable performance: First and foremost, the Graphene layers function as an excellent buffer for accommodating volume changes and an outstanding conductor of electrons, thereby preserving a stable cyclic structure and enhancing electronic conductivity. Furthermore, the nanosized SnO 2 particles offer a significantly increased specific surface area, reducing electron transfer distances and creating an abundance of active lithium storage sites, enabling rapid lithium diffusion. Most critically, the synergistic interplay between Graphene and CuS nanoparticles effectively hinders Sn coarsening within the SCG structure, a prevalent failure mechanism in SnO 2 -based electrodes. Consequently, the SCG composite material exhibits an impressive reversible capacity of 1106.7 mAh g − 1 after 200 cycles at a current density of 0.2 A g − 1 . It maintains a substantial capacity, even under varying rate tests, including 2.0 A g − 1 . Furthermore, SCG exhibits remarkable long-term cycling stability, holding a capacity of 986.6 mAh g − 1 even after 1000 cycles at 1.0 A g − 1 , with no observable signs of aggregation or detachment after long working hours. These findings collectively underscore the potential of SnO 2 -CuS-Graphene as a highly promising anode material, holding significant research value for further advancements in LIBs technology. Declarations 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. Author Contribution Jianpeng Cheng conducted experiments to obtain results and wrote the initial draft. Deping Xiong provided a plan. Wenqin Jiang has revised the initial draft. Wenbin Ye provided research methods. Peng Song,Zuyong Feng and Miao He reviewed the manuscript. Acknowledgements This work was generously supported by the National Natural Science Foundation of China (11874124) and the Science and Technology Planning Project of Guangdong Province, China (2014B03032013, 2015B010114007 and 2016B010129002). References F. Gu, J. Guo, X. Yao, P.A. Summers, S.D. Widijatmoko, P. Hall, An investigation of the current status of recycling spent lithium-ion batteries from consumer electronics in China, Journal of Cleaner Production, 161 (2017) 765-780. A. Gupta, A. 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He, Exfoliated graphite nanosheets wrapping on MoO2-SnO2 nanoparticles as a high performance anode material for lithium ion batteries, Journal of Power Sources, 467 (2020). W. Li, X. Deng, Y. Feng, D. Xiong, M. He, Synthesis of SnO2@MnO2@graphite nanosheet with high reversibility and stable structure as a high-performance anode material for lithium-ion batteries, Ceramics International, 47 (2021) 33405-33412. D.-c. Zuo, S.-c. Song, C.-s. An, L.-b. Tang, Z.-j. He, J.-c. Zheng, Synthesis of sandwich-like structured Sn/SnOx@MXene composite through in-situ growth for highly reversible lithium storage, Nano Energy, 62 (2019) 401-409. R. Chen, J. Lu, Z. Wang, Q. Zhou, M. Zheng, Microwave Synthesis of Cu/Cu2O/SnO2 Composite with Improved Photocatalytic Ability Using SnCl4 as a Protector, Journal of Materials Science, 53 (2018) 9557-9566. A. Chen, S. Xia, Z. Ji, J. Xi, H. Qin, Q. Mao, Effects of Cu doping on the structure, electronic and optical properties of SnO 2 thin films by spray pyrolysis: An experimental and density functional study, Surface and Coatings Technology, 322 (2017) 120-126. J. Yao, G.X. Wang, J.H. Ahn, H.K. Liu, S.X. Dou, Electrochemical studies of graphitized mesocarbon microbeads as an anode in lithium-ion cells, Journal of Power Sources, 114 (2003) 292-297. X. Xiong, Z. Wang, G. Yan, H. Guo, X. Li, Role of V2O5 coating on LiNiO2-based materials for lithium ion battery, Journal of Power Sources, 245 (2014) 183-193. Y. Feng, K. Wu, H. Dong, D. Xiong, M. He, Enhancing conductivity and stabilizing structure of the TiN/SnO2 embedded in ultrathin graphite nanosheets as a high performance anode material for lithium ion batteries, Colloids and Surfaces a-Physicochemical and Engineering Aspects, 607 (2020). H. Li, Y. Wang, J. Huang, Y. Zhang, J. Zhao, Microwave-assisted Synthesis of CuS/Graphene Composite for Enhanced Lithium Storage Properties, Electrochimica Acta, 225 (2017) 443-451. Additional Declarations No competing interests reported. Supplementary Files SupplementaryMaterial.docx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4570587","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":320576060,"identity":"df597ad5-1559-49ac-8e44-ad2df5004d65","order_by":0,"name":"Jianpeng Cheng","email":"","orcid":"","institution":"Guangdong University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Jianpeng","middleName":"","lastName":"Cheng","suffix":""},{"id":320576061,"identity":"6888f935-e877-41e4-8752-72d577289998","order_by":1,"name":"Deping Xiong","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA3ElEQVRIiWNgGAWjYDCCA2DEwAPEjA8SKmpI08Js8ODMMeK0wACb5MMWZsI6+I73Hjxc8OuwDL90+7WKxAY2Bv727gS8WiTPnEs4PLMvjUdyzpmyG4k7ZBgkzpzdgFeLwY0cg8O8PTY8QEbajcQzbAwGErkEtNx/A9IiAdZSkNjGTISWGzwGh3l+gGxJP8ZAlBbJM3kJh3kbgH6ZkcMskXDmGA9Bv/AdP3v4M8+fw/b8EukPP/6oqJHjb+/FrwUciYxtYIYBlEsQgNT8ATHYHxChehSMglEwCkYiAABsu07GW+FcFwAAAABJRU5ErkJggg==","orcid":"","institution":"Guangdong University of Technology","correspondingAuthor":true,"prefix":"","firstName":"Deping","middleName":"","lastName":"Xiong","suffix":""},{"id":320576062,"identity":"d882f399-8cb6-4721-bf7d-46f1f8018385","order_by":2,"name":"Wenqin Jiang","email":"","orcid":"","institution":"Guangdong University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Wenqin","middleName":"","lastName":"Jiang","suffix":""},{"id":320576064,"identity":"a96e4a0f-637f-4837-a4d1-8af279d81b53","order_by":3,"name":"Wenbin Ye","email":"","orcid":"","institution":"Guangdong University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Wenbin","middleName":"","lastName":"Ye","suffix":""},{"id":320576065,"identity":"3e77d129-a341-4c3b-8d45-c3c41d44e6a6","order_by":4,"name":"Peng Song","email":"","orcid":"","institution":"Guangdong University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Peng","middleName":"","lastName":"Song","suffix":""},{"id":320576066,"identity":"6a210f39-4456-46ce-a5b8-eefac2d081a0","order_by":5,"name":"Zuyong