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Aluminum-sulfur (Al-S) batteries are promising energy storage devices due to their high theoretical capacity, low cost, and high safety. However, the high viscosity and inferior ion transport of conventionally used ionic liquid electrolytes (ILEs) limit the kinetics of Al-S batteries, especially at sub-zero temperatures. Herein, locally concentrated ionic liquid electrolytes (LCILE) formed via diluting the ILEs with non-solvating 1,2-difluorobenzene (dFBn) co-solvent are proposed for wide-temperature-range Al-S batteries. The addition of dFBn effectively promotes the fluidity and ionic conductivity without affecting the AlCl4 - /Al2 Cl7 - equilibrium, which preserves the reversible stripping/plating of aluminum and further promotes the overall kinetics of Al-S batteries. As a result, Al-S cells employing the LCILE exhibit higher specific capacity, better cyclability, and lower polarization with respect to the neat ILE in a wide temperature range from -20 to 40 °C. For instance, Al-S batteries employing the LCILE sustain a remarkable capacity of 507â mAh g-1 after 300â cycles at 20 °C, while only 229â mAh g-1 is delivered with the dFBn-free electrolyte under the same condition. This work demonstrates the favorable use of LCILEs for wide-temperature Al-S batteries.
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A simple and scalable method to fabricate a novel high-energy asymmetric supercapacitor using tomato-leaf-derived hierarchical porous activated carbon (TAC) and electrochemically deposited polyaniline (PANI) for a battery-free heart-pulse-rate monitor is reported. In this study, TAC is prepared by simple pyrolysis, exhibiting nanosheet-type morphology and a high specific surface area of ≈1440 m2 g-1 , and PANI is electrochemically deposited onto carbon cloth. The TAC- and PANI- based asymmetric supercapacitor demonstrates an electrochemical performance superior to that of symmetric supercapacitors, delivering a high specific capacitance of 248 mF cm-2 at a current density of 1.0 mA cm-2 . The developed asymmetric supercapacitor shows a high energy density of 270 µWh cm-2 at a power density of 1400 µW cm-2 , as well as an excellent cyclic stability of ≈95% capacitance retention after 10 000 charging-discharging cycles while maintaining ≈98% Coulombic efficiency. Impressively, the series-connected asymmetric supercapacitors can operate a battery-free heart-pulse-rate monitor extremely efficiently upon solar-panel charging under regular laboratory illumination.
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The search for biocompatible and renewable materials for the next generation of energy devices has led to increasing interest in using biopolymers as a matrix component for the development of electric double-layer capacitors (EDLCs). However, using biopolymers as host matrices presents limitations in performance and scalability. At the same time, ionic liquids (ILs) have shown exceptional properties as non-aqueous electrolytes. This review intends to highlight the progress in integrating ILs and biopolymers for EDLC. While ILs have been used as solvents to process biopolymers and electrolyte materials, biopolymers have been utilized to provide novel chemistries of electrolyte materials via one of the following scenarios: (1) acting as host polymeric matrices for IL-support, (2) performing as polymeric fillers, and (3) serving as backbone polymer substrates for synthetic polymer grafting. Each of these scenarios is discussed in detail and supported with several examples. The use of biopolymers as electrode materials is another topic covered in this review, where biopolymers are used as a source of carbon or as a flexible support for conductive materials. This review also highlights current challenges in materials development, including improvements in robustness and conductivity, and proper dispersion and compatibility of biopolymeric and synthetic polymeric matrices for proper interface bonding.
