RESUMO
Given that both elemental sulfur (S8) and lithium sulfide (Li2S) exhibit insulating properties, the involvement of conductive host materials becomes crucial for facilitating charge transfer in sulfur cathodes within lithium-sulfur (Li-S) batteries. Furthermore, there has been a recent surge in the exploration of host materials for sulfur cathodes to address the "polysulfide shuttle" effect. This effect arises from the formation of polysulfide species during the charge-discharge cycles of the Li-S batteries and can be mitigated through physical or chemical interactions with specific materials. To qualitatively and accurately assess the interactions between polysulfides and the potential host materials, this study utilized a well-established high-performance liquid chromatography method for polysulfide analysis. The objective was to monitor the changes in polysulfide solutions after contact with 44 different carbon and inorganic materials. Based on both qualitative and quantitative chromatographic results, it was determined that 20 out of the 44 materials exhibit significant interactions with polysulfides. The primary form of interaction observed is the irreversible disproportionation reaction with elemental sulfur being one of the resulting products.
RESUMO
A long cycle-life Li-S battery (both the coin cell and pouch cell) is reported with minimum shuttle effect. The performance was achieved with a bifunctional carbon material with three unique features. The carbon can catalyze the disproportionation of dissolved long-chain polysulfide ions to elemental sulfur; the carbon can ensure homogeneous precipitation of Li sulfide on the host carbon, and the carbon has a honeycomb porous structure, which can store sulfur better. All the features are demonstrated experimentally and reported in this paper. Few dissolved polysulfides are found by high-performance liquid chromatography in the electrolyte of the Li-S batteries during cycling, and only dissolved elemental sulfur is detected. The unique porous structure of the carbon made from raw silk is revealed by scanning electron microscopy. The N-containing functionalities that were introduced to carbon from the amino acids of raw silk can catalyze the disproportionation of the dissolved Sn2- to solid S8 at the cathode side, thereby mitigating the shuttle effect. In addition, the hierarchical honeycomb porous structures generated by a carbonization process can physically trap high-order lithium polysulfides and sustain the volume change of sulfur. With the synergistic effects of the unique structures and characteristics of the carbon prepared at 800 °C, the sulfur/carbon composite delivers a high reversible capacity of over 1000 mAh g-1 after 100 cycles with a sulfur content of 1.2 mg cm-2 in a pouch cell.
RESUMO
Hard carbon has been extensively investigated as anode materials for high-energy lithium-ion batteries owing to its high capacity, long cycle life, good rate capability, and low cost of production. However, it suffers from a large irreversible capacity and thus low initial coulombic efficiency (ICE), which hinders its commercial use. Here, we developed a fast and controllable prelithiation method based on a chemical reaction using a lithium-containing reagent (1 M lithium biphenylide dissolved in tetrahydrofuran). The prelithiation extent can be easily controlled by tuning the reaction time. An SEI layer is formed during chemical prelithiation, and the ICE of prelithiated hard carbon in half-cell format can be increased to â¼106% in 30 s. When matched with a LiNi1/3Co1/3Mn1/3O2 cathode, the full cell with the prelithiated hard carbon anode exhibits a much improved ICE (90.2 vs 75%) and cycling performance than those of the pristine full cell. This facile prelithiation method is proved to be a practical solution for the commercial application of hard carbon materials.
RESUMO
Overcharge abuse can trigger thermal runaway when a device is left unattended. Redox shuttles, as economic and efficient electrolyte additives, have been proven to provide reliable and reversible protection for state-of-art Li-ion batteries (LIBs) against overcharge. Here, a functional organic salt, trisaminocyclopropenium perchlorate (TACâ¢ClO4), is developed and employed as a redox shuttle for overcharge protection in a Na-ion battery system. This type of novel redox shuttle molecule is reported for the first time. As a unique ionic compound with the smallest aromatic ring structure, TACâ¢ClO4 exhibits distinctive attributes of fast diffusion, high solubility, and ultrahigh chemical/electrochemical stability in both redox states. With merely 0.1 M TACâ¢ClO4 in electrolyte, Na3V2(PO4)3 cathode can carry overcharge current even up to 10C or 400% SOC. Na3V2(PO4)3/hard carbon cells demonstrated strong anti-overcharging ability of 176 cycles at 0.5C rate and 54 cycles at 1C rate with 100% overcharge. Moreover, TACâ¢ClO4 addition has little impact on the electrochemical performance of Na-ion batteries, especially on the rate performance and the initial Columbic efficiency. Interestingly, a unique and reversible electrochromic behavior of TACâ¢ClO4 electrolyte can promptly provide the device an overcharge alarm under a designed potential to further enhance the safety level.
RESUMO
Safety concerns have severely impeded the practical application of high-energy-density lithium-based batteries. Dendrite growth and overcharging can lead to particularly catastrophic thermal failure. Here we report an organic cation, trisaminocyclopropenium (TAC), as a bi-functional electrolyte additive to suppress dendrite growth and offer reversible overcharge protection for metallic lithium-based batteries. During the Li plating process, TAC cations with aliphatic chains can form a positively charged electrostatic shield around Li protrusions, repelling the approaching Li+ and thereby attaining a more uniform plating. A two times longer cycle life of 300 h at 1 mA cm-2 is achieved in a Li|Li symmetric cell in comparison with the control. During the overcharging process, the redox-active TAC can repeatedly shuttle between two electrodes, maintaining the cell voltage within a safe value. A solid protection of 117 cycles (~1640 h) at 0.2 C with a 100% overcharge is achieved in a LiFePO4/Li4Ti5O12 cell. This study sheds fresh light on the ability of organic cations to build safer batteries.
RESUMO
This study reports an ambient-air-tolerant approach for negative electrode prelithiation by using 1 M lithium-biphenyl (Li-Bp)/tetrahydrofuran (THF) solution as the prelithiation reagent. Key to this strategy are the relatively stable nature of 1 M Li-Bp/THF in ambient air and the unique electrochemical behavior of Bp in ether and carbonate solvents. With its low redox potential of 0.41 V vs Li/Li+, Li-Bp can prelithiate various active materials with high efficacy. The successful prelithiation of a phosphrous/carbon composite electrode and the notable improvement in its initial Coulombic efficiency (CE) demonstrates the practicality of this strategy.
RESUMO
The mechanism of the sulfur cathode in Li-S batteries has been proposed. It was revealed by the real-time quantitative determination of polysulfide species and elemental sulfur by means of high-performance liquid chromatography in the course of the discharge and recharge of a Li-S battery. A three-step reduction mechanism including two chemical equilibrium reactions was proposed for the sulfur cathode discharge. The typical two-plateau discharge curve for the sulfur cathode can be explained. A two-step oxidation mechanism for Li2S and Li2S2 with a single chemical equilibrium among soluble polysulfide ions was proposed. The chemical equilibrium among S52-, S62-, S72-, and S82- throughout the entire oxidation process resulted for a single flat recharge curve in Li-S batteries.