RESUMO
While the formation of an inorganic-rich solid electrolyte interphase (SEI) plays a crucial role, the persistent challenge lies in the formation of an organic-rich SEI due to the high solvent ratio in low-concentration electrolytes (LCEs), which hinders the achievement of high-performance lithium metal batteries. Herein, by incorporating di-fluoroethylene carbonate (DFEC) as a non-solvating cosolvent, a solvation structure dominated by anions is introduced in the innovative LCE, leading to the creation of a durable and stable inorganic-rich SEI. Leveraging this electrolyte design, the Li||NCM83 cell demonstrates exceptional cycling stability, maintaining 82.85% of its capacity over 500 cycles at 1 C. Additionally, Li||NCM83 cell with a low N/P ratio (≈2.57) and reduced electrolyte volume (30 µL) retain 87.58% of its capacity after 150 cycles at 0.5 C. Direct molecular information is utilized to reveal a strong correlation between solvation structures and reduction sequences, proving the anion-dominate solvation structure can impedes the preferential reduction of solvents and constructs an inorganic-rich SEI. These findings shed light on the pivotal role of solvation structures in dictating SEI composition and battery performance, offering valuable insights for the design of advanced electrolytes for next-generation lithium metal batteries.
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Sodium dual-ion batteries (Na-DIBs) have attracted increasing attention due to their high operative voltages and low-cost raw materials. However, the practical applications of Na-DIBs are still hindered by the issues, such as low capacity and poor Coulombic efficiency, which is highly correlated with the compatibility between electrode and electrolyte but rarely investigated. Herein, fluoroethylene carbonate (FEC) is introduced into the electrolyte to regulate cation/anion solvation structure and the stability of cathode/anode-electrolyte interphase of Na-DIBs. The FEC modulates the environment of PF6 - solvation sheath and facilitates the interaction of PF6 - on graphite. In addition, the NaF-rich interphase caused by the preferential decomposition of FEC effectively inhibits side reactions and pulverization of anodes with the electrolyte. Consequently, Sb||graphite full cells in FEC-containing electrolyte achieve an improved capacity, cycling stability and Coulombic efficiency. This work elucidates the underlying mechanism of bifunctional FEC and provides an alternative strategy of building high-performance dual ion batteries.
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Solid polymer electrolytes based on plastic crystals are promising for solid-state sodium metal (Na0) batteries, yet their practicality has been hindered by the notorious Na0-electrolyte interface instability issue, the underlying cause of which remains poorly understood. Here, by leveraging a model plasticized polymer electrolyte based on conventional succinonitrile plastic crystals, we uncover its failure origin in Na0 batteries is associated with the formation of a thick and non-uniform solid electrolyte interphase (SEI) and whiskery Na0 nucleation/growth. Furthermore, we design a new additive-embedded plasticized polymer electrolyte to manipulate the Na0 deposition and SEI formulation. For the first time, we demonstrate that introducing fluoroethylene carbonate (FEC) additive into the succinonitrile-plasticized polymer electrolyte can effectively protect Na0 against interfacial corrosion by facilitating the growth of dome-like Na0 with thin, amorphous, and fluorine-rich SEIs, thus enabling significantly improved performances of Na//Na symmetric cells (1,800â h at 0.5â mA cm-2) and Na//Na3V2(PO4)3 full cells (93.0 % capacity retention after 1,200 cycles at 1â C rate in coin cells and 93.1 % capacity retention after 250 cycles at C/3 in pouch cells at room temperature). Our work provides valuable insights into the interfacial failure of plasticized polymer electrolytes and offers a promising solution to resolving the interfacial instability issue.