Assuntos
Líquidos Iônicos , Líquidos Iônicos/química , Biopolímeros/química , Solventes , Polímeros/química , Eletrólitos/químicaRESUMO
This study investigates three carbide-derived carbon (CDC) materials (TiC, NbC, and Mo2C) characterized by uni-, bi-, and tri-modal pore sizes, respectively, for energy storage in both neat and acetonitrile-diluted 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. A distribution of micro- and mesopores was studied through low-temperature N2 and CO2 adsorption. To elucidate the relationships between porosity and the electrochemical properties of carbon materials, cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy measurements were conducted using three-electrode test cells. The ultramicroporous TiC-derived carbon is characterized by a high packing density of 0.85 g cm-3, resulting in superior cathodic and anodic capacitances for both neat ionic liquid (IL) and a 1.9 M IL/acetonitrile electrolyte (93.6 and 75.8 F cm-3, respectively, in the dilute IL). However, the bi-modal pore-sized microporous NbC-derived carbon, with slightly lower cathodic and anodic capacitances (i.e., 85.0 and 73.7 F cm-3 in the dilute IL, respectively), has a lower pore resistance, making it more suitable for real-world applications. A symmetric two-electrode capacitor incorporating microporous CDC-NbC electrodes revealed an acceptable cycle life. After 10,000 cycles, the cell retained approximately 75% of its original capacitance, while the equivalent series resistance (ESR) only increased by 13%.
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We investigated the performance of the computationally effective GFN2-xTB approach in molecular dynamics (MD) simulations of liquid electrolytes for lithium/sodium batteries. The studied systems were LiTFSI and NaTFSI solutions in ethylene carbonate or fluoroethylene carbonate and the neat solvents. We focused on the structure of the electrolytes and on the manifestations of ion-solvent interactions in the vibrational spectra. The IR spectra were calculated from MD trajectories as Fourier transforms of the dipole moment. The results were compared to the data obtained from ab initio MD. The spectral shifts of the carbonyl stretching mode calculated from the GFN2-xTB simulations were in satisfactory agreement with the ab initio MD data and the experimental results for similar systems. The performance in the region of molecular ring vibrations was significantly worse. We also found some differences in structural data, suggesting that the GFN2-xTB overestimates interactions of Me ions with TFSI anions and Na+ binding to solvent molecules. We conclude that the GFN2-xTB method is an alternative worth considering for MD simulations of liquids, but it requires testing of its applicability for new systems.
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Lithium metal is a promising anode material for next-generation high-energy-density batteries but suffers from low stripping/plating Coulombic efficiency and dendritic growth particularly at sub-zero temperatures. Herein, a poorly-flammable, locally concentrated ionic liquid electrolyte with a wide liquidus range extending well below 0 °C is proposed for low-temperature lithium metal batteries. Its all-anion Li+ solvation and phase-nano-segregation solution structure are sustained at low temperatures, which, together with a solid electrolyte interphase rich in inorganic compounds, enable dendrite-free operation of lithium metal anodes at -20 °C and 0.5â mA cm-2 , with a Coulombic efficiency of 98.9 %. As a result, lithium metal batteries coupling thin lithium metal anodes (4â mAh cm-2 ) and high-loading LiNi0.8 Co0.15 Al0.05 O2 cathodes (10â mg cm-2 ) retain 70 % of the initial capacity after 100â cycles at -20 °C. These results, as a proof of concept, demonstrate the applicability of locally concentrated ionic liquid electrolytes for low-temperature lithium metal batteries.
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Non-flammable ionic liquid electrolytes (ILEs) are well-known candidates for safer and long-lifespan lithium metal batteries (LMBs). However, the high viscosity and insufficient Li+ transport limit their practical application. Recently, non-solvating and low-viscosity co-solvents diluting ILEs without affecting the local Li+ solvation structure are employed to solve these problems. The diluted electrolytes, i.e., locally concentrated ionic liquid electrolytes (LCILEs), exhibiting lower viscosity, faster Li+ transport, and enhanced compatibility toward lithium metal anodes, are feasible options for the next-generation high-energy-density LMBs. Herein, the progress of the recently developed LCILEs are summarised, including their physicochemical properties, solution structures, and applications in LMBs with a variety of high-energy cathode materials. Lastly, a perspective on the future research directions of LCILEs to further understanding and achieve improved cell performances is outlined.
