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1.
Lithium–sulfur (Li–S) batteries present one of the most promising energy storage systems owing to their high energy density and low cost. However, the commercialization of Li–S batteries is still hindered by several technical issues; the notorious polysulfide shuttling and sluggish sulfur conversion kinetics. In this work, unique hierarchical Fe3‐xC@C hollow microspheres as an advanced sulfur immobilizer and promoter for enabling high‐efficiency Li–S batteries is developed. The porous hollow architecture not only accommodates the volume variation upon the lithiation–delithiation processes, but also exposes vast active interfaces for facilitated sulfur redox reactions. Meanwhile, the mesoporous carbon coating establishes a highly conductive network for fast electron transportation. More importantly, the defective Fe3‐xC nanosized subunits impose strong LiPS adsorption and catalyzation, enabling fast and durable sulfur electrochemistry. Attributed to these structural superiorities, the obtained sulfur electrodes exhibit excellent electrochemical performance, i.e., high areal capacity of 5.6 mAh cm?2, rate capability up to 5 C, and stable cycling over 1000 cycles with a low capacity fading rate of 0.04% per cycle at 1 C, demonstrating great promise in the development of practical Li–S batteries.  相似文献   

2.
One of the critical challenges to develop advanced lithium‐sulfur (Li‐S) batteries lies in exploring a high efficient stable sulfur cathode with robust conductive framework and high sulfur loading. Herein, a 3D flexible multifunctional hybrid is rationally constructed consisting of nitrogen‐doped carbon foam@CNTs decorated with ultrafine MgO nanoparticles for the use as advanced current collector. The dense carbon nanotubes uniformly wrapped on the carbon foam skeletons enhance the flexibility and build an interconnected conductive network for rapid ionic/electronic transport. In particular, a synergistic action of MgO nanoparticles and in situ N‐doping significantly suppresses the shuttling effect via enhanced chemisorption of lithium polysulfides. Owing to these merits, the as‐built electrode with an ultrahigh sulfur loading of 14.4 mg cm?2 manifests a high initial areal capacity of 10.4 mAh cm?2, still retains 8.8 mAh cm?2 (612 mAh g?1 in gravimetric capacity) over 50 cycles. The best cycling performance is achieved upon 800 cycles with an extremely low decay rate of 0.06% at 2 C. Furthermore, a flexible soft‐packaged Li‐S battery is readily assembled, which highlights stable electrochemical characteristics under bending and even folding. This cathode structural design may open up a potential avenue for practical application of high‐sulfur‐loading Li‐S batteries toward flexible energy‐storage devices.  相似文献   

3.
Li‐ion batteries containing cost‐effective, environmentally benign cathode materials with high specific capacities are in critical demand to deliver the energy density requirements of electric vehicles and next‐generation electronic devices. Here, the phase‐controlled synthesis of copper sulfide (CuxS) composites by the temperature‐controlled sulfurization of a prototypal Cu metal‐organic framework (MOF), HKUST‐1 is reported. The tunable formation of different CuxS phases within a carbon network represents a simple method for the production of effective composite cathode materials for Li‐ion batteries. A direct link between the sulfurization temperature of the MOF and the resultant CuxS phase formed with more Cu‐rich phases favored at higher temperatures is further shown. The CuxS/C samples are characterized through X‐ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy, and energy dispersive X‐ray spectroscopy (EDX) in addition to testing as Li‐ion cathodes. It is shown that the performance is dependent on both the CuxS phase and the crystal morphology with the Cu1.8S/C‐500 material as a nanowire composite exhibiting the best performance, showing a specific capacity of 220 mAh g?1 after 200 charge/discharge cycles.  相似文献   