Feng","email":"","orcid":"","institution":"Guangdong University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Zuyong","middleName":"","lastName":"Feng","suffix":""},{"id":320576067,"identity":"bce76185-7792-4e20-a8b0-434c99c8b82b","order_by":6,"name":"Miao He","email":"","orcid":"","institution":"Guangdong University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Miao","middleName":"","lastName":"He","suffix":""}],"badges":[],"createdAt":"2024-06-12 13:29:14","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4570587/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4570587/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":59388315,"identity":"06364dc5-1f03-4031-b22c-de31ea23c2f1","added_by":"auto","created_at":"2024-07-01 07:24:15","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":459370,"visible":true,"origin":"","legend":"\u003cp\u003e(A) The manufacturing process of the SCG composite materials. (B) XRD patterns of the SCG composite and the composites it is compared. (C) Raman spectra of the SCG composite. (D) SCG material thermogravimetric analysis.\u003c/p\u003e","description":"","filename":"Fig.1.png","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/20f2e501cce3a40089c4a14c.png"},{"id":59388871,"identity":"06846817-42d5-4179-bf0a-aa52031d5101","added_by":"auto","created_at":"2024-07-01 07:32:15","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":321433,"visible":true,"origin":"","legend":"\u003cp\u003e(A) XPS results of SCG and comparative materials. (B) High-resolution XPS spectra of Sn3d from SCG and comparative materials. (C) SCG composite with high-resolution XPS spectra of Cu2p. (D) SCG composite with high-resolution XPS spectra of C1s.\u003c/p\u003e","description":"","filename":"Fig.2.png","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/98e78732eb482bd0f316a110.png"},{"id":59388320,"identity":"43be5732-648d-4121-8c44-7f2791c2095a","added_by":"auto","created_at":"2024-07-01 07:24:15","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":308506,"visible":true,"origin":"","legend":"\u003cp\u003e(A), (B) SEM images and (C) high-resolution SEM image of the SCG composite.\u003c/p\u003e","description":"","filename":"Fig.3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/0a718c2f66a02045c4c338ae.jpg"},{"id":59388873,"identity":"8d5fb9ed-b36e-4174-8485-1bc427cf20b1","added_by":"auto","created_at":"2024-07-01 07:32:15","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":293435,"visible":true,"origin":"","legend":"\u003cp\u003e(A) CV curve diagram of the first three cycles of the SCG sample. (B) (C) (D) Charge-discharge curve of first three cycles of SCG, SG and SnO\u003csub\u003e2\u003c/sub\u003e samples.\u003c/p\u003e","description":"","filename":"Fig.4.png","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/43240def6bfff8a7db4797f6.png"},{"id":59388872,"identity":"1763bf3b-0b15-479a-ae2b-79c10577837e","added_by":"auto","created_at":"2024-07-01 07:32:15","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":288765,"visible":true,"origin":"","legend":"\u003cp\u003e(A) Cycle performance of SCG, SG and SnO\u003csub\u003e2\u003c/sub\u003e electrode materials at 0.2 A g\u003csup\u003e-1\u003c/sup\u003e. (B) Rate performance of SCG with reference samples at different current densities. (C) Cycle performance of SCG electrode materials at 1.0 A g\u003csup\u003e-1\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"Fig.5.png","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/c755bbe925680cbb82f2313d.png"},{"id":59388324,"identity":"7ae9f235-fa1f-4d14-a309-fb9d70be2ba8","added_by":"auto","created_at":"2024-07-01 07:24:15","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":90620,"visible":true,"origin":"","legend":"\u003cp\u003e(A) Nyquist curve of SCG and comparison electrode before cycling. (B) Nyquist curve of SCG before and after 200 cycles at 0.2 A g\u003csup\u003e-1\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"Fig.6.png","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/df0d59780a6f9d97e818ba1f.png"},{"id":59388319,"identity":"aad8d42b-176a-42b1-8a26-2c18bbc6cd3b","added_by":"auto","created_at":"2024-07-01 07:24:15","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":173422,"visible":true,"origin":"","legend":"\u003cp\u003e(A) SCG CV diagram under different scanning rates. (B) b-value obtained by the scan slope and the slope of the number of peak currents. (C) Capacitive contributions under 2.0 mVs\u003csup\u003e-1\u003c/sup\u003e. (D) Percent of Capacitive Contribution at Scan Rates from 0.1 to 2.0 mVs\u003csup\u003e-1\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"Fig.7.png","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/b2ba5b581d95b37bafa503ea.png"},{"id":59389440,"identity":"31db02d9-1fb3-4c19-bd09-b67a8c18281f","added_by":"auto","created_at":"2024-07-01 07:40:15","extension":"jpg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":972487,"visible":true,"origin":"","legend":"\u003cp\u003eSEM schemes of the SCG composite (A) (B) at 0.2 A g\u003csup\u003e-1\u003c/sup\u003e after 200 cycles, SG composite (C) (D) and SnO\u003csub\u003e2\u003c/sub\u003e (E) (F) at the same conditions\u003c/p\u003e","description":"","filename":"Fig.8.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/411f43d61abb6c518e26f014.jpg"},{"id":73489206,"identity":"a03d7e89-214a-44d4-b1c6-bb396f830ab7","added_by":"auto","created_at":"2025-01-10 13:02:21","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":3262087,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/d77f9cc2-e436-4ac6-bdca-0742b4b971e1.pdf"},{"id":59388317,"identity":"dc27e352-6207-45b8-8c3b-5b243b9c1b74","added_by":"auto","created_at":"2024-07-01 07:24:15","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":15830,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryMaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-4570587/v1/d4decd01dc6056455100d15b.