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Lithium batteries occupy the large-scale electric mobility market raising concerns about the environmental impact of cell production, especially regarding the use of poly(vinylidene difluoride) (teratogenic) and N-methyl-2-pyrrolidone (NMP, harmful). To avoid their use, an aqueous electrode processing route is utilized in which a water-soluble hybrid acrylic-fluoropolymer together with sodium carboxymethyl cellulose is used as binder, and a thin phosphate coating layer is in situ formed on the surface of the nickel-rich cathode during electrode processing. The resulting electrodes achieve a comparable performance to that of NMP-based electrodes in conventional organic carbonate-based electrolyte (LP30). Subsequently, an ionic liquid electrolyte (ILE) is employed to replace the organic electrolyte, building stable electrode/electrolyte interphases on the surface of the nickel-rich positive electrode (cathode) and metallic lithium negative electrode (anode). In such ILE, the aqueously processed electrodes achieve high cycling stability with a capacity retention of 91% after 1000 cycles (20 °C). In addition, a high capacity of more than 2.5 mAh cm-2 is achieved for high loading electrodes (≈15 mg cm-2 ) by using a modified ILE with 5% vinylene carbonate additive. A path to achieve environmentally friendly electrode manufacturing while maintaining their outstanding performance and structural integrity is demonstrated.
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The development of polymer electrolytes (PEs) is crucial for advancing safe, high-energy density batteries, such as lithium-metal and other beyond lithium-ion chemistries. However, reaching the optimum balance between mechanical stiffness and ionic conductivity is not a straightforward task. Zwitterionic (ZI) gel electrolytes comprising lithium salt and ionic liquid (IL) solutions within a fully ZI polymer network can, in this context, provide useful properties. Although such materials have shown compatibility with lithium metal in batteries, several fundamental structure-dynamic relationships regarding ionic transport and the Li+ coordination environment remain unclear. To better resolve such issues, molecular dynamics simulations were carried out for two IL-based electrolyte systems, N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP][TFSI]) with 1 M LiTFSI salt and a ZI gel electrolyte containing the IL and a ZI copolymer: poly(2-methacryloyloxyethyl phosphorylcholine-co-sulfobetaine vinylimidazole), poly(MPC-co-SBVI). The addition of ZI polymer decreases the [TFSI]- -[Li]+ interactions and increases the IL ion diffusivities, and consequently, the overall ZI gel ionic conductivity. The structural analyses showed a large preference for lithium-ion interactions with the polymer phosphonate groups, while the [TFSI]- anions interact directly with the sulfonate group and the [BMP]+ cations only display secondary interactions with the polymer. In contrast to previous experimental data on the same system, the simulated transference numbers showed smaller [Li]+ contributions to the overall ionic conductivities, mainly due to negatively charged lithium aggregates and the strong lithium-ion interactions in the systems.
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The dielectric constant is a crucial physicochemical property of liquids in tuning solute-solvent interactions and solvation microstructures. Herein the dielectric constant variation of liquid electrolytes regarding to temperatures and electrolyte compositions is probed by molecular dynamics simulations. Dielectric constants of solvents reduce as temperatures increase due to accelerated mobility of molecules. For solvent mixtures with different mixing ratios, their dielectric constants either follow a linear superposition rule or satisfy a polynomial function, depending on weak or strong intermolecular interactions. Dielectric constants of electrolytes exhibit a volcano trend with increasing salt concentrations, which can be attributed to dielectric contributions from salts and formation of solvation structures. This work affords an atomic insight into the dielectric constant variation and its chemical origin, which can deepen the fundamental understanding of solution chemistry.
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Stable operation at elevated temperature is necessary for lithium metal anode. However, Li metal anode generally has poor performance and safety concerns at high temperature (>55 °C) owing to the thermal instability of the electrolyte and solid electrolyte interphase in a routine liquid electrolyte. Herein a Li metal anode working at an elevated temperature (90 °C) is demonstrated in a thermotolerant electrolyte. In a Li|LiFePO4 battery working at 90 °C, the anode undergoes 100 cycles compared with 10â cycles in a practical carbonate electrolyte. During the formation of the solid electrolyte interphase, independent and incomplete decomposition of Li salts and solvents aggravate. Some unstable intermediates emerge at 90 °C, degenerating the uniformity of Li deposition. This work not only demonstrates a working Li metal anode at 90 °C, but also provides fundamental understanding of solid electrolyte interphase and Li deposition at elevated temperature for rechargeable batteries.
