RESUMO
A silicon-based lithium-ion battery (LIB) anode is extensively studied because of silicon's abundance, high theoretical specific capacity (4200 mAh/g), and low operating potential versus lithium. Technical barriers to large-scale commercial applications include the low electrical conductivity and up to about 400% volume changes of silicon due to alloying with lithium. Maintaining the physical integrity of individual silicon particles and the anode structure is the top priority. We use strong hydrogen bonds between citric acid (CA) and silicon to firmly coat CA on silicon. Carbonized CA (CCA) enhances electrical conductivity of silicon. Polyacrylic acid (PAA) binder encapsulates silicon flakes by strong bonds formed by abundant COOH functional groups in PAA and on CCA. It results in excellent physical integrity of individual silicon particles and the whole anode. The silicon-based anode shows high initial coulombic efficiency, around 90%, and the capacity retention of 1479 mAh/g after 200 discharge-charge cycles at 1 A/g current. At 4 A/g, the capacity retention of 1053 mAh/g was achieved. A durable high-ICE silicon-based LIB anode capable of high discharge-charge current has been reported.
RESUMO
Maintaining the physical integrity of a silicon-based anode, which suffers from damage caused by severe volume changes during cycling, is a top priority in its practical applications. The performance of silicon-flake-based anodes has been significantly improved by mixing nanodiamond powders with silicon flakes for the fabrication of anodes for lithium-ion batteries (LIBs). Nanodiamonds adhere to the surfaces of silicon flakes and are distributed in the binder between flakes. A consistent and robust solid electrolyte interphase (SEI) is promoted by the aid of abundant reactive surface-linked functional groups and exposed dangling bonds of nanodiamonds, leading to enhanced physical integrity of the silicon flakes and the anode. The battery's high-rate discharge capabilities and cycle life are thus improved. SEM, Raman spectroscopy, and XRD were applied to examine the structure and morphology of the anode. Electrochemical performance was evaluated to demonstrate a capacity retention of nearly 75% after 200 cycles, with the final specific capacity exceeding 1000 mAh/g at a test current of 4 mA/cm2. This is attributed to the improved stability of the solid electrolyte interphase (SEI) structure that was achieved by integrating nanodiamonds with silicon flakes in the anode, leading to enhanced cycling stability and rapid charge-discharge performance. The results from this study present an effective strategy of achieving high-cycling-performance by adding nanodiamonds to silicon-flake-based anodes.
RESUMO
Silicon-based anodes are promising to replace graphite-based anodes for high-capacity lithium-ion batteries (LIB). However, the charge-discharge cycling suffers from internal stresses created by large volume changes of silicon, which form silicon-lithium compounds, and excessive consumption of lithium by irreversible formation of lithium-containing compounds. Consumption of lithium by the initial conditioning of the anode, as indicated by low initial coulombic efficiency (ICE), and subsequently continuous formation of solid-electrolyte-phase (SEI) on the freshly exposed silicon surface, are among the main issues. A high-performance, silicon-based, high-capacity anode exhibiting 88.8% ICE and the retention of 2 mAh/cm2 areal capacity after 200 discharge-charge cycles at the rate of 1 A/g is reported. The anode is made on a copper foil using a mixture of 70%:10%:20% by weight ratio of silicon flakes of 100 × 800 × 800 nm in size, Super P conductivity enhancement additive, and an equal-weight mixture of CMC and SBR binders. Pyrolysis of fabricated anodes at 700 °C in argon environment for 1 h was applied to convert the binders into a porous graphitic carbon structure that encapsulates individual silicon flakes. The porous anode has a mechanically strong and electrically conductive graphitic carbon structure formed by the pyrolyzed binders, which protect individual silicon flakes from excessive reactions with the electrolyte and help keep small pieces of broken silicon flakes together within the carbon structure. The selection and amount of conductivity enhancement additives are shown to be critical to the achievement of both high-ICE and high-capacity retention after long cycling. The Super P conductivity enhancement additive exhibits a smaller effective surface area where SEI forms compared to KB, and thus leads to the best combination of both high-ICE and high-capacity retention. A silicon-based anode exhibiting high capacity, high ICE, and a long cycling life has been achieved by the facile and promising one-step fabrication process.
RESUMO
We report a facile pyrolysis process for the fabrication of a porous silicon-based anode for lithium-ion battery. Silicon flakes of 100 nm × 800 nm × 800 nm were mixed with equal weight of sodium carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR) as the binder and the conductivity enhancement additive, Ketjen Black (KB), at the weight ratio of silicon-binder-KB being 70%:20%:10%, respectively. Pyrolysis was carried out at 700 °C in an inert argon environment for one hour. The process converts the binder to graphitic carbon coatings on silicon and a porous carbon structure. The process led to initial coulombic efficiency (ICE) being improved from 67% before pyrolysis to 75% after pyrolysis with the retention of 2.1 mAh/cm2 areal capacity after 100 discharge-charge cycles at 1 A/g rate. The improved ICE and cycling performance are attributed to graphitic coatings, which protect silicon from irreversible reactions with the electrolyte to form compounds such as lithium-silicon-fluoride (Li2SiF6) and the physical integrity and buffer space provided by the porous carbon structure. By eliminating the adverse effects of KB, the anode made with silicon-to-binder weight ratio of 70%:30% exhibited further improvement of the ICE to approximately 90%. This demonstrated that pyrolysis is a facile and promising one-step process for the fabrication of silicon-based anode with high ICE and long cycling life. This is especially true when the amount and choice of conductivity enhancement additive are optimized.
RESUMO
Silicon flakes of about 100 × 1000 × 1000 nm in sizes recycled from wastes of silicon wafer manufacturing processes were coated with combined silicon carbide (SiC) and graphitic (Resorcinol-Formaldehyde (RF)) carbon coatings to serve as active materials of the anode of lithium ion battery (LIB). Thermal carbonization of silicon at 1000 °C for 5 h forms 5-nm SiC encapsulating silicon flakes. SiC provides physical strength to help silicon flakes maintain physical integrity and isolating silicon from irreversible reactions with the electrolyte. Lithium diffuses through SiC before alloying with silicon. The SiC buffer layer results in uniform alloying reactions between lithium and silicon on the surface around a silicon flake. RF carbon coatings provide enhanced electrical conductivity of SiC encapsulated silicon flakes. We characterized the coatings and anode by SEM, TEM, FTIR, XRD, cyclic voltammetry (CV), electrochemical impedance spectra (EIS), and electrical resistance measurements. Coin half-cells with combined SiC and RF carbon coatings exhibit an initial Coulombic efficiency (ICE) of 76% and retains a specific capacity of 955 mAh/g at 100th cycle and 850 mAh/g at 150th cycle of repetitive discharge and charge operation. Pre-lithiation of the anode increases the ICE to 97%. The SiC buffer layer reduces local stresses caused by non-uniform volume changes and improves the capacity retention and the cycling life.