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Graphene nanosheets wrapped on SnO 2 -CuS nanoparticles as high- performance anode materials for lithium-ion batteries","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eAs technology continues to advance, electronic devices such as smartphones, tablets, laptops, and the widespread adoption of new energy electric vehicles in urban transportation have become ubiquitous [1, 2]. It is widely recognized that battery longevity has consistently served as a pivotal selling point for these products. Therefore, investigating the stability and long-term usage capability of lithium-ion batteries is of significant research importance [3]. Rechargeable LIBs are fundamentally comprised of four essential components: two electrodes, a separator, and an electrolyte. During the charging phase, Li\u003csup\u003e+\u003c/sup\u003e liberated from the cathode migrate towards the anode, and during discharge, these Li\u003csup\u003e+\u003c/sup\u003e traverse from the anode to the cathode. Concurrently, the electrons discharged by lithium atoms at the anode traverse an external circuit to reach the cathode, where chemical reactions supply the electrical power [4, 5].\u003c/p\u003e \u003cp\u003eThe pursuit of advanced anode materials with high capacity is a pivotal stride in the advancement of energy storage devices. Nevertheless, the current landscape is dominated by graphite, which boasts a mere theoretical capacity of 372 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, constraining the evolution of LIBs [6]. Consequently, the imperative challenge is to identify a novel anode material characterized by a higher theoretical capacity. In many research endeavours, tin dioxide (SnO\u003csub\u003e2\u003c/sub\u003e) has emerged as a promising contender. Not only does it exhibit great attributes, such as the theoretical capacity reaching up to 1494 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and the lithium alloying potential of approximately 1.0 V, but it also received positive reviews for its environmental compatibility [7, 8]. The electrochemical processes of SnO\u003csub\u003e2\u003c/sub\u003e with Li\u003csup\u003e+\u003c/sup\u003e can be delineated through two principal equations: SnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;4Li\u003csup\u003e+\u003c/sup\u003e + 4e\u003csup\u003e\u0026minus;\u003c/sup\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\to\\)\u003c/span\u003e\u003c/span\u003e Sn\u0026thinsp;+\u0026thinsp;2Li\u003csub\u003e2\u003c/sub\u003eO and Sn\u0026thinsp;+\u0026thinsp;xLi\u003csup\u003e+\u003c/sup\u003e + xe\u003csup\u003e\u0026minus;\u003c/sup\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\leftrightarrow\\)\u003c/span\u003e\u003c/span\u003e Li\u003csub\u003ex\u003c/sub\u003eSn (0 \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\le\\)\u003c/span\u003e\u003c/span\u003e x \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\le\\)\u003c/span\u003e\u003c/span\u003e 4.4). The initial process involves an irreversible conversion, yielding a capacity of 731 mAh g\u003csup\u003e\u0026minus;1\u003c/sup\u003e, whereas the subsequent one manifests an alloying reaction, resulting in a capacity of 763 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e [9, 10]. However, it is worth noting that this alloying reaction accompany a substantial volumetric change exceeding 200%. As a result, significant internal stress, material decomposition, and electrical contact loss are caused in the electrode material. Finally, the capacity of the lithium battery during the long cycle shows a rapid decrease [11]. The implementation of SnO2-based anode materials as an anode material is challenging due to the major limitations associated with it.\u003c/p\u003e \u003cp\u003eIn order to tackle the challenges outlined above and elevate the electrochemical capabilities of SnO\u003csub\u003e2\u003c/sub\u003e-based anodes, scientists have invented various methodologies, which include nanostructuring [12, 13], morphology manipulation [14], and combinations with carbon-based materials or other compounds, such as metal oxides and metal sulfides [15, 16]. Among these strategies, the most successful method is the fusion of nanostructured SnO2 particles with a carbon-rich matrix, proving to be an optimal solution for mitigating volumetric expansion. On the one hand, the miniature SnO\u003csub\u003e2\u003c/sub\u003e particles at the nanoscale provide a more extensive interface for interaction with the electrolyte. This results in a decrease in the Li\u003csup\u003e+\u003c/sup\u003e transport distances and an increase in the quantity of active sites within the electrode material a decrease [17, 18]. On the other hand, the carbon-rich matrix functions adeptly as a buffer against volumetric expansion and an exceptionally efficient electron conductor [19]. Notably, Graphene has exhibited remarkable efficacy in curbing lithium dendrite growth and expediting swift charge transport by minimizing lithium diffusion lengths. There are reports of notable improvements in electrochemical performance when electroactive materials are anchored, encapsulated, or enveloped by Graphene [20]. Consequently, SnO\u003csub\u003e2\u003c/sub\u003e-Graphene composite materials have emerged as a viable solution. They effectively counteract material volumetric fluctuations, enhance conductivity, and sustain exceptional stability during the charging and discharging. This leads to the attainment of high capacity and an extended cycling lifespan.