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Lithium-air batteries are promising devices for electrochemical energy storage because of their ultrahigh energy density. However, it is still challenging to achieve practical Li-air batteries because of their severe capacity fading and poor rate capability. Electrolytes are the prime suspects for cell failure. In this Review, we focus on the opportunities and challenges of electrolytes for rechargeable Li-air batteries. A detailed summary of the reaction mechanisms, internal compositions, instability factors, selection criteria, and design ideas of the considered electrolytes is provided to obtain appropriate strategies to meet the battery requirements. In particular, ionic liquid (IL) electrolytes and solid-state electrolytes show exciting opportunities to control both the high energy density and safety.
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With ever-increasing efforts focused on basic research of sodium-ion batteries (SIBs) and growing energy demand, sodium-ion full cells (SIFCs), as unique bridging technology between sodium-ion half-cells (SIHCs) and commercial batteries, have attracted more and more interest and attention. To promote the development of SIFCs in a better way, it is essential to gain a systematic and profound insight into their key issues and research status. This Review mainly focuses on the interface issues, major challenges, and recent progresses in SIFCs based on diversified electrolytes (i.e., nonaqueous liquid electrolytes, quasi-solid-state electrolytes, and all-solid-state electrolytes) and summarizes the modification strategies to improve their electrochemical performance, including interface modification, cathode/anode matching, capacity ratio, electrolyte optimization, and sodium compensation. Outlooks and perspectives on the future research directions to build better SIFCs are also provided.
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We present an experimental approach for in situ measurement of elastic modulus of the solid electrolyte interphase (SEI), which is formed from reactions between a lithium thin-film [on a polydimethylsiloxane (PDMS) substrate] and a room-temperature ionic liquid (RTIL) electrolyte. The SEI forms under a state of compressive stress, which causes buckling of the sample surface. In situ atomic force microscopy is used to measure the dominant wavelength of the wrinkled surface topography. A mechanics analysis of strain-induced elastic buckling instability of a stiff thin film on a soft substrate is used to determine the plane strain modulus of the SEI from the measured wavelength. The measurements are performed for three RTIL electrolytes: 1-butyl 1-methylpiperidinium bis(trifluoromethylsulfonyl)imide (P14 TFSI) without any lithium salt, 1.0 M lithium bis(trifluoromethylsulfonyl)imide (Li TFSI) in P14 TFSI, and 1.0 M lithium bis(fluorosulfonyl)imide (Li FSI) in P14 TFSI to investigate the influence of lithium salts on the plane strain modulus of the SEI. The measurements yield plane-strain moduli of approximately 1.3 GPa for no-salt P14 TFSI and approximately 1.6 GPa for 1.0 M Li TFSI in P14 TFSI and 1.0 M Li FSI in P14 TFSI. The experimental technique presented here eliminates some of the uncertainties associated with traditional SEI mechanical characterization approaches and offers a platform to engineer an SEI with desired mechanical properties by approaches that include altering the electrolyte composition.
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The electrochemical performance of the aluminum-sulfur (Al-S) battery has very poor reversibility and a low charge/discharge current density owing to slow kinetic processes determined by an inevitable dissociation reaction from Al2 Cl7- to free Al3+ . Al2 Cl6 Br- was used instead of Al2 Cl7- as the dissociation reaction reagent. A 15-fold faster reaction rate of Al2 Cl6 Br- dissociation than that of Al2 Cl7- was confirmed by density function theory calculations and the Arrhenius equation. This accelerated dissociation reaction was experimentally verified by the increase of exchange current density during Al electro-deposition. Using Al2 Cl6 Br- instead of Al2 Cl7- , a kinetically accelerated Al-S battery has a sulfur utilization of more than 80 %, with at least four times the sulfur content and five times the current density than that of previous work.
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Sodium-ion batteries (SIBs) have been recognized as one of the most promising new energy storage devices for their rich sodium resources, low cost and high safety. The electrolyte, as a bridge connecting the cathode and anode electrodes, plays a vital role in determining the performance of SIBs, such as coulombic efficiency, energy density and cycle life. Therefore, the overall performance of SIBs could be significantly improved by adjusting the electrolyte composition or adding a small number of functional additives. In this review, the fundamentals of SIB electrolytes including electrode-electrolyte interface and solvation structure are introduced. Then, the mechanisms of electrolyte additive action on SIBs are discussed, with a focus on film-forming additives, flame-retardant additives and overcharge protection additives. Finally, the future research of electrolytes is prospected from the perspective of scientific concepts and practical applications.
