High-Performance LiF@C-Coated FeF3·0.33H2O Lithium-Ion Batteries with an Ionic Liquid Electrolyte.
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ABSTRACT:
SUBMITTER: Zeng C
PROVIDER: S-EPMC8756601 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.
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Project description:With the development of mobile electronic devices, there are more and more requirements for high-energy storage equipment. Traditional lithium-ion batteries, like lithium-iron phosphate batteries, are limited by their theoretical specific capacities and might not meet the requirements for high energy density in the future. Lithium-sulfur batteries (LSBs) might be ideal next-generation energy storage devices because they have nearly 10 times the theoretical specific capacities of lithium-ion batteries. However, the severe capacity decay of LSBs limits their application, especially at high currents. In this study, an ionic liquid (IL) electrolyte additive, TDA+TFSI, was reported. When 5% of the TDA+TFSI additive was added to a traditional ether-based organic electrolyte, the cycling performance of the LSBs was significantly improved compared with that of the LSBs with the pure traditional organic electrolyte. At a rate of 0.5 C, the discharge specific capacity in the first cycle of the LSBs with the 5% TDA+TFSI electrolyte additive was 1167 mAh g-1; the residual specific capacities after 100 cycles and 300 cycles were 579 mAh g-1 and 523 mAh g-1, respectively; and the average capacity decay rate per cycle was only 0.18% in 300 cycles. Moreover, the electrolyte with the TDA+TFSI additive had more obvious advantages than the pure organic ether-based electrolyte at high charge and discharge currents of 1.0 C. The residual discharge specific capacities were 428 mAh g-1 after 100 cycles and 399 mAh g-1 after 250 cycles, which were 13% higher than those of the LSBs without the TDA+TFSI additive. At the same time, the Coulombic efficiencies of the LSBs using the TDA+TFSI electrolyte additive were more stable than those of the LSBs using the traditional organic ether-based electrolyte. The results showed that the LSBs with the TDA+TFSI electrolyte additive formed a denser and more uniform solid electrolyte interface (SEI) film during cycling, which improved the stability of the electrochemical reaction.
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Project description:Polymerized ionic liquids (PIL) are an interesting substance class, which is discussed to transfer the outstanding properties and tunability of ionic liquids into a solid material. In this study we extend our previous research on ammonium based PIL and discuss the influence of additives and their usability as polymer electrolyte membranes for lithium ion batteries. The polymer electrolyte is thereby used as replacement for the commercially widespread system of a separator that is soaked with liquid electrolyte. The influence of the material composition on the ionic conductivity (via electrochemical impedance spectroscopy) and the diffusion coefficients (via pulsed-field-gradient nuclear magnetic resonance spectroscopy) were studied and cell tests with adapted membrane materials were performed. High amounts of the additional ionic liquid (IL) MPPyrr-TFSI (1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide) increased the ionic conductivity of the materials up to 1.3·10-4 S·cm-1 but made the usage of a cross-linker necessary to obtain mechanically stable membranes. The application of liquid electrolyte mixtures with ethylene carbonate (EC) and MPPyrr-TFSI decreased ionic conductivity values down to the 10-9 S·cm-1 range, but increased 7Li diffusion coefficients with increasing amounts of EC up to 1.7·10-10 m2·s-1. Cell tests with two membrane mixtures proofed that it is possible to build electrolyte membranes on basis of the polymerized ionic liquids, but also showed that further research is necessary to ensure stable and efficient cell cycling.
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Project description:A liquid-like poly(ionic liquid) (PIL) with a very low glass transition temperature of -51 °C and a thermal decomposition temperature of 202.7 °C was synthesized. A PIL-based electrolyte by mixing this poly(ionic liquid) with additives of 10 wt % propylene carbonate and 0.1 M LiClO4 is proved to be an excellent electrolyte for lithium-ion battery. The obtained PIL-based electrolyte exhibits a high ionic conductivity of 8.3 × 10-5 S cm-1 at 25 °C and 2.0 × 10-4 S cm-1 at 60 °C and a wide electrochemical potential window up to 5.61 V at 25 °C and 4.14 V at 60 °C. The Li/LiFePO4 batteries equipped with this PIL-based electrolyte achieve high capacity, outstanding cycling stability and rate capability at 25 °C, and even improved performance at high temperature like 60 °C. Such excellent performances of batteries are attributed to the formation of stable solid-electrolyte interface film at the lithium-electrolyte interface and the stability of electrolyte during cycling.
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Project description:Fast charging is of enormous concerns in the development of power batteries, while the low conductivity and lithium ion transference number in current electrolytes degraded the charge balance, limited the rate performance, and even cause safety issues for dendrite growth. Combine inorganic fillers and ionic liquid plasticizer, here in this paper we prepared a core-shell structured nanofibrous membrane, by incorporating with carbonate based electrolyte, a gel polymer electrolyte (GPE) with high conductivity, outstanding Li+ transference number was obtained. Notably, the Li/electrolyte/LiNi0.6Co0.2Mn0.2O2 (NCM622) half-cell with this composite electrolyte delivers a reversible capacity of 65 mAh/g at 20C, which is 13 times higher than that of with Celgard 2325 membrane. It also shows enhanced long-term cycle stability at both 3C and 5C for the suppression of lithium dendrite. This organic-inorganic co-modified GPE guarantees the fast charging ability and safety of LIBs, thus provides a promising method in high performance electrolyte design.