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The practical implementation of high-voltage lithium-rich manganese oxide (LRMO) cathode is limited by the unanticipated electrolyte decomposition and dissolution of transition metal ions. The present study proposes a bi-affinity electrolyte formulation, wherein the sulfonyl group of ethyl vinyl sulfone (EVS) imparts a highly adsorptive nature to LRMO, while fluoroethylene carbonate (FEC) exhibits a reductive nature towards Li metal. This interface modulation strategy involves the synergistic use of EVS and FEC as additives to form robust interphase layers on the electrode. As-formed S-endorsed but LiF-assisted configuration cathode electrolyte interphase with a more dominant -SO2 - component may promote the interface transport kinetics and prevent the dissolution of transition metal ions. Furthermore, the incorporation of S component into the solid electrolyte interphase and the reduction of its poorly conducting component can effectively inhibit the growth of lithium dendrites. Therefore, a 4.8â V LRMO/Li cell with optimized electrolyte may demonstrate a remarkable retention capacity of 97 % even after undergoing 300â cycles at 1â C.
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Concentration of electrolyte has significant effects on performances of rechargeable batteries. Previous studies mainly focused on concentrated electrolytes. So far, only several recipes on low-concentration electrolytes were studied, performing enhanced performance in advanced rechargeable batteries. Here, based on common electrolyte components, a low-concentration electrolyte composed of 0.2â M lithium hexafluorophosphate (LiPF6 ) solvated in fluoroethylene carbonate (FEC) and ethyl methyl carbonate (EMC) is employed for high-voltage Li metal battery. The synergistic working mechanisms of introducing fluorine-containing solvent in the solvated structure and low salt concentration effect are revealed, resulting in LiF-rich, uniform, and robust solid electrolyte interphase layer and fewer unfavorable decomposition products. As a result, this low-concentration electrolyte significantly enhances electrochemical performances of Li||Li symmetric cells and high-voltage LiCoO2 ||Li batteries.
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Lithium primary batteries are still widely used in military, aerospace, medical, and civilian applications despite the omnipresence of rechargeable Li-ion batteries. However, these current primary chemistries are exclusively based on inorganic materials with high cost, low energy density or severe safety concerns. Here, a novel lithium-organic primary battery chemistry that operates through a synergetic reduction of 9,10-anthraquinone (AQ) and fluoroethylene carbonate (FEC) is reported. In FEC-presence, the equilibrium between the carbonyl and enol structures is disabled, and replaced by an irreversible process that corresponds to a large capacity along with methylene and inorganic salts (such as LiF, Li2 CO3 ) generated as products. This irreversible chemistry of AQ yields a high energy density of 1300 Wh/(kg of AQ) at a stable discharge voltage platform of 2.4 V as well as high rate capability (up to 313 mAh g-1 at a current density of 1000 mA g-1 ), wide temperature range of operation (-40 to 40 °C) and low self-discharge rate. Combined with the advantages of low toxicity, facile and diverse synthesis methods, and easy accessibility of AQ, Li-organic primary battery chemistry promises a new battery candidate for applications that requires low cost, high environmental friendliness, and high energy density.
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As a high-capacity anode for lithium-ion batteries (LIBs), MoS2 suffers from short lifespan that is due in part to its unstable solid electrolyte interphase (SEI). The cycle life of MoS2 can be greatly extended by manipulating the SEI with a fluoroethylene carbonate (FEC) additive. The capacity of MoS2 in the electrolyte with 10â wt % FEC stabilizes at about 770â mAh g-1 for 200 cycles at 1â A g-1 , which far surpasses the FEC-free counterpart (ca. 40â mAh g-1 after 150 cycles). The presence of FEC enables a robust LiF-rich SEI that can effectively inhibit the continual electrolyte decomposition. A full cell with a LiNi0.5 Co0.3 Mn0.2 O2 cathode also gains improved performance in the FEC-containing electrolyte. These findings reveal the importance of controlling SEI formation on MoS2 toward promoted lithium storage, opening a new avenue for developing metal sulfides as high-capacity electrodes for LIBs.