\u003c/p\u003e \u003cp\u003eWhen Graphene serves as an anode, it typically demonstrates a high specific capacity during the initial lithiation stage, but it struggles to fully release this capacity during subsequent delithiation processes [21]. This indicates that a significant portion of Li\u003csup\u003e+\u003c/sup\u003e are irreversibly consumed rather than being stored reversibly, resulting in a diminished Coulombic efficiency for the battery. Recent studies have shown that transition metals can effectively prevent the aggregation of tin (Sn) in reversible conversion reactions and create an abundance of oxygen vacancies, leading to a high reversible capacity. This phenomenon arises because the transformation reaction of transition metals with Li\u003csub\u003e2\u003c/sub\u003eO requires a lower energy barrier than the conversion of Sn to SnO\u003csub\u003e2\u003c/sub\u003e through the Sn/Li\u003csub\u003e2\u003c/sub\u003eO pathway [22]. Transition metal sulfides have garnered significant attention due to their impressive specific capacity. Replacing oxygen with sulfur, a less electronegative element, has enhanced performance compared to transition metal oxides [23]. Additionally, copper (Cu) nanoparticles exhibit excellent electron conductivity, offering multiple pathways for electron flow and improving charge transfer kinetics. This, in turn, promotes the presence of more active reaction sites within SnO\u003csub\u003e2\u003c/sub\u003e [24]. As a result, CuS has become a subject of extensive research and interest, owing to its cost-effectiveness, minimal environmental impact, prolonged and stable discharge voltage plateau, and high conductivity (10\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003eS cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) [25\u0026ndash;27]. Moreover, the potential of CuS exceeds that of lithium precipitation, discouraging the growth of lithium dendrites, enhancing the safety of CuS in practical applications. Consequently, it is feasible to introduce doping with high theoretical capacity materials like SnO\u003csub\u003e2\u003c/sub\u003e and CuS, uniformly dispersing them on Graphene, to create a novel ternary anode material known as SnO\u003csub\u003e2\u003c/sub\u003e-CuS-Graphene (SCG). This material maintains exceptional cycling stability, achieves reversible capacity, and boasts an extended cycling lifespan, all while upholding excellent initial coulombic efficiency (ICE).\u003c/p\u003e \u003cp\u003eThus, by integrating the advantages of the strategies as mentioned above, this work adopted hydrothermal and ball-milling techniques to synthesize SCG composite nanomaterials. In the initial phase of ball milling, SnO\u003csub\u003e2\u003c/sub\u003e and CuS were thoroughly blended, and in the subsequent milling phase, they were uniformly anchored onto a few-layer Graphene. In this unique structural configuration, CuS assumed a dual role: inhibiting the coarsening of Sn and aiding in the reduction of Li2O. This led to an increased reversible capacity and improved ICE. The anchoring of SnO\u003csub\u003e2\u003c/sub\u003e-CuS nanoparticles onto Graphene effectively curbed material aggregation, minimized volume fluctuations, and bolstered structural stability. Consequently, when assessing the SCG composite nanomaterials, highly favourable results were obtained. The SCG samples exhibited outstanding cycling stability, retaining a capacity of 1106.7 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 200 cycles at a current density of 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and maintaining 991 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e even after 1000 cycles at 1.0 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Furthermore, they displayed exceptional stability in ten-cycle tests conducted at varying current densities. Given its outstanding cycling stability and reversible capacity, the SnO2-CuS-Graphene composite nanomaterial emerges as an up-and-coming candidate for future generations of lithium-ion batteries as an anode material.\u003c/p\u003e"},{"header":"2. Results and discussion","content":"\u003cp\u003e \u003c/p\u003e \u003cp\u003eThe procedure for synthesizing SCG composite nanomaterials is delineated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eA. Initially, nanostructured SnO\u003csub\u003e2\u003c/sub\u003e material was produced using a hydrothermal technique, employing Na\u003csub\u003e2\u003c/sub\u003eSnO\u003csub\u003e3\u003c/sub\u003e\u0026middot;3H\u003csub\u003e2\u003c/sub\u003eO and urea as source materials. Subsequently, the hydrothermally derived nanostructured SnO\u003csub\u003e2\u003c/sub\u003e material was blended with CuS, and the resulting mixture underwent planetary ball milling for 15 hours to yield SnO\u003csub\u003e2\u003c/sub\u003e-CuS composite nanomaterials. The final phase entailed the incorporation of the few-layer Graphene into the composite SnO\u003csub\u003e2\u003c/sub\u003e-CuS, followed by an additional 5 hours of ball milling, to from the SCG composite nanomaterial. After adding Graphene for further ball milling, the size of the composite material will be further reduced, and SnO\u003csub\u003e2\u003c/sub\u003e-CuS composite nanomaterials will be uniformly embedded in Graphene. In this distinctive structural configuration, Graphene played a pivotal role in impeding the migration of SnO\u003csub\u003e2\u003c/sub\u003e and CuS particles between individual grains throughout charge and discharge processes.\u003c/p\u003e \u003cp\u003eX-ray diffraction (XRD), is a widely recognized technique, which is elucidating the crystalline structure of composite materials [28]. Consequently, a comparative analysis of the XRD patterns was conducted for SCG, SG, and SnO\u003csub\u003e2\u003c/sub\u003e. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eB, owing to the well-defined crystallinity of these samples, distinct diffraction peaks were discerned at 26.6\u0026deg;, 33.8\u0026deg;, and 51.7\u0026deg;, which correspond to the (1 1 0), (1 0 1), and (2 1 1) crystal planes of SnO\u003csub\u003e2\u003c/sub\u003e [29]. Additionally, SCG and SG exhibited prominent and sharp diffraction peaks at 26.7\u0026deg; due to the superimposition of Graphene and SnO\u003csub\u003e2\u003c/sub\u003e. It is noteworthy that the SCG spectrum did not reveal any prominent CuS diffraction peaks, which is likely attributed to the relatively low CuS content within the SCG composite material.\u003c/p\u003e \u003cp\u003eRaman spectroscopy is the most widely utilized technique for characterizing carbon hybridization and identifying impurity characteristics. It is pivotal in evaluating the impact of doping modifications on hybrid carbon anode materials. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eC, the Raman spectra exhibit two distinct peaks, notably the D peak at 1345 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and the G peak at 1698 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The ratio of I(D) representing disordered carbon and I(G) meaning graphite carbon serves as an indicator of the disordered carbon content within the composite material. After investigation, it was found that SCG had a higher I(D)/I(G) ratio, and proved the enhancement in electronic conductivity, which was attributed to the introduction of CuS inducing more outstanding defects within the Graphene matrix. Furthermore, to ascertain the Graphene content in the SCG composite material. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eD, thermal gravimetric analysis (TGA) was performed. A slight drop due to the evaporation of water vapour was observed before 150 degrees, and there was a substantial 29.1% reduction in curve magnitude during the heating process from 150 to 750 degrees, primarily attributable to carbon oxidation. Therefore, it can be concluded that the proportion of Graphene is 29.1%\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eXPS was employed for a comprehensive analysis of the elemental composition and chemical states within the composite materials. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eA, it can be confirmed that the SCG composite material consists of four elements: Sn, O, Cu, and C. This observation indirectly validates the successful amalgamation of SnO\u003csub\u003e2\u003c/sub\u003e, CuS, and Graphene through the ball-milling technique. Additionally, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eB provides high-resolution XPS spectra for SCG, SG, and SnO\u003csub\u003e2\u003c/sub\u003e. Two prominent peaks at 495.9 eV and 487.3 eV correspond to Sn3d\u003csub\u003e3/2\u003c/sub\u003e and Sn3d\u003csub\u003e5/2\u003c/sub\u003e, respectively, confirming the presence of Sn\u003csup\u003e4+\u003c/sup\u003e in the SCG [30]. What catches the eye is that, compared to SG and SnO\u003csub\u003e2\u003c/sub\u003e materials, both Sn3d peaks of the SCG composite nanomaterial shift towards higher binding energies. This indicates an augmented electron density surrounding SnO\u003csub\u003e2\u003c/sub\u003e and strengthened electron interaction between SnO\u003csub\u003e2\u003c/sub\u003e and CuS. These improvements amplify electrochemical performance and foster structural stability during lithium alloying and dealloying processes [31]. Subsequently, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eC presents high-resolution XPS spectra of Cu2p, where peaks at 952.3 eV and 935.0 eV correspond to the binding energies of Cu2p\u003csub\u003e1/2\u003c/sub\u003e and Cu2p\u003csub\u003e3/2\u003c/sub\u003e. The high-resolution XPS spectrum of C1s in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eD reveals two clear peaks at 284.7 eV and 286.5 eV, which are associated with C-C and C-O bonds, respectively. Hence, it is observed that SnO\u003csub\u003e2\u003c/sub\u003e particles, CuS particles, and Graphene are well integrated in the microstructural characterization.\u003c/p\u003e\u003cp\u003eIn this work, scanning electron microscopy (SEM) was employed to observe the morphological attributes of the SCG composite nanomaterial. As portrayed in Fig.\u0026nbsp;3A, Graphene facilitates the aggregation of numerous nanoparticles, demonstrating that the incorporation of graphene effectively integrates these three materials. The amplified SEM depiction in Fig.\u0026nbsp;3B unveils a substantial accumulation of layer-stacked Graphene within the SCG composite nanomaterial, accompanied by the attachment of SnO\u003csub\u003e2\u003c/sub\u003e and CuS materials. The high-resolution SEM illustration in Fig.\u0026nbsp;3C demonstrates the uniform arrangement of layered Graphene in the SCG mixture, signifying the incorporation of SnO\u003csub\u003e2\u003c/sub\u003e within CuS nanoparticles, with Graphene enveloping the entire structure consistently, culminating in the formation of the SCG composite nanomaterial.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo investigate the kinetics of lithium insertion/extraction in the electrode material, the obtained SCG electrode was subjected to initial three cycles of cyclic voltammetry (CV) in a potential range of 0.01-3.0 V at a scan rate of 0.1 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, as depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003eA [32]. In the first cathodic cycle of the SCG sample, a prominent reduction peak near 0.82 V is visible. However, this same peak is absent in the second and third cycles, where a significant decline occurs, attributed to electrolyte decomposition and the formation of the solid electrolyte interface (SEI) film [33]. The cathodic and anodic peaks at 0.01 V and 0.1 V are linked to the lithium extraction and insertion into Graphene, respectively [34]. Furthermore, a conspicuous peak around 0.55 V corresponds to an alloying reaction, represented as Sn\u0026thinsp;+\u0026thinsp;xLi\u003csup\u003e+\u003c/sup\u003e + xe\u003csup\u003e\u0026minus;\u003c/sup\u003e \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\to\\)\u003c/span\u003e\u003c/span\u003e Li\u003csub\u003ex\u003c/sub\u003eSn (0\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\le\\)\u003c/span\u003e\u003c/span\u003ex\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\le\\)\u003c/span\u003e\u003c/span\u003e4.4), whereas the oxidation peaks near 0.49 V are associated with the dealloying of Li\u003csub\u003ex\u003c/sub\u003eSn. Subsequent oxidation peaks around 1.28 V and 1.89 V indicate the oxidation of Sn to SnO and SnO\u003csub\u003e2\u003c/sub\u003e [35\u0026ndash;37]. Moreover, the minor reduction peaks near 0.18 V and 1.23 V correspond to the reduction of CuS and SnO\u003csub\u003e2\u003c/sub\u003e with Li\u003csup\u003e+\u003c/sup\u003e, as described by CuS\u0026thinsp;+\u0026thinsp;2Li\u003csup\u003e+\u003c/sup\u003e + 2e\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026rarr; Cu\u0026thinsp;+\u0026thinsp;LiS and SnO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;4Li\u003csup\u003e+\u003c/sup\u003e + 4e\u003csup\u003e\u0026minus;\u003c/sup\u003e \u0026rarr; Sn\u0026thinsp;+\u0026thinsp;2Li\u003csub\u003e2\u003c/sub\u003eO [38, 39]. In summary, after three cycles, the second and third scan curves largely overlap, indicating the formation of a well-functioning SEI layer and ensuring cycling stability [40].