Core-Shell Si@SiOC Particles Synthesized Using Supercritical Carbon Dioxide Fluid for Superior Li-Ion Storage Performance.

A supercritical carbon dioxide (SCCO2) fluid, characterized by gas-like diffusivity, near-zero surface tension, and excellent mass transfer properties, is used as a precursor to produce silicon oxycarbide (SiOC) coating. SCCO2 disperses and reacts with Si particles to form an interfacial layer consisting of Si, O, and C. After an 850 °C annealing process, a conformal SiOC coating layer forms, resulting in core-shell Si@SiOC particles. High-resolution transmission electron microscopy and its X-ray line-scan spectroscopy, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and Raman spectroscopy, are used to examine the SiOC formation mechanism. Effects of SCCO2 interaction time on the SiOC properties are investigated. The SiOC layer connects the Si@SiOC particles, improving electron and Li+ transport. Cyclic voltammetry, galvanostatic intermittent titration technique, and electrochemical impedance spectroscopy are employed to examine the role of SiOC during charging/discharging. Operando X-ray diffraction data reveal that the SiOC coating reduces crystal size of the formed Li15Si4 and increases its formation/elimination reversibility during cycling. The Si@SiOC electrode shows a capacitiy of 2250 mAh g-1 at 0.2 A g-1. After 500 cycles, the capacity retention is 72% with Coulombic efficiency above 99.8%. A full cell consisting of Si@SiOC anode and LiNi0.8Co0.1Mn0.1O2 cathode is constructed, and its performance is evaluated.

Engineering of Aromatic Naphthalene and Solvent Molecules to Optimize Chemical Prelithiation for Lithium-Ion Batteries.

A cost-effective chemical prelithiation solution, which consists of Li+, polyaromatic hydrocarbon (PAH), and solvent, is developed for a model hard carbon (HC) electrode. Naphthalene and methyl-substituted naphthalene PAHs, namely 2-methylnaphthalene and 1-methylnaphthalene, are first compared. Grafting an electron-donating methyl group onto the benzene ring can decrease electron affinity and thus reduce the redox potential, which is validated by density functional theory calculations. Ethylene glycol dimethyl ether (G1), diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether solvents are then compared. The G1 solution has the highest conductivity and least steric hindrance, and thus the 1-methylnaphthalene/G1 solution shows superior prelithiation capability. In addition, the effects of the interaction time between Li+ and 1-methylnaphthalene in G1 solvent on the electrochemical properties of a prelithiated HC electrode are investigated. Nuclear magnetic resonance data confirm that 10-h aging is needed to achieve a stable solution coordination state and thus optimal prelithiation efficacy. It is also found that appropriate prelithiation creates a more Li+-conducing and robust solid-electrolyte interphase, improving the rate capability and cycling stability of the HC electrode.

Metal-Doped NASICON/Polymer Composite Solid Electrolyte for Lithium Titania Anode in Lithium-Ion Batteries.

This study reports five types of metal-doped (Co, Cu, Sn, V, and Zr) NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP)/polymer composite solid electrolytes (CSEs) enabling Li4Ti5O12 (LTO) anodes to have high rate capability and excellent cycling performance. The high Li+-conductivity LATP samples are successfully synthesized through a modified sol-gel method followed by thermal calcination. We find that the cation dopants clearly influence the substitution of Al for Ti, with the type of dopant serving as a crucial factor in determining the ionic conductivity and interfacial resistance of the solid electrolyte. The CSE containing poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and Sn-LATP shows an ionic conductivity of 1.88 × 10-4 S cm-1 at ambient temperature. The optimum conductivity can be attributed to alterations in the lattice parameters and Li+ transport pathways owing to Sn doping. The solid-state cell equipped with the LTO-supported CSE containing Sn-LATP fillers demonstrates both excellent high rate capability at 5 C (with a capacity retention of 86% compared to the value measured at 0.2 C) and superior cycling stability, maintaining high Coulombic efficiency (>99.0%) over 510 cycles. These findings indicate that the proposed CSE is highly promising for use in solid-state lithium batteries with desirable charge-discharge properties and high durability.

Double Nitrogenation Layer Formed Using Nitric Oxide for Enhancing Li+ Storage Performance, Cycling Stability, and Safety of Si Electrodes.