RESUMO
Anovel lithiated Si-S battery exploiting an optimized solid-like electrolyte is presented. This electrolyte is fabricated by integrating ether-based liquid electrolyte with SiO2 hollow nanosphere layer to suppress the shuttle effect and fluoroethylene carbonate additive to optimize the anodic solid electrolyte interface. The prepared lithiated Si-S batteries exhibit enhanced cycle life, low flammability, and strong recovery ability against short-circuit.
RESUMO
The development of advanced liquid electrolytes for high-voltage/high-energy rechargeable Li metal batteries is an important strategy to attain an effective protective surface film on both the Li metal anode and the high-voltage composite cathode. Herein, we report a study of two CF3-substituted ethylene carbonates as components of the electrolyte solutions for Li metal|NCM811 cells. We evaluated trifluoromethyl ethylene carbonate (CF3-EC) and trans-ditrifluoromethylethylene carbonate Di-(CF3)-EC as cosolvents and additives to the electrolyte solutions. Using CF3-substituted ethylene carbonates as additives to a fluoroethylene carbonate (FEC)-based electrolyte solution enables improved capacity retention of high-power Li metal|NCM811 cells. The composition of the products from the transformations of CF3-EC and Di-(CF3)-EC in Li|NCM811 cells was studied by FTIR, XPS, and 19F NMR spectroscopy. We concluded that fluorinated Li alkyl carbonates are the main reaction products formed from these cyclic carbonates during the cycling of Li|NCM 811 cells, and fragmentation of the ring with the formation of CO2, CO, or olefins is not characteristic of CF3-substituted ethylene carbonates. The NCM 811 cathodes and Li metal anodes were characterized by X-ray diffraction, SEM, XPS, and FTIR spectroscopy. The role of CF3-substituted ethylene carbonate additives in stabilizing high energy density secondary batteries based on Li metal anodes was discussed. A bright horizon for developing sustainable rechargeable batteries with the highest possible energy density is demonstrated.
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Sodium-ion and potassium-ion batteries (NIBs and KIBs) are considered promising alternatives to replace lithium-ion batteries (LIBs) in energy storage applications due to the natural abundance and low cost of Na and K. Nevertheless, a critical challenge is that the large size of Na+ /K+ leads to a huge volume change of the hosting material during electrochemical cycling, resulting in rapid capacity decay. Among negative candidates for alkali-metal-ion batteries, SnS2 is attractive due to the competitively high specific capacity, low redox potential and high abundance. Porous few-layer SnS2 nanosheets are inâ situ grown on reduced graphene oxide, forming a SnS2 -rGO sandwich structure via strong C-O-Sn bonds. This nano-scaled sandwich structure not only shortens Na+ /K+ and electron transport pathways but also accommodates volume expansion, thereby enabling high and stable electrochemical cycling performance of SnS2 -rGO. This work explores the influence of different conductive carbons (Superâ P and C65) on the SnS2 -rGO electrode. In addition, the effects of the electrolyte additive fluoroethylene carbonate (FEC) on the electrochemical performance in NIBs and KIBs is evaluated. This work provides guidelines for optimized electrode structure design, electrolyte additives and carbon additives for the realization of better NIBs and KIBs.
RESUMO
The film-forming electrolyte additive/co-solvent fluoroethylene carbonate (FEC) can play a crucial role in enabling high-energy-density lithium metal batteries (LMBs). Its beneficial impact on homogeneous and compact lithium (Li) deposition morphology leads to improved Coulombic efficiency (CE) of the resulting cell chemistry during galvanostatic cycling and consequently an extended cell lifetime. Herein, the impact of this promising additive/co-solvent on selected properties of LMBs is systematically investigated by utilizing an in-house developed lithium pretreatment method. The results reveal that as long as FEC is present in the organic carbonate-based electrolyte, a dense mosaic-like lithium morphology of Li deposits with a reduced polarization of only 20 mV combined with a prolonged cycle life is achieved. When the pretreated Li electrodes with an FEC-derived preformed SEI (pSEI) are galvanostatically cycled with the FEC-free electrolyte, the described benefits induced by the additive are not observable. These results underline that the favorable properties of the FEC-derived SEI are beneficial only if there is unreacted FEC in the electrolyte formulation left to constantly reform the interphase layer, which is especially important for anodes with high-volume changes and dynamic surfaces like lithium metal and lithiated silicon.