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Project description:Reduced graphene oxide (RGO)-coated TiO2 microcones have been synthesized via simple anodization and cyclic voltammetry for use in lithium-ion batteries (LIBs). Microcones had a perpendicularly oriented hollow core, an anatase structure, and a high surface area, allowing higher capacity than other nanosized TiO2 structures. TiO2 has low electrical conductivity, leading to the limitation of fast charging and high capacity; however, this was improved by the application of an RGO coating in this work. As anode materials of LIB, the obtained RGO microcone showed a capacity of 157 mAh g-1 at 10C (fully charged within ∼360 s) and sustained 1000 cycles with only 0.02% capacity fading per cycle. The capacity was 1.5 times higher than that of conventional microcone. We speculated that the decrease in the charge-transfer resistance (R ct) played a crucial role in increasing the capacity with fast charging.
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Project description:In this work, the use of N-methyl-N-propylpiperidinium difluoro(oxalato)borate Pip13DFOB ionic liquid (IL), originally synthesized in our laboratory, as an additive for liquid electrolytes in lithium-ion batteries (LIBs), is proposed. The synthesized IL exhibits glass and melting transitions at -70.9 °C and 17.1 °C, respectively, and a thermal decomposition temperature over 230 °C. A mixture based on 1.0 M LiPF6 in 1:1 v/v ethylene carbonate (EC): dimethyl carbonate (DMC) electrolyte solution (so called LP30) and the IL was prepared and tested in lithium metal cells versus two different commercially available carbonaceous electrodes, i.e., graphite (KS6) and graphene (GnP), and versus a high voltage LiNi0.5Mn1.5O4 (LNMO) cathode. A noticeable improvement was observed for Li|LNMO cells with an IL-added electrolyte, which exhibited a high specific capacity above 120 mAh g-1 with a Coulombic efficiency above 93% throughout 200 cycles, while the efficiency fell below 80% after 80 cycles with the absence of IL. The results confirm that the IL is promising additive for the electrolyte, especially for a longer cycle life of high-voltage cells.
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Project description:Transition-metal dissolution from cathode materials, manganese in particular, has been held responsible for severe capacity fading in lithium-ion batteries, with the deposition of the transition-metal cations on anode surface, in elemental form or as chelated-complexes, as the main contributor for such degradations. In this work we demonstrate with diverse experiments and calculations that, besides interfacial manganese species on anode, manganese(II) in bulk electrolyte also significantly destabilizes electrolyte components with its unique solvation-sheath structure, where the decompositions of carbonate molecules and hexafluorophosphate anion are catalyzed via their interactions with manganese(II). The manganese(II)-species eventually deposited on anode surface resists reduction to its elemental form because of its lower electrophilicity than carbonate molecule or anion, whose destabilization leads to sustained consumption. The reveal understanding of the once-overlooked role of manganese-dissolution in electrolytes provides fresh insight into the failure mechanism of manganese-based cathode chemistries, which serves as better guideline to electrolyte design for future batteries.
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Project description:Today, the requirement for clean, highly efficient, and safe energy seems to be higher and higher due to non-renewable energy and pollution of the environment. At this moment, lithium-ion batteries (LIBs) look like a reliable solution for this dilemma since they have huge energy density. However, the flammability of the conventional electrolyte used in the LIBs is one of critical disadvantages of LIBs, which compromises the safety issue of LIBs. Herein, we reported a non-flammable zwitterionic ionic liquid-based electrolyte named TLPEC, which was fabricated by simply mixing a novel zwitterionic ionic liquid TLP (93 wt%) and ethylene carbonate (EC, 7 wt%). The TLPEC electrolyte exhibited a wide electrochemical potential window of 1.65-5.10 V and a robust ionic conductivity of 1.0 × 10-3 S cm-1 at 20 °C, which renders TLPEC to be a suitable electrolyte for LIBs with enhanced safety performance. The LIBs, with TLPEC as the electrolyte, exhibited an excellent performance in terms of excellent rate capability, cycling stability, and high specific capacity at 25 and 60 °C, which were attributed to the stability and high ionic conductivity of TLPEC electrolyte during cycling as well as the excellent interface compatibility of TLPEC electrolyte with lithium anode.
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Project description:Lithium-ion batteries have been attracting much attention which enables the revolution of wireless global communication. Ionic liquids are regarded as promising candidates for lithium-ion battery electrolytes because they can overcome the limitations of high operating temperatures and flammability concerns of traditional electrolytes. However, at low temperatures they suffer from low ionic conductivity and phase transition. In this paper mixed electrolyte systems are described based on N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide (Pyr1,2O1TFSI) and lithium difluoro(oxalate)borate (LiODFB) lithium salt, with ethylene sulphite (ES) or dimethyl sulphite (DMS) as a cosolvent. The mixed electrolyte system exhibits good ion transport properties (a conductivity of 8.163 mS cm-1), a wide electrochemical window (5.2 V), non-flammability, the ability to form films to protect the anode and a large operating temperature range (-40 °C to 60 °C). We compare the performance and function of the new mixed electrolyte system with a variety of ionic liquid/cosolvent electrolyte systems developed in previous studies. The ring-chain synergy takes advantage of the availability of both high permittivities based on the ring-like components and low viscosities based on the chain-like components in the mixed electrolyte system and causes the electrolyte to exhibit a good overall performance in safety, ion transport and compatibility with electrodes.
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