4.
Herein, high‐content N‐doped carbon nanotube (CNT) microspheres (HNCMs) are successfully synthesized through simple spray drying and one‐step pyrolysis. HNCM possesses a hierarchically porous architecture and high‐content N‐doping. In particular, HNCM800 (HNCM pyrolyzed at 800 °C) shows high nitrogen content of 12.43 at%. The porous structure derived from well‐interconnected CNTs not only offers a highly conductive network and blocks diffusion of soluble lithium polysulfides (LiPSs) in physical adsorption, but also allows sufficient sulfur infiltration. The incorporation of N‐rich CNTs provides strong chemical immobilization for LiPSs. As a sulfur host for lithium–sulfur batteries, good rate capability and high cycling stability is achieved for HNCM/S cathodes. Particularly, the HNCM800/S cathode delivers a high capacity of 804 mA h g?1 at 0.5 C after 1000 cycles corresponding to low fading rate (FR) of only 0.011% per cycle. Remarkably, the cathode with high sulfur loading of 6 mg cm?2 still maintains high cyclic stability (capacity of 555 mA h g?1 after 1000 cycles, FR 0.038%). Additionally, CNT/Co3O4 microspheres are obtained by the oxidation of CNTs/Co in the air. The as‐prepared CNT/Co3O4 microspheres are employed as an anode for lithium‐ion batteries and present excellent cycling performance.  相似文献   

5.
As one important component of sulfur cathodes, the carbon host plays a key role in the electrochemical performance of lithium‐sulfur (Li‐S) batteries. In this paper, a mesoporous nitrogen‐doped carbon (MPNC)‐sulfur nanocomposite is reported as a novel cathode for advanced Li‐S batteries. The nitrogen doping in the MPNC material can effectively promote chemical adsorption between sulfur atoms and oxygen functional groups on the carbon, as verified by X‐ray absorption near edge structure spectroscopy, and the mechanism by which nitrogen enables the behavior is further revealed by density functional theory calculations. Based on the advantages of the porous structure and nitrogen doping, the MPNC‐sulfur cathodes show excellent cycling stability (95% retention within 100 cycles) at a high current density of 0.7 mAh cm‐2 with a high sulfur loading (4.2 mg S cm‐2) and a sulfur content (70 wt%). A high areal capacity (≈3.3 mAh cm‐2) is demonstrated by using the novel cathode, which is crucial for the practical application of Li‐S batteries. It is believed that the important role of nitrogen doping promoted chemical adsorption can be extended for development of other high performance carbon‐sulfur composite cathodes for Li‐S batteries.  相似文献   

6.
Freestanding, robust electrodes with high capacity and long lifetime are of critical importance to the development of advanced lithium–sulfur (Li–S) batteries for next‐generation electronics, whose potential applications are greatly limited by the lithium polysulfide (LiPS) shuttle effect. Solutions to this issue have mostly focused on the design of cathode hosts with a polar, sulfurphilic, conductive network, or the introduction of an extra layer to suppress LiPS shuttling, which either results in complex fabrication procedures or compromises the mechanical flexibility of the device. A robust Ti3C2Tx/S conductive paper combining the excellent conductivity, mechanical strength, and unique chemisorption of LiPSs from MXene nanosheets is reported. Importantly, repeated cycling initiates the in situ formation of a thick sulfate complex layer on the MXene surface, which acts as a protective membrane, effectively suppressing the shuttling of LiPSs and improving the utilization of sulfur. Consequently, the Ti3C2Tx/S paper exhibits a high capacity and an ultralow capacity decay rate of 0.014% after 1500 cycles, the lowest value reported for Li–S batteries to date. A robust prototype pouch cell and full cell of Ti3C2Tx/S paper // lithium foil and prelithiated germanium are also demonstrated. The preliminary results show that Ti3C2Tx/S paper holds great promise for future flexible and wearable electronics.  相似文献   

7.
3D metal carbide@mesoporous carbon hybrid architecture (Ti3C2Tx@Meso‐C, TX ≈ FxOy) is synthesised and applied as cathode material hosts for lithium‐sulfur batteries. Exfoliated‐metal carbide (Ti3C2Tx) nanosheets have high electronic conductivity and contain rich functional groups for effective trapping of polysulfides. Mesoporous carbon with a robust porous structure provides sufficient spaces for loading sulfur and effectively cushion the volumetric expansion of sulfur cathodes. Theoretical calculations have confirmed that metal carbide can absorb sulfur and polysulfides, therefore extending the cycling performance. The Ti3C2Tx@Meso‐C/S cathodes have achieved a high capacity of 1225.8 mAh g?1 and more than 300 cycles at the C/2 current rate. The Ti3C2Tx@Meso‐C hybrid architecture is a promising cathode host material for lithium‐sulfur batteries.  相似文献   