\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003eB-D exhibits the initial three charge-discharge profiles for SCG, SnO\u003csub\u003e2\u003c/sub\u003e-Graphene (SG), and SnO\u003csub\u003e2\u003c/sub\u003e materials. Initially, in the discharge curve of the first cycle, a conspicuous plateau emerges near 0.85 V, stemming from the formation of the SEI film. Subsequently, the plateaus appearing around 0.55 V correspond to the alloying of Li\u003csub\u003ex\u003c/sub\u003eSn. Thereafter, upon examining the charging curve, the stable potential plateau around 0.5 V is attributed to dealloying reactions. Additionally, the oxidation of Sn to SnO\u003csub\u003ex\u003c/sub\u003e is reflected by the elongated plateau between 1.23 V and 1.88 V. Remarkably, these results closely align with the oxidation-reduction peaks observed in the CV as mentioned above analysis. Furthermore, the achieved ICE for the prepared SCG sample reaches 53.9%, whereas SG and SnO\u003csub\u003e2\u003c/sub\u003e materials exhibit lower ICE values of only 47.5% and 20.2%, respectively. The significant irreversible capacity loss can be attributed to electrolyte decomposition and the formation of the SEI film [41]. Significantly, among the three electrodes, the SCG composite nanomaterial demonstrates superior ICE and higher reversible capacity. This superiority can be attributed to the CuS nanoparticles in the SCG composite nanomaterial, which facilitate the reoxidation of Sn to SnO\u003csub\u003e2\u003c/sub\u003e, thereby enhancing the reversibility of the conversion reaction and achieving a higher ICE [42].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003eA presents the cyclic performance of SCG composite nanomaterials, SG synthesized materials, and SnO\u003csub\u003e2\u003c/sub\u003e materials at a current density of 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The SCG composite nanomaterials exhibit a remarkable reversible capacity of 1106.7 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 200 cycles. Notably, Coulombic efficiency of SCG increases from 53.9% in the initial cycle to an impressive 97.92% after five cycles, maintaining above 98% in subsequent cycles. In contrast, SG materials, cycled at 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, display a gradual decline in reversible capacity after 43 cycles, ultimately reaching a final reversible capacity of only 594.1 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Similarly, for SnO\u003csub\u003e2\u003c/sub\u003e materials, the reversible capacity gradually diminishes from the initial 577.5 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 197.1 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 200 cycles at the same current density of 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Moreover, SCG exhibits a progressive increase in reversible capacity after 100 cycles, reaching a stable plateau. This behaviour may be attributed to the rise in the number of dynamic sites for Li\u003csup\u003e+\u003c/sup\u003e storage within the SCG composite nanomaterial [43]. In summary, SCG not only surpasses SG and SnO\u003csub\u003e2\u003c/sub\u003e in terms of reversible capacity but also demonstrates superior cycling stability. To delve further into the electrochemical performance of SCG, its cyclic behaviour at a higher current density of 1.0 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003eC. As observed, after 200 cycles, the reversible capacity of SCG stabilizes, possibly due to the beneficial confinement effect of CuS, which effectively mitigates the localization of Li\u003csub\u003ex\u003c/sub\u003eSn precipitates and amorphous Li\u003csub\u003e2\u003c/sub\u003eO [44, 45]. Impressively, even after 1000 cycles, the capacity remains high at 991 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, accompanied by a Coulombic efficiency of 99.47%. Based on these results, it can be concluded that SCG composite nanomaterials exhibit exceptional reversible capacity and remarkable long-term cycling stability, potentially attributable to several factors: (1) CuS nanoparticles play a significant role in inhibiting the coarsening of Sn, effectively preventing the aggregation of SnO\u003csub\u003e2\u003c/sub\u003e particles. (2) The inclusion of Graphene in SnO\u003csub\u003e2\u003c/sub\u003e-CuS composites contributes to the establishment of maintaining a stable structure throughout the conversion reaction.\u003c/p\u003e \u003cp\u003eFor a more comprehensive assessment of the performance with SCG composite nanomaterial, a comparative study was conducted with SG and SnO\u003csub\u003e2\u003c/sub\u003e materials. Each material underwent ten cycles of cycling at current densities of 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 0.5 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 1.0 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and 2.0 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, followed by a return to a current density of 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to evaluate its rate capability. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003eB, SCG consistently delivered high-rate capacities of 1147.5, 1058.3, 976.1, 858.6, and 1145.9 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e at these current densities. Importantly, it demonstrated exceptional stability throughout ten cycles at each current density. In contrast, SG (921.6, 743.5, 609.3, 521.5, and 768.4 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and pure SnO\u003csub\u003e2\u003c/sub\u003e (382.8, 161.5, 2.1, 4.6, and 223.5 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) materials exhibited lower rate capacities at the corresponding current densities. Furthermore, SG and pure SnO\u003csub\u003e2\u003c/sub\u003e materials displayed diminished stability during the ten-cycle tests at various current densities compared to SCG. These results from the evaluation of both cycling and rate performance consistently reinforce the superior performance of the SCG composite nanomaterial. Its distinctive structure, where each component is synergistic, contributes significantly to its exceptional performance.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eSubsequently, the electrode process kinetics of the SCG composite material were probed using electrochemical impedance spectroscopy (EIS) measurements. In Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003eA, the Nyquist plot exhibits a distinct dual-component structure: a high-frequency semicircle denoting charge transfer resistance (R\u003csub\u003ect\u003c/sub\u003e) and a low-frequency linear segment representing impedance arising from diffusion processes, known as the Warburg component [46]. Notably, SCG displays the smallest semicircle compared to SG and pure SnO\u003csub\u003e2\u003c/sub\u003e, indicating superior electron transfer capability. Moreover, SCG exhibits the steepest slope in the linear portion, signifying a relatively rapid Li\u003csup\u003e+\u003c/sup\u003e diffusion rate [47]. These findings underscore the role of layered Graphene in enhancing electronic conductivity, while CuS effectively disrupts SnO\u003csub\u003e2\u003c/sub\u003e aggregation, serving as a bridge to reduce electron and Li\u003csup\u003e+\u003c/sup\u003e transport distances. Furthermore, EIS assessed the SCG composite material before and after 200 cycles. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003eB, following 200 cycles at a rate of 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, the semicircle diminishes in size, accompanied by an increased slope. The performance improvement is primarily ascribed to activating active materials, significantly impacting the insertion and extraction of Li\u003csup\u003e+\u003c/sup\u003e [48].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIt is widely recognized that CV conducted at various current rates offers a more comprehensive insight into the electrochemical performance. Thus, in this work, performance evaluation of the SCG composite nanomaterial was carried out at elevated rates within the voltage range of 0.1 to 3.0 V and current rates ranging from 0.1 to 2.0 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003eA illustrates that the CV curves obtained at these six different current rates closely resemble each other, with substantial overlap in the positions of oxidation-reduction peaks. This observation underscores the excellent reversibility and rate capability of the electrodes fabricated with SCG. Moreover, the entire charge storage process can be analyzed by separating it into diffusion-controlled processes and capacitive contributions. This analysis utilizes the 'b' values in the equation: I\u0026thinsp;=\u0026thinsp;aν\u003csup\u003eb\u003c/sup\u003e, where 'ν' and 'i' represent the scanning rate and peak current during the work [40]. Meanwhile, 0.5 represents the absolute diffusion control process, while 1.0 represents the entire capacitance contribution. Therefore, we computed the 'b' values for the fabricated electrodes using the formula mentioned above, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003eB. Clearly, the measured b values for the anode and cathode are 0.80 and 0.82, respectively, validating that the charge storage behaviour of the SCG electrode is governed by a combination of diffusion and capacitive contributions. Subsequently, the capacitive and diffusion-controlled contributions were quantified using the equation i(ν)\u0026thinsp;=\u0026thinsp;k\u003csub\u003e1\u003c/sub\u003eν\u0026thinsp;+\u0026thinsp;k\u003csub\u003e2\u003c/sub\u003eν\u003csup\u003e1/2\u003c/sup\u003e, where k\u003csub\u003e1\u003c/sub\u003ev represents the capacitive contribution, and k\u003csub\u003e2\u003c/sub\u003eν describes the diffusion-controlled process [41, 49]. Additionally, in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003eC, at a scan rate of 2.0 mV s\u0026thinsp;\u0026minus;\u0026thinsp;1, the shaded region highlights that capacitive contributions constitute 75.29%. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003eD summarizes the capacitive contribution rates at different scan rates, namely 0.1 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 0.2 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 0.4 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 0.7 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and 1.0 mV s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which are 40.75%, 45.51%, 49.50%, 55.36%, and 62.33%, respectively.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo assess the intricate morphological alterations following extensive charge-discharge cycles, scanning electron microscopy (SEM) was employed. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003eA and Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003eB, the structure of the SCG composite electrode underwent substantial restoration, exhibiting minimal aggregation, following 200 cycles at 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. On the contrary, Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003eC and Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003eD reveal that after 200 cycles at 0.2A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, the SG composite electrode exhibits significant aggregation and slight surface cracks. However, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003eE and Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003eF, significant gaps and substantial aggregation were evident in the SnO\u003csub\u003e2\u003c/sub\u003e composite electrode after 200 cycles at 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. These findings underscore the stability of the SCG composite nanomaterial, likely attributed to the ability of CuS nanoparticles to curtail SnO\u003csub\u003e2\u003c/sub\u003e aggregation during the charge and discharge processes. Furthermore, the Graphene coating on SnO\u003csub\u003e2\u003c/sub\u003e-CuS nanoparticles contributes to accommodating volume changes during lithium insertion.