To enhance Li storage properties, nitrogenation methods are developed for Si anodes. First, melamine, urea, and nitric oxide (NO) precursors are used to nitrogenize carbon-coated Si particles. The properties of the obtained particles are compared. It is found that the NO process can maximize the graphitic nitrogen (N) content and electronic conductivity of a sample. In addition, optimized N functional groups and O─C species on the electrode surface increase electrolyte wettability. However, with a carbon barrier layer, NO hardly nitrogenizes the Si cores. Therefore, bare Si particles are reacted with NO. Core-shell Si@amorphous SiNx particles are produced using a facile and scalable NO treatment route. The effects of the NO reaction time on the physicochemical properties and charge-discharge performance of the obtained materials are systematically examined. Finally, the Si@SiNx particles are coated with N-doped carbon. Superior capacities of 2435 and 1280 mAh g-1 are achieved at 0.2 and 5 A g-1, respectively. After 300 cycles, 90% of the initial capacity is retained. In addition, differential scanning calorimetry data indicate that the multiple nitrogenation layers formed by NO significantly suppress electrode exothermic reactions during thermal runaway.

Enhanced Electrochemical Performance of Ca-Doped Na3V2(PO4)2F3/C Cathode Materials for Sodium-Ion Batteries.

Na3V2(PO4)2F3 (NVPF) with a NASICON structure has garnered attention as a cathode material owing to its stable 3D structure, rapid ion diffusion channels, high operating voltage, and impressive cycling stability. Nevertheless, the low intrinsic electronic conductivity of the material leading to a poor rate capability presents a significant challenge for practical application. Herein, we develop a series of Ca-doped NVPF/C cathode materials with various Ca2+ doping levels using a simple sol-gel and carbon thermal reduction approach. X-ray diffraction analysis confirmed that the inclusion of Ca2+ does not alter the crystal structure of the parent material but instead expands the lattice spacing. Density functional theory calculations depict that substituting Ca2+ ions at the V3+ site reduces the band gap, leading to increased electronic conductivity. This substitution also enhanced the structural stability, preventing lattice distortion during the charge/discharge cycles. Furthermore, the presence of the Ca2+ ion introduces two localized states within the band gap, resulting in enhanced electrochemical performance compared to that of Mg-doped NVPF/C. The optimal NVPF-Ca-0.05/C cathode exhibits superior specific capacities of 124 and 86 mAh g-1 at 0.1 and 10 C, respectively. Additionally, the NVPF-Ca-0.05/C demonstrates satisfactory capacity retention of 70% after 1000 charge/discharge cycles at 10 C. These remarkable results can be attributed to the optimized particle size, excellent structural stability, and enhanced ionic and electronic conductivity induced by the Ca doping. Our findings provide valuable insight into the development of cathode material with desirable electrochemical properties.

Charge-Discharge Mechanism of High-Entropy Co-Free Spinel Oxide Toward Li+ Storage Examined Using Operando Quick-Scanning X-Ray Absorption Spectroscopy.

Transition metal high-entropy oxides (HEOs) are an attractive class of anode materials for high-performance lithium-ion batteries (LIBs). However, owing to the multiple electroactive centers of HEOs, the Li+ storage mechanism is complex and debated in the literature. In this work, operando quick-scanning X-ray absorption spectroscopy (XAS) is used to study the lithiation/delithiation mechanism of the Cobalt-free spinel (CrMnFeNiCu)3 O4 HEO. A monochromator oscillation frequency of 2 Hz is used and 240 spectra are integrated to achieve a 2 min time resolution. High-photon-flux synchrotron radiation is employed to increase the XAS sensitivity. The results indicate that the Cu2+ and Ni2+ cations are reduced to their metallic states during lithiation but their oxidation reactions are less favorable compared to the other elements upon delithiation. The Mn2+/3+ and Fe2+/3+ cations undergo two-step conversion reactions to form metallic phases, with MnO and FeO as the intermediate species, respectively. During delithiation, the oxidation of Mn occurs prior to that of Fe. The Cr3+ cations are reduced to CrO and then Cr0 during lithiation. A relatively large overpotential is required to activate the Cr reoxidation reaction. The Cr3+ cations are found after delithiation. These results can guide the material design of HEOs for improving LIB performance.

Hierarchical Carbon Composites for High-Energy/Power-Density and High-Reliability Supercapacitors with Low Aging Rate.

A facile method for preparing hierarchical carbon composites that contain activated carbon (AC), carbon nanospheres (CNSs), and carbon nanotubes (CNTs) for use as the electrode material in supercapacitors (SCs) was developed. The CNS/CNT network enabled the formation of three-dimensional conducting pathways within the highly porous AC matrix, effectively reducing the internal resistance of an SC electrode. The specific capacitance, cyclability, voltage window, temperature profile during charging/discharging, leakage current, gas evolution, and self-discharge of the fabricated SCs were systematically investigated and the optimal CNS/CNT ratio was determined. A 2.5 V floating aging test at 70 °C was performed on SCs made with various hierarchical carbon electrodes. Electrochemical impedance spectroscopy, postmortem electron microscopy, Raman spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses were conducted to examine the electrode aging behavior. A hierarchical carbon architecture with an appropriate AC/CNS/CNT constituent ratio could significantly improve charge-discharge performance, increase cell reliability, and decrease the aging-related degradation rate.