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Although gel polymer electrolytes (GPEs) represent a promising candidate to address the individual limitations of liquid and solid electrolytes, their extensive development is still hindered due to the veiled Li-ion conduction mechanism. Herein, the related mechanism in GPEs is extensively studied by developing an in situ polymerized GPE comprising fluoroethylene carbonate (FEC) solvent and carbonate ester segments (F-GPE). Practically, although with high dielectric constant, FEC fails to effectively transport Li ions when acting as the sole solvent. By sharp contrast, F-GPE demonstrates superior electrochemical performances, and the related Li-ion transfer mechanism is investigated using molecular dynamics simulations and 7 Li/6 Li solid-state nNMR spectroscopy. The polymer segments are extended with the swelling of FEC, then an electron-delocalization interface layer is generated between abundant electron-rich groups of FEC and the polymer ingredients, which works as an electron-rich "Milky Way" and facilitates the rapid transfer of Li ions by lowering the diffusion barrier dramatically, resulting in a high conductivity of 2.47 × 10-4 S cm-1 and a small polarization of about 20 mV for Li//Li symmetric cell after 8000 h. Remarkably, FEC provides high flame-retardancy and makes F-GPE remains stable under ignition and puncture tests.
Assuntos
Eletrólitos , Compostos de Vinila , Carbonatos , Géis , Lítio , PolímerosRESUMO
Composite solid electrolytes (CSEs) are considered crucial materials for next-generation solid-state lithium batteries with high energy density and reliable safety, and they make full use of the advantages of both organic and inorganic solid-state electrolytes. However, few CSEs have sufficiently high ionic conductivity at room temperature for practical applications. Here, a traditional CSE consisting of poly(ethylene oxide) (PEO) matrix and Li1.3Al0.3Ti1.7(PO4)3 (LATP) fillers was optimized by introducing a fluoroethylene carbonate (FEC) additive, resulting in an improved high ionic conductivity of 1.99 × 10-4 S cm-1 at 30 °C. The symmetric Li||Li cell assembled with the optimized CSE exhibited a low overpotential and a good cycling stability of more than 1500 h at room temperature. Moreover, the Li||LiFePO4 battery with the optimized CSE delivered a discharge capacity of 132 mAh g-1 at 0.2 C after 300 cycles at room temperature. Comparisons between the LATP-containing CSE and control electrolytes indicated that the enhanced ion conductivity of the former resulted from the synergistic effect of LATP and FEC. Comprehensive characterizations and DFT calculations suggest that with the presence of LATP, FEC additives in the precursor could transform into some other species in the preparation process of CSE. It is believed that these FEC-derived species improve the ion conductivity of the CSEs. The results reported here may open up new approaches to developing composite electrolytes with high ionic conductivity at room temperature by introducing organic additives in the precursor and converting them into species that facilitate ion conduction in the CSE preparation process.
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Because of the abundance and cost effectiveness of sodium, rechargeable sodium metal batteries have been widely studied to replace current lithium-ion batteries. However, there are some critical unresolved issues including the high reactivity of sodium, an unstable solid-electrolyte interphase (SEI), and sodium dendrite formation. While several studies have been conducted to understand sodium plating/stripping processes, only a very limited number of studies have been carried out under operando conditions. We have employed operando X-ray and optical imaging techniques to understand the mechanistic behavior of Na metal plating. The morphology of sodium metal plated on a copper electrode depends strongly on the salts and solvents used in the electrolyte. The addition of a fluorine-containing additive to a carbonate-based electrolyte, NaClO4 in propylene carbonate (PC):fluoroethylene carbonate (FEC), results in uniform sodium plating processes and much more stable cycling performance, compared to NaClO4 in PC, because of the formation of a stable SEI containing NaF. A NaF layer, on top of the sodium metal, leads to a much more uniform deposition of sodium and greatly enhanced cyclability.
