Electrodeposition and characterization of C/Sn thin films as a high-performance anode for li-ion batteries: effect of pulsed electrodeposition parameters

Materials for Renewable and Sustainable Energy https://doi.org/10.1007/s40243-025-00302-0 (2025) 14:30 ORIGINAL PAPER Electrodeposition and characterization of C/Sn thin films as a high‑performance anode for li‑ion batteries: effect of pulsed electrodeposition parameters R. Abdel‑Karim1 · E. El‑Sheikh2 · M. E. Mitwally3 Received: 14 November 2024 / Accepted: 4 March 2025 © The Author(s) 2025 Abstract A two-step electrodeposition approach was applied to deposit Sn/C layers on a Ni foam substrate. The first step was the deposition of the Sn layer using two electrodeposition modes (direct and pulsed electrodeposition) with different parameters (duty cycle, time on/off, and effective time). The second step was to deposit carbon on the Sn layer by direct electrodeposition. The surface morphology, chemical composition, and phases of deposited layers were investigated and the electrochemical behavior of Sn/Ni and C/Sn/Ni anodes was characterized. The pulsed electrodeposition technique with a lower duty cycle (15% duty cycle with time ratio ton/off = 3/17 for 2 min) produced more uniform and compacted deposits, compared to the non-uniform and dendritic morphology obtained after high duty cycles (50%) as well as direct electrodeposition. After the direct electrodeposition of carbon on the pulsed electrodeposited Sn, a uniform layer containing ~ 10% C, 38% Sn, 45% Ni, and 7% O, was detected. Analysis of this layer confirmed the presence of Ni, Sn, and amorphous C. Electrochemical characterization showed that the C/Sn/Ni anodes with a 94 Ω polarization resistance, a 0.105 V/decade anodic Tafel slope and 0.202 V/decade cathodic Tafel slope manifested the highest apparent and intrinsic catalytic activities. The peak current for the C/Sn/Ni samples was higher than the peak current for the Sn/Ni samples at all scan rates, indicating higher electrochemical reactivity. The linear relationship between the peak current and the scan rate's square root suggests that diffusion controls the charge transfer process. Keywords Sn · Ni foam · Pulse electrodeposition · Duty Cycle · Time ratio · Cyclic voltammetry Introduction Although not commercially available until 1991, lithiumion batteries have been extensively researched and developed for over a decade [1]. Since their introduction less than three decades ago, lithium-ion batteries have evolved into the power source for our daily activities on land, at sea and in space [2]. * M. E. Mitwally 1 Faculty of Engineering, Heliopolis University, Al Salam City, Cairo, Egypt 2 Department of Metallurgy, Faculty of Engineering, Cairo University, Giza, Egypt 3 Department of Materials Engineering, Faculty of Engineering and Material Science, GUC, New Cairo, Egypt Several factors are considered while selecting electrode materials for Li-ion batteries such as the material abundance in the earth's crust, environmental impact, usage, recycling ability, cost and technical performance (voltage range, cyclability, energy density, and power density) [3]. Electrode materials must possess substantial reversible storage capacity at a voltage that is considered acceptable [4]. Based on Faraday principles, elements with lower atomic masses have higher specific capacities. Therefore, lighter elements are preferred as electrode materials [5, 6]. Anode materials can be categorized into three groups based on their lithium storing mechanisms; intercalation type, conversion-reaction type and alloying type anodes [7, 8]. Active anode materials however face several challenges hindering their performance. These challenges include change in microstructure, change in volume, phase transformations and the creation of insulating phases [9, 10]. Among intercalation type anodes, the most commonly used materials are natural and synthetic graphite due to Vol.:(0123456789) 30 Page 2 of 13 their high specific capacities. Natural graphite has a specific capacity of 372 mAh/g while synthetic graphite has a specific capacity of 342 mAh/g [2]. Other materials that follow the intercalation type mechanism include hard carbons (200–more than 500 mAh/g), CNTS (1116 mAh/g), Li4Ti5O12 (175 mAh/g), and TiO2 (330 mAh/g). Conversion type anodes include metal oxides ( Fe2O3, Fe3O4, CoO, Co3O4, MnxOy, Cu2O/CuO, NiO, Cr2O3, RuO2, MoO2/ MoO3, etc.), having a specific capacity ranging from 500 to 1200 mAh/g. Similarly, metal phosphides/sulfides/nitrides (MXy; M = Fe, Mn, Ni, Cu, Co, etc., and X = P, S, N) have a specific capacity of 500–1800 mAh/g. Alloying type materials are based on Group IV metals such as tin (994 mAh/g), silicon (4200 mAh/g), Germanium (1624 mAh/g) and antimony (660 mAh/g) [11]. Sn-based anodes have attracted researchers due to the announcement by Idota et al. [12] that a tin-based amorphous oxide had a high specific capacity of over 600 mAh/g. However, the volume expansion of the pure Sn anode during charge/discharge cycling has a detrimental impact on performance and cycle life [13, 14]. Reducing the particle size to the nanoscale and the use of nanoporous materials (NPMs) has been proposed as a solution to address the challenges associated with Sn-based anode materials. NPMs offer a wide range of structurerelated properties, including electrical, magnetic, mechanical, optical, catalytic, and electrocatalytic properties [15]. Accordingly, Li-ion anode systems based on Sn were supported on three-dimensional ordered porous (3DOP) structures to improve electrical conductivity and reduce volume expansion via chemical vapor deposition (CVD), Physical vapor deposition (PVD), Atomic layer deposition (ALD), electrodeposition and other techniques [16, 17]. Studies considered Sn-based anodes in composite form to utilize the advantages of the multicomponent system in terms of electrochemical and structural behavior [18–24]. Carbon is the element commonly added to the composite structure to improve the limited capacity of pure Sn to be cycled [25]. Tin-carbon nanocomposites have proven to be an effective solution to this problem. By reducing the particle size to the nanoscale, the mechanical stress is reduced, and the presence of an inert matrix helps prevent particle aggregation. This ultimately leads to a significant increase in the lifespan of the electrode [15, 23, 24, 26]. Among synthesis methods, electrodeposition has the advantages of simple processing, controllable conditions, high safety, environmental friendliness and low processing temperature. It is also a promising method for industrial scale production [27]. Sun et al. [28] created a 3D-structured Sn/C with a high capacity in terms of both area and volume. They achieved this by employing a two-step electroplating technique. An electrode containing 20% by volume of tin (Sn) showed a significant volumetric capacity Materials for Renewable and Sustainable Energy (2025) 14:30 of approximately 879 mAh/cm3 and an actual capacity of 6.59 mAh/cm2 after undergoing 100 cycles at a rate of 0.5C. It also showed good rate (...truncated)