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1.
Narrow electrochemical stability window (1.23 V) of aqueous electrolytes is always considered the key obstacle preventing aqueous sodium‐ion chemistry of practical energy density and cycle life. The sodium‐ion water‐in‐salt electrolyte (NaWiSE) eliminates this barrier by offering a 2.5 V window through suppressing hydrogen evolution on anode with the formation of a Na+‐conducting solid‐electrolyte interphase (SEI) and reducing the overall electrochemical activity of water on cathode. A full aqueous Na‐ion battery constructed on Na0.66[Mn0.66Ti0.34]O2 as cathode and NaTi2(PO4)3 as anode exhibits superior performance at both low and high rates, as exemplified by extraordinarily high Coulombic efficiency (>99.2%) at a low rate (0.2 C) for >350 cycles, and excellent cycling stability with negligible capacity losses (0.006% per cycle) at a high rate (1 C) for >1200 cycles. Molecular modeling reveals some key differences between Li‐ion and Na‐ion WiSE, and identifies a more pronounced ion aggregation with frequent contacts between the sodium cation and fluorine of anion in the latter as one main factor responsible for the formation of a dense SEI at lower salt concentration than its Li cousin.  相似文献   

2.
The insulating nature of sulfur, polysulfide shuttle effect, and lithium‐metal deterioration cause a decrease in practical energy density and fast capacity fade in lithium‐sulfur (Li‐S) batteries. This study presents an integrated strategy for the development of hybrid Li‐S batteries based on a gel sulfur cathode, a solid electrolyte, and a protective anolyte composed of a highly concentrated salt electrolyte containing mixed additives. The dense solid electrolyte completely blocks polysulfide diffusion, and also makes it possible to investigate the cathode and anode independently. This gel cathode effectively traps the polysulfide active material while maintaining a low electrolyte to sulfur ratio of 5.2 mL g?1. The anolyte effectively protects the Li metal and suppresses the consumption of liquid electrolyte, enabling stable long‐term cycling for over 700 h in Li symmetric cells. This advanced design can simultaneously suppress the polysulfide shuttle, protect Li metal, and reduce the liquid electrolyte usage. The assembled hybrid batteries exhibit remarkably stable cycling performance over 300 cycles with high capacity. Finally, surface‐sensitive techniques are carried out to directly visualize and probe the interphase formed on the surface of the Li1.5Al0.5Ge1.5(PO4)3 (LAGP) pellet, which may help stabilize the solid–liquid interface.  相似文献   

3.
Aqueous lithium/sodium‐ion batteries (AIBs) have received increasing attention because of their intrinsic safety. However, the narrow electrochemical stability window (1.23 V) of the aqueous electrolyte significantly hinders the development of AIBs, especially the choice of electrode materials. Here, an aqueous electrolyte composed of LiClO4, urea, and H2O, which allows the electrochemical stability window to be expanded to 3.0 V, is developed. Novel [Li (H2O)x(organic)y]+ primary solvation sheath structures are developed in this aqueous electrolyte, which contribute to the formation of solid–electrolyte interface layers on the surfaces of both the cathode and anode. The expanded electrochemical stability window enables the construction of full aqueous Li‐ion batteries with LiMn2O4 cathodes and Mo6S8 anodes, demonstrating an operating voltage of 2.1 V and stability over 2000 cycles. Furthermore, a symmetric aqueous Na‐ion battery using Na3V2(PO4)3 as both the cathode and anode exhibits operating voltage of 1.7 V and stability over 1000 cycles at a rate of 5 C.  相似文献   