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Nickel-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) with respect to Li metal can enhance the energy density of lithium batteries effectively. However, the unstable Li deposition, together with the dissolution and migration of transition metal (TM) ions toward the anode deteriorate the cycle performance of NCM811||Li battery, especially when commercial carbonate electrolyte is used. Herein, tris(trimethylsilyl)phosphite (TMSPi) and fluoroethylene carbonate (FEC) are used to construct a dual-additive electrolyte, by which both electrodes can be protected. It is found that TMSPi can be preferentially adsorbed on the cathode surface through its strong coordination with Ni4+, playing the role as a HF scavenger and suppressing TM ions dissolution, as well as mitigating the structural degradation of the cathode effectively. When it comes to the lithium anode, the presence of TMSPi may lead to side reactions with Li metal, accompanied by fast dendrite growth. The introduction of FEC could facilitate the formation of stable electrode/electrolyte interfaces on both sides. Particularly, reduce the direct contact between TMSPi and Li anode, thus ameliorate the incompatibility issue. Consequently, the NCM811||Li cell with dual-additive demonstrates excellent capacity retention of 81.2% after 500 cycles at 1 C rate. As a sharp contrast, it only retains 13.9% in the one with blank electrolyte. The findings of this work provide a new insight into enhancing the cycle performance of NCM811||Li system via the synergistic effect between additives.
RESUMO
This work investigated the possibility of increasing the cycle life and rate capability of silicon anodes, made of macroporous membranes, by adding fluoroethylene carbonate (FEC) to the complex commercial electrolyte. It was found that FEC leads to a decrease in the degradation rate; for a sample without FEC addition, the discharge capacity at the level of Qdch = 1000 mAh/g remained unchanged for 220 cycles and the same sample with 3% FEC added to the electrolyte remained unchanged for over 600 cycles. FEC also improves the power characteristics of the anodes by 5-18%. Studies of impedance hodographs showed that in both electrolytes (with 0% and 3% FEC, respectively) the charge transfer resistance grows with an increasing number of cycles, while Solid Electrolyte Interphase (SEI) parameters, such as its resistance and capacitance, show little change. However, the addition of FEC more than halves the overall system impedance and reduces the resistance of the liquid electrolyte and all current carrying parts as well as the SEI film and charge transfer resistances.
RESUMO
Lithium metal anodes are promising for their high energy density and low working potential. However, high reactivity and dendrite growth of lithium metal lead to serious safety issues. Lithium dendrite may form "dead lithium" or pierce the separator, which will cause low efficiency and short-circuit inside the battery. A nonflammable phosphate-based electrolyte can effectively solve the flammability problem. Also, it shows poor compatibility with lithium metal anodes, resulting in an unstable solid electrolyte interface (SEI), which leads to dendrite growth and poor electrochemical performance. In this study, trimethyl phosphate is used to ensure the safety of lithium metal batteries. By adjusting the concentration of lithium salt and introducing fluoroethylene carbonate, a stable SEI layer is formed on the surface of the lithium metal anode and dendrite growth of the lithium metal anode is inhibited. Lithium metal batteries with a modified electrolyte achieved stable electrochemical plating/stripping, and the full cell has 93.4% capacity left and the coulombic efficiency is nearly 100%. In addition, the modified electrolyte can also enable reversible intercalation and de-intercalation of Li+ in the commercial graphite anode. This work may provide an alternative direction for the development of lithium metal batteries with high safety and high energy density.