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The behaviour and compatibility of monoclinic sodium manganite, α-NaMnO2, cathodes at the interface with electrolytes based on the 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIFSI) and N-trimethyl-N-butylammonium bis(fluorosulfonyl)imide (N1114FSI) ionic liquids is presented and discussed. The Na+ insertion process was analysed through cyclic voltammetry tests combined with impedance spectroscopy measurements and the cell performance was tested by charge-discharge cycles. XPS and FIB-SEM measurements allowed analysis of the surface composition and the morphology of post-mortem cathodes. Overall, the α-NaMnO2 cathode showed high reversibility in N1114FSI-based electrolyte, delivering 60 % of the initial capacity after 1200 cycles in conjunction with a Coulombic efficiency above 99 %. To our knowledge, these very promising results are the best result obtained till now for monolithic α-NaMnO2 cathodes, are ascribable to the formation of a stable passive layer onto the electrode surface, as confirmed by spectroscopic analysis.
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Herein, we review notable points from observations of electrochemical reactions in a liquid electrolyte by liquid-phase electron microscopy. In situ microscopic observations of electrochemical reactions are urgently required, particularly to solve various battery issues. Battery performance is evaluated by various electrochemical measurements of bulk samples. However, it is necessary to understand the physical/chemical phenomena occurring in batteries to elucidate the reaction mechanisms. Thus, in situ microscopic observation is effective for understanding the reactions that occur in batteries. Herein, we focus on two methods, of the liquid phase (scanning) transmission electron microscopy and liquid phase scanning electron microscopy, and summarize the advantages and disadvantages of both methods.
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Lewis acid-base interactions are common in chemical processes presented in diverse applications, such as synthesis, catalysis, batteries, semiconductors, and solar cells. The Lewis acid-base interactions allow precise tuning of material properties from the molecular level to more aggregated and organized structures. This review will focus on the origin, development, and prospects of applying Lewis acid-base interactions for the materials design and mechanism understanding in the advancement of battery materials and chemistries. The covered topics relate to aqueous batteries, lithium-ion batteries, solid-state batteries, alkali metal-sulfur batteries, and alkali metal-oxygen batteries. In this review, the Lewis acid-base theories will be first introduced. Thereafter the application strategies for Lewis acid-base interactions in solid-state and liquid-based batteries will be introduced from the aspects of liquid electrolyte, solid polymer electrolyte, metal anodes, and high-capacity cathodes. The underlying mechanism is highlighted in regard to ion transport, electrochemical stability, mechanical property, reaction kinetics, dendrite growth, corrosion, and so on. Last but not least, perspectives on the future directions related to Lewis acid-base interactions for next-generation batteries are like to be shared.
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Potassium metal batteries (PMBs) show great potential as next-generation energy storage systems yet face challenges such as the dendritic growth of the potassium anode, leading to issues with cycle life and safety. This study reports a potassium salt-concentrated ionic liquid electrolyte (PCIL) consisting of potassium bis(fluorosulfonyl)imide (KFSI) and 1-methyl-1-propyl pyrrolidinium bis(fluorosulfonyl)imide (Pyr13FSI) to achieve long-life and, safe PMBs. PCIL presents several advantages including outstanding oxidation stability (≈5.2 V), decent ionic conductivity (4.0 mS cm-1 at 25 °C), and negligible flammability. Moreover, PCIL promotes the development of anion-derived solid-electrolyte interphase (SEI) with high inorganic content. This not only hinders the growth of potassium dendrites but also facilitates facile interfacial charge transfer kinetics. Benefiting from these advantages, PMBs (K||KVPO4F) employing PCIL exhibit remarkable cycle performances at both ambient and elevated temperatures (capacity retention after 300 cycles: 74.8% at 25 °C and 82.9% at 45 °C), surpassing the performance of conventional carbonate (1 M KPF6 EC/PC) and dilute potassium ionic liquid electrolyte (PIL). This work demonstrates the tangible capability of PCIL in realizing practical PMBs.