4.
As an alternative to commercial Ni‐ and Co‐based intercalation‐type cathode materials, conversion‐type metal fluoride (MFx) cathodes are attracting more interest due to their promises to increase cell‐level energy density when coupled with lithium (Li) or silicon (Si)‐based anodes. Among metal fluorides, iron fluorides (FeF2 and FeF3) are regarded as some of the most promising candidates due to their high capacity, moderately high potential and the very low cost of Fe. In this study, the impacts of electrolyte composition on the performance and stability of nanostructured FeF2 cathodes are systematically investigated. Dramatic impacts of Li salt composition, Li salt concentration, solvent composition, and cycling potential range on the cathode's most critical performance parameters—stability, capacity, rate, and voltage hysteresis are discovered. In contrast to previous beliefs, it is observed that even if the Fe2+ cation dissolution could be avoided, the dissolution of F? anions may still negatively affect cathode performance. Formation of the more favorable cathode solid electrolyte interface (CEI) is found to minimize both processes.  相似文献   

5.
LiNixMnyCo1?x?yO2 (NMC) cathode materials with Ni ≥ 0.8 have attracted great interest for high energy‐density lithium‐ion batteries (LIBs) but their practical applications under high charge voltages (e.g., 4.4 V and above) still face significant challenges due to severe capacity fading by the unstable cathode/electrolyte interface. Here, an advanced electrolyte is developed that has a high oxidation potential over 4.9 V and enables NMC811‐based LIBs to achieve excellent cycling stability in 2.5–4.4 V at room temperature and 60 °C, good rate capabilities under fast charging and discharging up to 3C rate (1C = 2.8 mA cm?2), and superior low‐temperature discharge performance down to ?30 °C with a capacity retention of 85.6% at C/5 rate. It is also demonstrated that the electrode/electrolyte interfaces, not the electrolyte conductivity and viscosity, govern the LIB performance. This work sheds light on a very promising strategy to develop new electrolytes for fast‐charging high‐energy LIBs in a wide‐temperature range.  相似文献   

6.
Although the “water‐in‐salt” electrolyte has significantly expanded the electrochemical stability window of aqueous electrolytes from 1.23 to 3 V, its inevitable hydrogen evolution under 1.9 V versus Li+/Li prevents the practical use of many energy‐dense anodes. Meanwhile, its liquidus temperature at 17 °C restricts its application below ambient temperatures. An advanced hybrid electrolyte is proposed in this work by introducing acetonitrile (AN) as co‐solvent, which minimizes the presence of interfacial water at the negatively charged electrode surface, and generates a thin and uniform interphase consisting of an organic outer layer based on nitrile (C?N) and sulfamide (R‐S‐N‐S) species and an inner layer rich in LiF. Such an interphase significantly suppresses water reduction and expands the electrochemical stability window to an unprecedented width of 4.5 V. Thanks to the low freezing point (?48 °C) and low viscosity of AN, the hybrid electrolyte is highly conductive in a wide temperature range, and enables a LiMn2O4/Li4Ti5O12 full cell at both ambient and sub‐ambient temperatures with excellent cycling stability and rate capability. Meanwhile, such a hybrid electrolyte also inherits the nonflammable nature of aqueous electrolyte. The well‐balanced merits of the developed electrolyte make it suitable for high energy density aqueous batteries.  相似文献   

7.
Dual‐ion batteries (DIBs) with high operation voltage offer promising candidates for low‐cost clean energy chemistries. However, there still exist tough issues, including structural collapse of the graphite cathode due to solvent co‐intercalation and electrolyte decomposition on the electrode/electrolyte interface, which results in unsatisfactory cyclability and fast battery failure. Herein, Li4Ti5O12 (LTO) modified mesocarbon microbeads (MCMBs) are proposed as a cathode material. The LTO layer functions as a skeleton and offers electrocatalytic active sites for in situ generation of a favorable and compatible cathode electrolyte interface (CEI) layer. The synergetic LTO‐CEI network can change the thermodynamic behavior of the PF6? intercalation process and maintain the structural integrity of the graphite cathode, as a “Great Wall” to protect the cathode from structural collapse and electrolyte decomposition. Such LTO‐CEI reinforced cathode exhibits a prolonged cyclability with 85.1% capacity retention after 2000 cycles even at cut‐off potential of 5.4 V versus Li+/Li. Moreover, the LTO‐modified MCMB (+)//prelithiated MCMB (?) full cell exhibits a high energy density of ≈200 Wh kg?1, remarkably enhanced cyclability with 93.5% capacity retention after 1000 cycles. Undoubtedly, this work offers in‐depth insight into interface chemistry, which can arouse new originality to boost the development of DIBs.  相似文献   