8.
Lithium and sodium thiophosphates (and related compounds) have recently attracted attention because of their potential use as solid electrolytes in solid‐state batteries. These compounds, however, exhibit only limited stability in practice as they react with the electrodes. The decomposition products partially remain redox active hence leading to excess capacity. The redox activity of thiophosphates is explicitly used to act as electrode for sodium‐ion batteries. Copper thiophosphate (Cu3PS4) is used as a model system. The storage behavior between 0.01 and 2.5 V versus Na+/Na is studied in half cells using different electrolytes with 1 m NaPF6 in diglyme showing the best result. Cu3PS4 shows highly reversible charge storage with capacities of about 580 mAh g?1 for more than 200 cycles @120 mA g?1 and about 450 mAh g?1 for 1400 cycles @1 A g?1. The redox behavior is studied by operando X‐ray diffraction and X‐ray photoelectron spectroscopy. During initial sodiation, Cu3PS4 undergoes a conversion reaction including the formation of Cu and Na2S. During cycling, the redox activity seems dominated by sulfur. Interestingly, the capacity of Cu3PS4 for lithium storage is smaller, leading to about 170 mAh g?1 after 200 cycles. The results demonstrate that thiophosphates can lead to reversible charge storage over several hundred cycles without any notable capacity decay.  相似文献   

9.
To achieve a high sulfur loading is critical for high‐energy lithium–sulfur batteries. However, high sulfur loading, especially at a low electrolyte/sulfur ratio (E/S), usually causes low sulfur utilization, mainly caused by the slow redox kinetics of polysulfides and the passivation of the discharge product, poor electrically/ionically conducting Li2S. Herein, by using cobalt‐based metal organic frameworks (Co‐MOFs) as precursors, a Co, N‐doped carbonaceous composite (Co, N‐CNTs (carbon nanotubes)‐CNS (carbon nanosheet)/CFC (carbon fiber cloth)) is fabricated with hierarchically ordered structure, which consists of a free‐standing 3D carbon fiber skeleton decorated with a vertical 2D carbon nanosheets array rooted by interwoven 1D CNTs. As an effective polysulfides host, the hierarchically ordered 3D conductive network with abundant active sites and voids can effectively trap polysulfides and provide fast electron/ions pathways to convert them. In addition, Co and N heteroatoms can strengthen the interaction with polysulfides and accelerate its reaction kinetics. More importantly, the interwoven CNTs with Co, N‐doping can induce 3D Li2S deposition instead of conventional 2D deposition, which benefits improving sulfur utilization. Therefore, for Co, N‐CNTs‐CNS/CFC electrodes, even at a high sulfur loading of 10.20 mg cm?2 with a low E/S of 6.94, a high reversible areal capacity of 7.42 mAh cm?2 can be achieved with excellent cycling stability.  相似文献   

10.
Realizing long cycling stability under a high sulfur loading is an essential requirement for the practical use of lithium–sulfur (Li–S) batteries. Here, a lamellar aerogel composed of Ti3C2Tx MXene/carbon nanotube (CNT) sandwiches is prepared by unidirectional freeze-drying to boost the cycling stability of high sulfur loading batteries. The produced materials are denoted parallel-aligned MXene/CNT (PA-MXene/CNT) due to the unique parallel-aligned structure. The lamellae of MXene/CNT/MXene sandwich form multiple physical barriers, coupled with chemical trapping and catalytic activity of MXenes, effectively suppressing lithium polysulfide (LiPS) shuttling under high sulfur loading, and more importantly, substantially improving the LiPS confinement ability of 3D hosts free of micro- and mesopores. The assembled Li–S battery delivers a high capacity of 712 mAh g−1 with a sulfur loading of 7 mg cm−2, and a superior cycling stability with 0.025% capacity decay per cycle over 800 cycles at 0.5 C. Even with sulfur loading of 10 mg cm−2, a high areal capacity of above 6 mAh cm−2 is obtained after 300 cycles. This work presents a typical example for the rational design of a high sulfur loading host, which is critical for the practical use of Li–S batteries  相似文献   