\u003c/p\u003e"},{"header":"3. Conclusion","content":"\u003cp\u003eIn summary, the SCG composite nanomaterial was synthesized through hydrothermal processing and surface ball milling, ensuring the homogeneous dispersion of SnO\u003csub\u003e2\u003c/sub\u003e and CuS nanoparticles on the Graphene matrix. Within this composite architecture, several vital attributes contribute to its remarkable performance: First and foremost, the Graphene layers function as an excellent buffer for accommodating volume changes and an outstanding conductor of electrons, thereby preserving a stable cyclic structure and enhancing electronic conductivity. Furthermore, the nanosized SnO\u003csub\u003e2\u003c/sub\u003e particles offer a significantly increased specific surface area, reducing electron transfer distances and creating an abundance of active lithium storage sites, enabling rapid lithium diffusion. Most critically, the synergistic interplay between Graphene and CuS nanoparticles effectively hinders Sn coarsening within the SCG structure, a prevalent failure mechanism in SnO\u003csub\u003e2\u003c/sub\u003e-based electrodes. Consequently, the SCG composite material exhibits an impressive reversible capacity of 1106.7 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 200 cycles at a current density of 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. It maintains a substantial capacity, even under varying rate tests, including 2.0 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Furthermore, SCG exhibits remarkable long-term cycling stability, holding a capacity of 986.6 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e even after 1000 cycles at 1.0 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, with no observable signs of aggregation or detachment after long working hours. These findings collectively underscore the potential of SnO\u003csub\u003e2\u003c/sub\u003e-CuS-Graphene as a highly promising anode material, holding significant research value for further advancements in LIBs technology.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eDeclaration of competing interest\u003c/h2\u003e \u003cp\u003eThe 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.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eJianpeng Cheng conducted experiments to obtain results and wrote the initial draft. Deping Xiong provided a plan. Wenqin Jiang has revised the initial draft. Wenbin Ye provided research methods. Peng Song,Zuyong Feng and Miao He reviewed the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThis work was generously supported by the National Natural Science Foundation of China (11874124) and the Science and Technology Planning Project of Guangdong Province, China (2014B03032013, 2015B010114007 and 2016B010129002).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eF. Gu, J. Guo, X. Yao, P.A. Summers, S.D. Widijatmoko, P. Hall, An investigation of the current status of recycling spent lithium-ion batteries from consumer electronics in China, Journal of Cleaner Production, 161 (2017) 765-780.\u003c/li\u003e\n\u003cli\u003eA. Gupta, A. Manthiram, Designing Advanced Lithium-Based Batteries for Low-Temperature Conditions, Advanced Energy Materials, 10 (2020).\u003c/li\u003e\n\u003cli\u003eY. Zhang, L. Liu, L. Zhao, C. Hou, M. Huang, H. Algadi, D. Li, Q. Xia, J. Wang, Z. Zhou, X. Han, Y. Long, Y. Li, Z. Zhang, Y. 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Zhao, Microwave-assisted Synthesis of CuS/Graphene Composite for Enhanced Lithium Storage Properties, Electrochimica Acta, 225 (2017) 443-451.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"SnO2, Anode, CuS, Graphene, Lithium-ion batteries","lastPublishedDoi":"10.21203/rs.3.rs-4570587/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4570587/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe synthesis of the ternary composite nanomaterial, SnO\u003csub\u003e2\u003c/sub\u003e-CuS-Graphene, involved a combination of hydrothermal and ball-milling techniques. Within the composite structure, the SnO2-CuS composite nanomaterials are evenly adhered to the Graphene, effectively shortening the diffusion pathways for electrons and Li\u003csup\u003e+\u003c/sup\u003e. This results in reduced volume fluctuations of the electrode during cycling, ultimately amplifying the conductivity of the hybrid material and offering plentiful active sites for lithium absorption. As a result, the SnO\u003csub\u003e2\u003c/sub\u003e-CuS-Graphene composite nanomaterial demonstrates exceptional electrochemical performance, achieving an impressive reversible capacity of 1106.7 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after 200 cycles at 0.2 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and maintaining a high reversible capacity of 991 mAh g\u003csup\u003e\u0026ndash;1\u003c/sup\u003e after 1000 cycles at 1.0 A g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. These results underscore its remarkable cycling stability and substantial reversible capacity.\u003c/p\u003e","manuscriptTitle":"Graphene nanosheets wrapped on SnO 2 -CuS nanoparticles as high- performance anode materials for lithium-ion batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-07-01 07:24:10","doi":"10.21203/rs.3.rs-4570587/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"83349240-cb39-4248-bf35-5f89b8c28c11","owner":[],"postedDate":"July 1st, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-01-10T12:54:02+00:00","versionOfRecord":[],"versionCreatedAt":"2024-07-01 07:24:10","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4570587","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4570587","identity":"rs-4570587","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}