8.
High‐capacity Li‐rich layered oxide cathodes along with Si‐incorporated graphite anodes have high reversible capacity, outperforming the electrode materials used in existing commercial products. Hence, they are potential candidates for the development of high‐energy‐density lithium‐ion batteries (LIBs). However, structural degradation induced by loss of interfacial stability is a roadblock to their practical use. Here, the use of malonic acid‐decorated fullerene (MA‐C60) with superoxide dismutase activity and water scavenging capability as an electrolyte additive to overcome the structural instability of high‐capacity electrodes that hampers the battery quality is reported. Deactivation of PF5 by water scavenging leads to the long‐term stability of the interfacial structures of electrodes. Moreover, an MA‐C60‐added electrolyte deactivates the reactive oxygen species and constructs an electrochemically robust cathode‐electrolyte interface for Li‐rich cathodes. This work paves the way for new possibilities in the design of electrolyte additives by eliminating undesirable reactive substances and tuning the interfacial structures of high‐capacity electrodes in LIBs.  相似文献   

9.
The development of all‐solid‐state lithium–sulfur batteries is hindered by the poor interfacial properties at solid electrolyte (SE)/electrode interfaces. The interface is modified by employing the highly concentrated solvate electrolyte, (MeCN)2?LiTFSI:TTE, as an interlayer material at the electrolyte/electrode interfaces. The incorporation of an interlayer significantly improves the cycling performance of solid‐state Li2S batteries compared to the bare counterpart, exhibiting a specific capacity of 760 mAh g?1 at cycle 100 (330 mAh g?1 for the bare cell). Electrochemical impedance spectroscopy shows that the interfacial resistance of the interlayer‐modified cell gradually decreases as a function of cycle number, while the impedance of the bare cell remains almost constant. Cross‐section scanning electron microscopy (SEM)/ energy dispersive X‐ray spectroscopy (EDS) measurements on the interlayer‐modified cell confirm the permeation of solvate into the cathode and the SE with electrochemical cycling, which is related to the decrease in cell impedance. In order to mimic the full permeation of the solvate across the entire cell, the solvate is directly mixed with the SE to form a “solvSEM” electrolyte. The hybrid Li2S cell using a solvSEM electrolyte exhibits superior cycling performance compared to the solid‐state cells, in terms of Li2S loading, Li2S utilization, and cycling stability. The improved performance is due to the favorable ionic contact at the battery interfaces.  相似文献   

10.
Tunnel‐type sodium manganese oxide is a promising cathode material for aqueous/nonaqueous sodium‐ion batteries, however its storage mechanism is not fully understood, in part due to the complicated sodium intercalation process. In addition, low cyclability due to manganese dissolution has limited its practical application in rechargeable batteries. Here, the intricate sodium intercalation mechanism of Na0.44MnO2 is revealed by combination of electrochemical characterization, structure determination from powder X‐ray diffraction data, 3D bond valence difference maps, and barrier‐energy calculations of the sodium diffusion. NaI is proposed as an important electrolyte solution additive. It is shown to form a thin, beneficial, and durable cathode surface film that prevents manganese dissolution. The addition of 0.01 m NaI to electrolyte solutions based on alkyl carbonate solvents and NaClO4 greatly improves the cycling efficiency, raising the capacity retention from 86% to 96% after 600 cycles. This study determines the core aspects of the sodium intercalation mechanism in tunnel‐type sodium manganese oxide and shows how it can serve as a durable cathode material for rechargeable Na batteries.  相似文献   