Manipulation of Nitrogen-Heteroatom Configuration for Enhanced Charge-Storage Performance and Reliability of Nanoporous Carbon Electrodes.

In this study, various nitrogen-containing functional groups, namely, pyridine (N-6), pyrrole (N-5), oxidized N (N-O), and quaternary N (N-Q), are created on activated carbon (AC) surface via melamine, ammonia, and nitric oxide doping methods. N-5 and N-6 groups markedly alter the specific surface area and pore size of AC. N-O is found to affect electrolyte wettability, and the N-Q content is closely associated with AC electronic conductivity. The nitrogen-containing groups do not contribute to pseudocapacitance in propylene carbonate and acetonitrile electrolytes. However, the nitric-oxide-treated carbon (AC-NO) exhibits the best high-rate charge-discharge performance among the investigated materials. The N-Q-enriched and N-5/N-6-depleted AC-NO most effectively suppresses the leakage current and gas evolution of supercapacitors. Online gas chromatography is used to analyze the gaseous species produced from AC electrodes. With an appropriate surface functionality on carbon, the cell voltage can be increased to ∼3 V, increasing the energy and power densities. The aging behavior of the carbon electrodes with and without nitrogen modification after being floated at 2.5 V and 70 °C for 3 days is investigated. An effective strategy for enhancing supercapacitor performance and reliability is proposed.

A Holey Graphene Additive for Boosting Performance of Electric Double-Layer Supercapacitors.

We demonstrate a facile and effective method, which is low-cost and easy to scale up, to fabricate holey graphene nanosheets (HGNSs) via ultrafast heating during synthesis. Various heating temperatures are used to modify the material properties of HGNSs. First, we use HGNSs as the electrode active materials for electric double-layer capacitors (EDLCs). A synthesis temperature of 900 °C seems to be optimal, i.e., the conductivity and adhesion of HGNSs reach a compromise. The gravimetric capacitance of this HGNS sample (namely HGNS-900) is 56 F·g-1. However, the volumetric capacitance is low, which hinders its practical application. Secondly, we incorporate activated carbon (AC) into HGNS-900 to make a composite EDLC material. The effect of the AC:HGNS-900 ratio on the capacitance, high-rate performance, and cycling stability are systematically investigated. With a proper amount of HGNS-900, both the electrode gravimetric and volumetric capacitances at high rate charging/discharging are clearly higher than those of plain AC electrodes. The AC/HGNS-900 composite is a promising electrode material for nonaqueous EDLC applications.

Composition Modulation of Ionic Liquid Hybrid Electrolyte for 5 V Lithium-Ion Batteries.

Electrolyte is a key component in high-voltage lithium-ion batteries (LIBs). Bis(trifluoromethanesulfonyl)imide-based ionic liquid (IL)/organic carbonate hybrid electrolytes have been a research focus owing to their excellent balance of safety and ionic conductivity. Nevertheless, corrosion of Al current collectors at high potentials usually happens for this kind of electrolyte. In this study, this long-standing problem is solved via the modulation of the IL/carbonate ratio and LiPF6 concentration in the hybrid electrolyte. The proposed electrolyte suppresses Al dissolution and electrolyte oxidation at 5 V (vs Li+/Li) and thus allows for ideal lithiation/delithiation performance of a high-voltage LiNi0.5Mn1.5O4 (LNMO) cathode even at 55 °C. The underlying mechanism is examined in this work. Excellent cycling stability (97% capacity retention) for an LNMO cathode after 300 cycles is achieved. This electrolyte shows good wettability toward a polyethylene separator and low flammability. In addition, satisfactory compatibility with both graphite and Si-based anodes is confirmed. The proposed electrolyte design strategies have great potential for applications in high-voltage LIBs.

Carbonaceous Anodes Derived from Sugarcane Bagasse for Sodium-Ion Batteries.

To realize the sustainability of Na-ion batteries (NIBs) for large-scale energy storage applications, a resource-abundant and cost-effective anode material is required. In this study, sugarcane bagasse (SB), one of the most abundant types of biowaste, is chosen as the carbon precursor to produce a hard carbon (HC) anode for NIBs. SB has a great balance of cellulose, hemicellulose, and lignin, which prevents full graphitization of the pyrolyzed carbon but ensures a sufficiently ordered carbon structure for Na+ transport. Compared with HC derived from waste apples, which are pectin-rich and have less cellulose than SB, SB-derived HC (SB-HC) has fewer defects and a lower oxygen content. SB-HC thus has a higher first-cycle sodiation/desodiation coulombic efficiency and better cycling stability. In addition, SB-HC has a unique flake-like morphology, which can shorten the Na+ diffusion length, and higher electronic conductivity (owing to more sp2 -hybridized carbon), resulting in superior high-rate charge-discharge performance to apple-derived HC. The effects of pyrolysis temperature on the material characteristics and electrochemical properties, evaluated by using chronopotentiometry, cyclic voltammetry, and electrochemical impedance spectroscopy, are systematically investigated for both kinds of HC.