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While Li-ion is the prevailing commercial battery chemistry, the development of batteries that use earth-abundant alkali metals (e.g., Na and K) alleviates reliance on Li with potentially cheaper technologies. Electrolyte engineering has been a major thrust of Li-ion battery (LIB) research, and it is unclear if the same electrolyte design principles apply to K-ion batteries (KIBs). Fluoroethylene carbonate (FEC) is a well-known additive used in Li-ion electrolytes because the products of its sacrificial decomposition aid in forming a stable solid electrolyte interphase (SEI) on the anode surface. Here, we show that FEC addition to KIBs containing hard carbon anodes results in a dramatic decrease in capacity and cell failure in only two cycles, whereas capacity retention remains high (> 90% over 100 cycles at C/10 for both KPF6 and KFSI) for electrolytes that do not contain FEC. Using a combination of 19F solid-state nuclear magnetic resonance (SSNMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS), we show that FEC decomposes during galvanostatic cycling to form insoluble KF and K2CO3 on the anode surface, which correlates with increased interfacial resistance in the cell. Our results strongly suggest that KIB performance is sensitive to the accumulation of an inorganic SEI, likely due to poor K transport in these compounds. This mechanism of FEC decomposition was confirmed in two separate electrolyte formulations using KPF6 or KFSI. Interestingly, the salt anions do not decompose themselves, unlike their Li analogues. Insight from these results indicates that electrolyte decomposition pathways and favorable SEI components are significantly different in KIBs and LIBs, suggesting that entirely new approaches to KIB electrolyte engineering are needed.
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A key issue in the development of sustainable Na-ion batteries (NIBs) is the stability of the electrolyte solution and its ability to form effective passivation layers on both cathode and anode. In this regard, the use of fluorine-based additives is considered a promising direction for improving electrode performance. Fluoroethylene carbonate (FEC) and trans-difluoroethylene carbonate (DFEC) were demonstrated as additives or cosolvents that form effective passivating surface films in Li-ion batteries. Their effect is evaluated for the first time with cathodes in NIBs. By application of systematic electrochemical and postmortem investigations, the role of fluorinated additives in the good performance of Na0.44MnO2 (NMO) cathodes was deciphered. Despite the significant improvement in the performance of Li-ion cells enabled by the use of FEC and FEC + DFEC, the highest stability for NIBs was observed when only FEC was used as an additive. Mechanistic insights and analytical characterizations were carried out to shed light on the inferior effect of FEC + DFEC in NIBs, in contrast to its positive effect on the stability of Li-ion batteries.
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This study examines the compatibility of multielectrolyte additives for NMC-silicon lithium-ion batteries. Research studies with Si-based anodes have shown stable reversible cycling using electrolytes containing fluoroethylene carbonate (FEC). At the same time, the electrolyte additive, tris(trimethylsilyl) phosphite (TTMSP), has shown to improve the electrochemical performance of nickel-rich layered cathodes, such as LiNi0.5Mn0.3Co0.2O2 (NMC). However, the combination of these electrolyte additives for the realization of a full-cell NMC-Si lithium-ion battery has not been previously explored. Changes in the electrochemical performance (capacity retention, internal cell resistance, and electrochemical impedance) in half-cells are studied as the ratio of TTMSP and FEC is tuned. At the optimal TTMSP/FEC ratio of 0.33 (T1F3), the NMC-Si full-cells achieve a 2× longer cycle life when compared to the FEC-rich (T0F4) electrolyte. Moreover, T1F3 full-cells demonstrate 1.5 mAh/cm2 areal capacities and high-capacity retention (25% more than T0F4). A detailed investigation of the electrode-electrolyte interfaces is conducted by using time-of-flight secondary ion mass spectroscopy (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS). The chemical species depth profiles and elemental analysis illustrate adequate hydrogen fluoride (HF) scavenging. These results demonstrate the synergistic effects of electrolyte additives in minimizing the capacity degradation in NMC-Si full-cells by effectively stabilizing the electrode-electrolyte interfaces.