11.
Owing to the high voltage of lithium‐ion batteries (LIBs), the dominating electrolyte is non‐aqueous. The idea of an aqueous rechargeable lithium battery (ARLB) dates back to 1994, but it had attracted little attention due to the narrow stable potential window of aqueous electrolytes, which results in low energy density. However, aqueous electrolytes were employed during the 2000s for the fundamental studies of electrode materials in the absence of side reactions such as the decomposition of organic species. The high solubility of lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in water has introduced new opportunities for high‐voltage ARLBs. Nonetheless, these ideas are somehow overshadowed by the common perception about the essential limitation of the aqueous electrolyte. The electrochemical behaviour of conventional electrode materials can be substantially tuned in the water‐in‐salt electrolytes. The latest idea of utilising a graphite anode in the aqueous water‐in‐salt electrolytes has paved the way towards not only 4‐V ARLB but also a new generation of Li?S batteries with a higher operating voltage and energy efficiency. Furthermore, aqueous electrolytes can provide a cathodically stable environment for Li?O2 batteries. The present paper aims to highlight these emerging opportunities possibly leading to a new generation of LIBs, which can be substantially cheaper and safer.  相似文献   

12.
Solid‐state lithium metal batteries (SSLMBs) may become one of the high‐energy density storage devices for the next generation of electric vehicles. High safety and energy density can be achieved by utilizing solid electrolytes and Li metal anodes. Therefore, developing cathode materials which can match with Li metal anode efficiently is indispensable. In SSLMBs, Li metal anodes can afford the majority of active lithium ions, then lithium‐depleted cathode materials can be a competitive candidate to achieve high gravimetric energy density as well as save lithium resources. Li0.33MnO2 lithium‐depleted material is chosen, which also has the advantages of low synthesis temperature and low cost (cobalt‐free). Notably, solid‐state electrolyte can greatly alleviate the problem of manganese dissolution in the electrolyte, which is beneficial to improve the cycling stability of the battery. Thus, SSLMBs enable practical applications of lithium‐depleted cathode materials.  相似文献   

13.
The migration of zinc‐ion batteries from alkaline electrolyte to neutral or mild acidic electrolyte promotes research into their flexible applications. However, discharge voltage of many reported zinc‐ion batteries is far from satisfactory. On one hand, the battery voltage is substantially restricted by the narrow voltage window of aqueous electrolytes. On the other hand, many batteries yield a low‐voltage discharge plateau or show no plateau but capacitor‐like sloping discharge profiles. This impacts the battery's practicability for flexible electronics where stable and consistent high energy is needed. Herein, an aqueous zinc hybrid battery based on a highly concentrated dual‐ion electrolyte and a hierarchically structured lithium‐ion‐intercalative LiVPO4F cathode is developed. This hybrid battery delivers a flat and high‐voltage discharge plateau of nearly 1.9 V, ranking among the highest reported values for all aqueous zinc‐based batteries. The resultant high energy density of 235.6 Wh kg?1 at a power density of 320.8 W kg?1 also outperforms most reported zinc‐based batteries. A designed solid‐state and long‐lasting hydrogel electrolyte is subsequently applied in the fabrication of a flexible battery, which can be integrated into various flexible devices as powerful energy supply. The idea of designing such a hybrid battery offers a new strategy for developing high‐voltage and high‐energy aqueous energy storage systems.  相似文献   

