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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.
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A rechargeable aqueous hybrid ion alkaline battery, using a proton and a potassium ion as charge carriers for the anode and cathode, respectively, is proposed in this study by using well-developed potassium nickel hexacyanoferrate as the cathode material and mesoporous carbon sheets as the anode material, respectively. The constructed battery operates in a concentrated KOH solution, in which the energy storage mechanism for potassium nickel hexacyanoferrate involves the redox reaction of Fe2+/Fe3+ associated with potassium ion insertion/extraction and the redox reaction of Ni(OH)2/NiOOH. The mechanism for the carbon anode is electrochemical hydrogen storage. The cathode made of potassium nickel hexacyanoferrate exhibits both an ultrahigh capacity of 232.7 mAh g-1 under 100 mA g-1 and a consistent performance of 214 mAh g-1 at 2000 mA g-1 (with a capacity retention of 92.8% after 200 cycles). The mesoporous carbon sheet anode exhibits a capacity of 87.6 mAh·g-1 at 100 mA g-1 with a good rate and cyclic performance. The full cell provides an operational voltage of 1.55 V, a capacity of 93.6 mAh g-1 at 100 mA g-1, and 82.4% capacity retention after 1000 cycles at 2000 mA g-1 along with a low self-discharge rate. The investigation and discussion about the energy storage mechanisms for both electrode materials are also provided.
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Tris(pentafluorophenyl)borane (TPFPB) was found to be an efficient catalyst for rapid superoxide (O2(-)) disproportionation. The kinetics for the catalytic disproportionation reaction is much faster than the reaction between O2(-) and propylene carbonate. Therefore, the negative impact of the reaction between the electrolyte and O2(-) produced by the O2 reduction is minimized. The cathodic current for O2 reduction can be doubled in the presence of TPFPB. The high reduction current resulted from the pseudo two-electron O2-reduction reaction due to the replenishment of O2 at the electrode surface. This discovery could lead to a new avenue for the development of high-capacity, high-rate, rechargeable Li-air batteries.
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Recycling spent lithium iron phosphate (LFP) cathodes in an economically sustainable way remains a great challenge due to their low-value elemental composition. Thus, both low-cost technology together with a high-value product are critical for the recovery of the LFP materials. In this study, the commercially mature ion-exchange (IX) method was explored to recover Li from LFP material for the first time. The feasibility of Li-H and Li-K IX reactions using strong and weak acid cation exchange resins was systematically investigated from the thermodynamic and kinetic perspectives. Different organic and inorganic acids were explored to obtain the feeding solution. The IX efficiency was greatly affected by the pH of the feeding solutions. Oxalic acid leaching solution with mild pH value and low iron impurity were determined to be the optimal feeding solution for IX reaction. The kinetics of IX and regeneration reaction were fast, and the resins can be reused several times without loss of IX capacity. Along with the P element remaining in the leaching solution, the Li-K IX reaction delivered a potential product of multi-elemental fertilizer. This simple and economical technology provides a practical recycling strategy for the spent LFP batteries.
Assuntos
Lítio , Reciclagem , Eletrodos , Fontes de Energia Elétrica , Íons , FerroRESUMO
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.
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The high temperature cycling performance of a wide temperature electrolyte and the solid electrolyte interphase (SEI) along the cycling were investigated using a three-electrode pouch cell. The electrolyte developed in our lab demonstrated outstanding low temperature performance. The electrolyte was found to have a good and stable cycling performance at a high temperature in comparison with a state-of-the-art baseline electrolyte. Electrochemical impedance spectroscopy (EIS) was conducted on the anode, the cathode and the full cell independently with a reference embedded pouch cell. The distribution of relaxation times (DRT) transformation was calculated from the EIS spectrum. An equivalent circuit model was used to fit the anode EIS data and the electrochemical process on the anode was revealed. We concluded that a denser SEI layer was built on the anode of the improved electrolyte.
Assuntos
Espectroscopia Dielétrica , Eletrólitos , Impedância Elétrica , Eletrodos , TemperaturaRESUMO
The ever-growing market of portable electronics and electric vehicles has spurred extensive research for advanced lithium-ion batteries (LIBs) with high energy density. High-capacity alloy- and conversion-type anodes are explored to replace the conventional graphite anode. However, one common issue plaguing these anodes is the large initial capacity loss caused by the solid electrolyte interface formation and other irreversible parasitic reactions, which decrease the total energy density and prevent further market integration. Prelithiation becomes indispensable to compensate for the initial capacity loss, enhance the full cell cycling performance, and bridge the gap between laboratory studies and the practical requirements of advanced LIBs. This review summarizes the various emerging anode and cathode prelithiation techniques, the key barriers, and the corresponding strategies for manufacturing-compatible and scalable prelithiation. Furthermore, prelithiation as the primary Li+ donor enables the safe assembly of new-configured "beyond LIBs" (e.g., Li-ion/S and Li-ion/O2 batteries) and high power-density Li-ion capacitors (LICs). The related progress is also summarized. Finally, perspectives are suggested on the future trend of prelithiation techniques to propel the commercialization of advanced LIBs/LICs.
