Unlocking High-Current Performance in Silicon Anode: Synergistic Phosphorus Doping and Nitrogen-Doped Carbon Encapsulation to Enhance Lithium Diffusivity.

The silicon (Si) offers enormous theoretical capacity as a lithium-ion battery (LIB) anode. However, the low charge mobility in Si particles hinders its application for high current loading. In this study, ball-milled phosphorus-doped Si nanoparticles encapsulated with nitrogen-doped carbon (P-Si@N-C) are employed as an anode for LIBs. P-doped Si nanoparticles are first obtained via ball-milling and calcination of Si with phosphoric acid. N-doped carbon encapsulation is then introduced via carbonization of the surfactant-assisted polymerization of pyrrole monomer on P-doped Si. While P dopant is required to support the stability at high current density, the encapsulation of Si particles with N-doped carbon is influential in enhancing the overall Li+ diffusivity of the Si anode. The combined approaches improve the anode's Li+ diffusivity up to tenfold compared to the untreated anode. It leads to exceptional anode stability at a high current, retaining 87 % of its initial capacity under a large current rate of 4000 mA g-1. The full-cell comprising P-Si@N-C anode and LiFePO4 cathode demonstrates 94 % capacity retention of its initial capacity after 100 cycles at 1 C. This study explores the effective strategies to improve Li+ diffusivity for high-rate Si-based anode.

Understanding SEI evolution during the cycling test of anode-free lithium-metal batteries with LiDFOB salt.

Anode-free lithium-metal batteries (AFLMBs) have the potential to double the energy density of Li-ion batteries, but face the challenges of mossy dendritic lithium plating and an unstable solid electrolyte interphase (SEI). Previous studies have shown that the AFLMBs with an electrolyte containing lithium difluoro(oxalato)borate (LiDFOB) salt outperform those with lithium hexafluorophosphate (LiPF6), but the mechanism behind this improvement is not fully understood. In this study, X-ray photoelectron spectroscopy (XPS) depth profile analysis and electrochemical impedance spectroscopy (EIS) were conducted to investigate the SEI on plated Li from the two conducting salts and their evolution in Cu‖NMC full cells during cycling. XPS results revealed that an inorganic-rich SEI layer is formed in the cell with LiDFOB-based electrolyte, with a low carbon/oxygen ratio of 0.56 compared to 1.42 in the LiPF6-based cell. With the inorganic-rich SEI, a dense electroplated Li with a shining surface on the Cu substrate can be retained after ten cycles. The inorganic-rich SEI enhances the reversibility of Li plating and stripping, with a high average CE of ∼98% and a stable charge/discharge voltage profile. The changes in SEI resistance and cathode electrolyte interphase resistance are more prominent compared to the changes in solution and charge transfer resistances, which further validate the role of the passivation films on Li deposits and NMC cathode surfaces in stabilizing AFLMB cycling performance.

Vertically Aligned n-Type Silicon Nanowire Array as a Free-Standing Anode for Lithium-Ion Batteries.

Due to its high theoretical specific capacity, a silicon anode is one of the candidates for realizing high energy density lithium-ion batteries (LIBs). However, problems related to bulk silicon (e.g., low intrinsic conductivity and massive volume expansion) limit the performance of silicon anodes. In this work, to improve the performance of silicon anodes, a vertically aligned n-type silicon nanowire array (n-SiNW) was fabricated using a well-controlled, top-down nano-machining technique by combining photolithography and inductively coupled plasma reactive ion etching (ICP-RIE) at a cryogenic temperature. The array of nanowires ~1 µm in diameter and with the aspect ratio of ~10 was successfully prepared from commercial n-type silicon wafer. The half-cell LIB with free-standing n-SiNW electrode exhibited an initial Coulombic efficiency of 91.1%, which was higher than the battery with a blank n-silicon wafer electrode (i.e., 67.5%). Upon 100 cycles of stability testing at 0.06 mA cm-2, the battery with the n-SiNW electrode retained 85.9% of its 0.50 mAh cm-2 capacity after the pre-lithiation step, whereas its counterpart, the blank n-silicon wafer electrode, only maintained 61.4% of 0.21 mAh cm-2 capacity. Furthermore, 76.7% capacity retention can be obtained at a current density of 0.2 mA cm-2, showing the potential of n-SiNW anodes for high current density applications. This work presents an alternative method for facile, high precision, and high throughput patterning on a wafer-scale to obtain a high aspect ratio n-SiNW, and its application in LIBs.

Versatilely tuned vertical silicon nanowire arrays by cryogenic reactive ion etching as a lithium-ion battery anode.

Production of high-aspect-ratio silicon (Si) nanowire-based anode for lithium ion batteries is challenging particularly in terms of controlling wire property and geometry to improve the battery performance. This report demonstrates tunable optimization of inductively coupled plasma reactive ion etching (ICP-RIE) at cryogenic temperature to fabricate vertically-aligned silicon nanowire array anodes with high verticality, controllable morphology, and good homogeneity. Three different materials [i.e., photoresist, chromium (Cr), and silicon dioxide (SiO2)] were employed as masks during the subsequent photolithography and cryogenic ICP-RIE processes to investigate their effects on the resulting nanowire structures. Silicon nanowire arrays with a high aspect ratio of up to 22 can be achieved by tuning several etching parameters [i.e., temperature, oxygen/sulfur hexafluoride (O2/SF6) gas mixture ratio, chamber pressure, plasma density, and ion energy]. Higher compressive stress was revealed for longer Si wires by means of Raman spectroscopy. Moreover, an anisotropy of lattice stress was found at the top and sidewall of Si nanowire, indicating compressive and tensile stresses, respectively. From electrochemical characterization, half-cell battery integrating ICP-RIE-based silicon nanowire anode exhibits a capacity of 0.25 mAh cm-2 with 16.67% capacity fading until 20 cycles, which has to be improved for application in future energy storage devices.

Facile synthesis of battery waste-derived graphene for transparent and conductive film application by an electrochemical exfoliation method.

One of the emerging challenges in tackling environmental issues is to treat electronic waste, with fast-growing battery waste as a notable threat to the environment. Proper recycling processes, particularly the conversion of waste to useful & value-added materials, are of great importance but not readily available. In this work, we report a facile and fast production of graphene from graphite extracted from spent Zn-C batteries. The graphene flakes are produced by electrochemically exfoliating graphite under varying DC voltages in poly(sodium 4-styrenesulfonate) (PSS) solution of different concentrations. The exfoliation takes place via the insertion of PSS into the interlayers of graphite to form C-S bonds as confirmed by FTIR and XPS studies. Under an applied voltage of 5 V and in 0.5 M PSS, high quality graphene flakes are obtained in a good yield, giving an I D/I G ratio of about 0.86 in Raman spectroscopy. The transparent conductive film prepared from the dispersion of high quality graphene flakes shows great promise due to its low sheet resistance (R s) of 1.1 kΩ sq-1 and high transmittance of 89%. This work illustrates an effective and low-cost method to realize large scale production of graphene from electronic waste.