14.
In this study, a new dual‐ion battery (DIB) concept based on an aqueous/non‐aqueous electrolyte is reported, combining high safety in the form of a nonflammable water‐in‐salt electrolyte, a high cathodic stability by forming a protective interphase on the negative electrode (non‐aqueous solvent), and improved sustainability by using a graphite‐based positive electrode material. Far beyond the anodic stability limit of water, the formation of a stage‐2 acceptor‐type graphite intercalation compound (GIC) of bis(trifluoromethanesulfonyl) imide (TFSI) anions from an aqueous‐based electrolyte is achieved for the first time, as confirmed by ex‐situ X‐ray diffraction. The choice of negative electrode material shows a huge impact on the performance of the DIB cell chemistry, i.e., discharge capacities up to 40 mAh g?1 are achieved even at a high specific current of 200 mA g?1. In particular, lithium titanium phosphate (LiTi2(PO4)3; LTP) and lithium titanium oxide (Li4Ti5O12; LTO) are evaluated as negative electrodes, exhibiting specific advantages for this DIB setup. In this work, a new DIB storage concept combining an environmentally friendly, transition‐metal‐free, abundant graphite positive electrode material, and a nonflammable water‐based electrolyte is established, thus paving the path toward a sustainable and safe alternative energy storage technology.  相似文献   

15.
All‐solid‐state batteries are promising candidates for the next‐generation safer batteries. However, a number of obstacles have limited the practical application of all‐solid‐state Li batteries (ASSLBs), such as moderate ionic conductivity at room temperature. Here, unlike most of the previous approaches, superior performances of ASSLBs are achieved by greatly reducing the thickness of the solid‐state electrolyte (SSE), where ionic conductivity is no longer a limiting factor. The ultrathin SSE (7.5 µm) is developed by integrating the low‐cost polyethylene separator with polyethylene oxide (PEO)/Li‐salt (PPL). The ultrathin PPL shortens Li+ diffusion time and distance within the electrolyte, and provides sufficient Li+ conductance for batteries to operate at room temperature. The robust yet flexible polyethylene offers mechanical support for the soft PEO/Li‐salt, effectively preventing short‐circuits even under mechanical deformation. Various ASSLBs with PPL electrolyte show superior electrochemical performance. An initial capacity of 135 mAh g?1 at room temperature and the high‐rate capacity up to 10 C at 60 °C can be achieved in LiFePO4/PPL/Li batteries. The high‐energy‐density sulfur cathode and MoS2 anode employing PPL electrolyte also realize remarkable performance. Moreover, the ASSLB can be assembled by a facile process, which can be easily scaled up to mass production.  相似文献   

16.
Aqueous Zn‐based batteries are attracting extensive interest because of their economic feasibility and potentially high energy density. However, poor rechargeability of Zn anode in conventional electrolytes resulting from dendrite formation and self‐corrosion hinders their practical implementation. Herein, a Zn molten hydrate composed of inorganic Zn salt and water is demonstrated as an advantageous electrolyte for solving these issues. In this electrolyte, dendrite‐free Zn deposition/dissolution reaction with a high Coulombic efficiency (≈99%) as well as long‐term stability, free from CO2 poisoning are realized. The resultant Zn–air cell exhibits a reversible capacity of 1000 mAh g(catalyst)?1 over 100 cycles at 30 °C. Combined with the intrinsic safety associated with aqueous chemistry and cost benefit of the raw material, the present Zn–air battery makes a strong candidate for large‐scale energy storage.  相似文献   

17.
Layered lithium–nickel–cobalt–manganese oxide (NCM) materials have emerged as promising alternative cathode materials owing to their high energy density and electrochemical stability. Although high reversible capacity has been achieved for Ni‐rich NCM materials when charged beyond 4.2 V versus Li+/Li, full lithium utilization is hindered by the pronounced structural degradation and electrolyte decomposition. Herein, the unexpected realization of sustained working voltage as well as improved electrochemical performance upon electrochemical cycling at a high operating voltage of 4.9 V in the Ni‐rich NCM LiNi0.895Co0.085Mn0.02O2 is presented. The improved electrochemical performance at a high working voltage at 4.9 V is attributed to the removal of the resistive Ni2+O rock‐salt surface layer, which stabilizes the voltage profile and improves retention of the energy density during electrochemical cycling. The manifestation of the layered Ni2+O rock‐salt phase along with the structural evolution related to the metal dissolution are probed using in situ X‐ray diffraction, neutron diffraction, transmission electron microscopy, and X‐ray absorption spectroscopy. The findings help unravel the structural complexities associated with high working voltages and offer insight for the design of advanced battery materials, enabling the realization of fully reversible lithium extraction in Ni‐rich NCM materials.  相似文献   