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Rechargeable lithium-ion batteries have built much of our modern society. Developing high-loading and high-energy batteries have become an inevitable trend to satisfy the ever-growing demand of energy consumption. However, issues related to mechanical instability and electrochemical polarization have become more prominent accompanying the increase of electrode thickness. How to establish a robust and rapid charge transport network within the electrode architecture plays a vital role for the mechanical property and the reaction dynamics of thick electrodes. In this review, principles of charge transport mechanism and challenges of thick electrode development are elaborated. Next, recent progress on advanced electrode architecture design focused on structural engineering is summarized. Finally, a transmission line model is proposed as an effective tool to guide the engineering of thick electrodes.
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Organic electrode materials have been considered as promising candidates for the next generation rechargeable battery systems due to their high theoretical capacity, versatility, and environmentally friendly nature. Among them, organosulfur compounds have been receiving more attention in conjunction with the development of lithium-sulfur batteries. Usually, organosulfide electrodes can deliver a relatively high theoretical capacity based on reversible breakage and formation of disulfide (S-S) bonds. In this review, we provide an overview of organosulfur materials for rechargeable lithium batteries, including their molecular structural design, structure related electrochemical performance study and electrochemical performance optimization. In addition, recent progress of advanced characterization techniques for investigation of the structure and lithium storage mechanism of organosulfur electrodes are elaborated. To further understand the perspective application, the additive effect of organosulfur compounds for lithium metal anodes, sulfur cathodes and high voltage inorganic cathode materials are reviewed with typical examples. Finally, some remaining challenges and perspectives of the organosulfur compounds as lithium battery components are also discussed. This review is intended to serve as general guidance for researchers to facilitate the development of organosulfur compounds.
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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.
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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.
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SnO2 is an attractive anodic material for advanced lithium-ion batteries (LIBs). However, its low electronic conductivity and large volume change in lithiation/delithiation lead to a poor rate/cycling performance. Moreover, the initial Coulombic efficiencies (CEs) of SnO2 anodes are usually too low to build practical full LIBs. Herein, a two-step hydrothermal synthesis and pyrolysis method is used to prepare a SnO2/C nanocomposite, in which aggregated SnO2 nanosheets and a carbon network are well-interpenetrated with each other. The SnO2/C nanocomposite exhibits a good rate/cycling performance in half-cell tests but still shows a low initial CE of 45%. To overcome this shortage and realize its application in a full-cell assembly, the SnO2/C anode is controllably prelithiated by the lithium-biphenyl reagent and then coupled with a LiCoO2 cathode. The resulting full LIB displays a high capacity of over 98 mAh g-1LCO in 300 cycles at 1 C rate.
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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.
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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.
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A high capacity alkaline redox storage chemistry is explored based on a novel, environmentally benign zirconia stabilized Fe(6+)/B(2-) chemistry, which sustains an electrochemical potential matched to the pervasive, conventional MnO(2)-Zn battery chemistry, however with a much higher electrochemical capacity.
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A Co@nitrogen-doped carbon nanoparticle composite was synthesized via a facile molecular self-assembling procedure. The material was used as the host for the electrochemical storage of hydrogen. The hydrogen storage capacity of the material was over 300 mAh g-1 at a rate of 100 mAg-1. It also exhibited superior stability for storage of hydrogen, high rate capability, and good cyclic life. Hybridizing metallic cobalt nanoparticle with nitrogen-doped mesoporous carbon is found to be a good approach for the electrochemical storage of hydrogen.
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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.
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By means of high performance liquid chromatography-mass spectroscopy, the concentration of sulfur and polysulfides was determined in nonaqueous electrolytes. The stability of sulfur and Li in eight electrolytes was studied quantitatively. It was found that sulfur reacted with Li in most of the commonly used electrolytes for lithium-sulfur batteries. The reaction products between sulfur and Li were qualitatively identified. In some cases, the solid electrolyte interface on the Li can successfully prevent the interaction between S and Li; however, it was found that the solid electrolyte interface was damaged by polysulfide ions.
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The reaction between polysulfides and a lithium anode in a Li-S battery was examined using HPLC. The results demonstrated that the polysulfide species with six sulfur atoms or more were reactive with regard to lithium metal. Although the reaction can be greatly inhibited by the addition of LiNO3 in the electrolyte, LiNO3 cannot form a stable protection layer on the Li anode to prevent the reaction during storage.