Supercapacitive Properties of Micropore- and Mesopore-Rich Activated Carbon in Ionic-Liquid Electrolytes with Various Constituent Ions.

Ionic-liquid (IL) electrolytes, characterized by large potential windows, intrinsic ionic conductivity, low environmental hazard, and high safety, are used for micropore- and mesopore-rich activated-carbon (ACmicro and ACmeso ) supercapacitors. IL electrolytes consisting of various cations [1-ethyl-3-methylimidazolium (EMI+ ), N-propyl-N-methylpyrrolidinium (PMP+ ), and N-butyl-N-methylpyrrolidinium (BMP+ )] and various anions [bis(trifluoromethylsulfonyl)imide (TFSI- ), BF4 - , and bis(fluorosulfonyl)imide (FSI- )] are investigated. The electrolyte conductivity, viscosity, and ion transport properties at the ACmicro and ACmeso electrodes are studied. In addition, the capacitance, rate capability, and cycling stability of the two types of AC electrodes are systematically examined and post-mortem material analyses are conducted. The effects of IL composition on the charge-discharge capacitances of the ACmicro electrodes are more pronounced than those for the ACmeso electrodes. The FSI-based IL electrolytes, for which electrochemical properties are cation dependent, are found to be promising. Incorporating EMI+ with FSI- results in a low electrolyte viscosity and a fast ion transport, giving rise to optimized electrode capacitance and rate capability. Replacing EMI+ with PMP+ increases the cell voltage (to 3.5 V) and maximum energy density (to 42 Wh kg-1 ) of the ACmicro cell at the cost of cycling stability.

A Water-Soluble NaCMC/NaPAA Binder for Exceptional Improvement of Sodium-Ion Batteries with an SnO2 -Ordered Mesoporous Carbon Anode.

SnO2 @CMK-8 composite, a highly promising anode for Na-ion batteries (NIBs), was incorporated with polyvinylidene difluoride (PVDF), sodium carboxymethylcellulose (NaCMC), sodium polyacrylate (NaPAA), and NaCMC/NaPAA mixed binders to optimize the electrode sodiation/desodiation properties. Synergistic effects between NaCMC and NaPAA led to the formation of an effective protective film on the electrode. This coating layer not only increased the charge-discharge Coulombic efficiency, suppressing the accumulation of solid-electrolyte interphases, but also kept the SnO2 nanoparticles in the CMK-8 matrix, preventing the agglomeration and removal of oxide upon cycling. The adhesion strength and stability towards the electrolyte of the binders were evaluated. In addition, the charge-transfer resistance and apparent Na+ diffusion of the SnO2 @CMK-8 electrodes with various binders were examined and post-mortem analyses were conducted. With NaCMC/NaPAA binder, exceptional electrode capacities of 850 and 425 mAh g-1 were obtained at charge-discharge rates of 20 and 2000 mA g-1 , respectively. After 300 cycles, 90 % capacity retention was achieved. The thermal reactivity of the sodiated electrodes was studied by using differential scanning calorimetry. The binder effects on NIB safety, in terms of thermal runaway, are discussed.

Three-dimensional interpenetrating mesoporous carbon confining SnO2 particles for superior sodiation/desodiation properties.

Nanosized SnO2 particles (∼2 nm in diameter) are embedded in ordered mesoporous CMK-8 carbon with unique three-dimensional interconnected pore channels and used as a sodium-ion battery (NIB) anode. Due to the CMK-8 confinement effects, the growth of SnO2 is suppressed during synthesis, leading to high material electroactivity. The CMK-8 not only serves as an electronic conducting pathway, but also creates interpenetrating tunnels, which guarantee electrolyte accessibility and thus Na+ transport throughout the electrode. Moreover, the change in the SnO2 volume during sodiation/desodiation can be accommodated by the CMK-8 framework. With a high tap density of ∼1000 mg cm-3 (vs. ∼800 mg cm-3 for the conventional NIB anode, hard carbon), the SnO2/CMK-8 anode shows a high reversible capacity of 800 mA h g-1 and excellent rate capability, delivering 330 mA h g-1 in ∼10 min. The electrode charge storage mechanism is examined using synchrotron X-ray diffraction. We confirm that CMK-8 incorporation can effectively promote the SnO2-Sn conversion reaction and Sn-Na alloying reaction, which are known to be thermodynamically/kinetically difficult, increasing the electrode charge-discharge performance.