18.
Li2S is a fully lithiated sulfur‐based cathode with a high theoretical capacity of 1166 mAh g?1 that can be coupled with lithium‐free anodes to develop high‐energy‐density lithium–sulfur batteries. Although various approaches have been pursued to obtain a high‐performance Li2S cathode, there are still formidable challenges with it (e.g., low conductivity, high overpotential, and irreversible polysulfide diffusion) and associated fabrication processes (e.g., insufficient Li2S, excess electrolyte, and low reversible capacity), which have prevented the realization of high electrochemical utilization and stability. Here, a new cathode design composed of a homogeneous Li2S‐TiS2‐electrolyte composite that is prepared by a simple two‐step dry/wet‐mixing process is demonstrated, allowing the liquid electrolyte to wet the powder mixture consisting of insulating Li2S and conductive TiS2. The close‐contact, three‐phase boundary of this system improves the Li2S‐activation efficiency and provides fast redox‐reaction kinetics, enabling the Li2S‐TiS2‐electrolyte cathode to attain stable cyclability at C/7 to C/3 rates, superior long‐term cyclability over 500 cycles, and promising high‐rate performance up to 1C rate. More importantly, this improved performance results from a cell design attaining a high Li2S loading of 6 mg cm?2, a high Li2S content of 75 wt%, and a low electrolyte/Li2S ratio of 6.  相似文献   

19.
New energy storage and conversion systems require large‐scale, cost‐effective, good safety, high reliability, and high energy density. This study demonstrates a low‐cost and safe aqueous rechargeable lithium‐nickel (Li‐Ni) battery with solid state Ni(OH)2/NiOOH redox couple as cathode and hybrid electrolytes separated by a Li‐ion‐conductive solid electrolyte layer. The proposed aqueous rechargeable Li‐Ni battery exhibits an approximately open‐circuit potential of 3.5 V, outperforming the theoretic stable window of water 1.23 V, and its energy density can be 912.6 W h kg‐1, which is much higher than that of state‐of‐the‐art lithium ion batteries. The use of a solid‐state redox couple as cathode with a metallic lithium anode provides another postlithium chemistry for practical energy storage and conversion.  相似文献   

20.
Herein, the successful synthesis of MnPO4‐coated LiNi0.4Co0.2Mn0.4O2 (MP‐NCM) as a lithium battery cathode material is reported. The MnPO4 coating acts as an ideal protective layer, physically preventing the contact between the NCM active material and the electrolyte and, thus, stabilizing the electrode/electrolyte interface and preventing detrimental side reactions. Additionally, the coating enhances the lithium de‐/intercalation kinetics in terms of the apparent lithium‐ion diffusion coefficient. As a result, MP‐NCM‐based electrodes reveal greatly enhanced C‐rate capability and cycling stability—even under exertive conditions like extended operational potential windows, elevated temperature, and higher active material mass loadings. This superior electrochemical behavior of MP‐NCM compared to as‐synthesized NCM is attributed to the superior stability of the electrode/electrolyte interface and structural integrity when applying a MnPO4 coating. Employing an ionic liquid as an alternative, intrinsically safer electrolyte system allows for outstanding cycling stabilities in a lithium‐metal battery configuration with a capacity retention of well above 85% after 2000 cycles. Similarly, the implementation in a lithium‐ion cell including a graphite anode provides stable cycling for more than 2000 cycles and an energy and power density of, respectively, 376 Wh kg?1 and 1841 W kg?1 on the active material level.  相似文献   

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