11.
The lithium–sulfur (Li–S) battery is regarded as the most promising rechargeable energy storage technology for the increasing applications of clean energy transportation systems due to its remarkable high theoretical energy density of 2.6 kWh kg?1, considerably outperforming today's lithium‐ion batteries. Additionally, the use of sulfur as active cathode material has the advantages of being inexpensive, environmentally benign, and naturally abundant. However, the insulating nature of sulfur, the fast capacity fading, and the short lifespan of Li–S batteries have been hampered their commercialization. In this paper, a functional mesoporous carbon‐coated separator is presented for improving the overall performance of Li–S batteries. A straightforward coating modification of the commercial polypropylene separator allows the integration of a conductive mesoporous carbon layer which offers a physical place to localize dissolved polysulfide intermediates and retain them as active material within the cathode side. Despite the use of a simple sulfur–carbon black mixture as cathode, the Li–S cell with a mesoporous carbon‐coated separator offers outstanding performance with an initial capacity of 1378 mAh g?1 at 0.2 C, and high reversible capacity of 723 mAh g?1, and degradation rate of only 0.081% per cycle, after 500 cycles at 0.5 C.  相似文献   

12.
Mg batteries as the most typical multivalent batteries are attracting increasing attention because of resource abundance, high volumetric energy density, and smooth plating/stripping of Mg anodes. However, current limitations for the progress of Mg batteries come from the lack of high voltage electrolytes and fast Mg‐insertable structure prototypes. In order to improve their energy or power density, hybrid systems combining Li‐driven cathode reaction with Mg anode process appear to be a potential solution by bypassing the aforementioned limitations. Here, FeS x (x = 1 or 2) is employed as conversion cathode with 2–4 electron transfers to achieve a maximum energy density close to 400 Wh kg?1, which is comparable with that of Li‐ion batteries but without serious dendrite growth and polysulphide dissolution. In situ formation of solid electrolyte interfaces on both sulfide and Mg electrodes is likely responsible for long‐life cycling and suppression of S‐species passivation at Mg anodes. Without any decoration on the cathode, electrolyte additive, or anode protection, a reversible capacity of more than 200 mAh g?1 is still preserved for Mg/FeS2 after 200 cycles.  相似文献   

13.
Metal oxide‐based nanomaterials are widely studied because of their high‐energy densities as anode materials in lithium‐ion batteries. However, the fast capacity degradation resulting from the large volume expansion upon lithiation hinders their practical application. In this work, the preparation of walnut‐like multicore–shell MnO encapsulated nitrogen‐rich carbon nanocapsules (MnO@NC) is reported via a facile and eco‐friendly process for long‐cycling Li‐ion batteries. In this hybrid structure, MnO nanoparticles are uniformly dispersed inside carbon nanoshells, which can simultaneously act as a conductive framework and also a protective buffer layer to restrain the volume variation. The MnO@NC nanocapsules show remarkable electrochemical performances for lithium‐ion batteries, exhibiting high reversible capability (762 mAh g?1 at 100 mA g?1) and stable cycling life (624 mAh g?1 after 1000 cycles at 1000 mA g?1). In addition, the soft‐packed full batteries based on MnO@NC nanocapsules anodes and commercial LiFePO4 cathodes present good flexibility and cycling stability.  相似文献   

14.
Cathode design is indispensable for building Li‐O2 batteries with long cycle life. A composite of carbon‐wrapped Mo2C nanoparticles and carbon nanotubes is prepared on Ni foam by direct hydrolysis and carbonization of a gel composed of ammonium heptamolybdate tetrahydrate and hydroquinone resin. The Mo2C nanoparticles with well‐controlled particle size act as a highly active oxygen reduction reactions/oxygen evolution reactions (ORR/OER) catalyst. The carbon coating can prevent the aggregation of the Mo2C nanoparticles. The even distribution of Mo2C nanoparticles results in the homogenous formation of discharge products. The skeleton of porous carbon with carbon nanotubes protrudes from the composite, resulting in extra voids when applied as a cathode for Li‐O2 batteries. The batteries deliver a high discharge capacity of ≈10 400 mAh g?1 and a low average charge voltage of ≈4.0 V at 200 mA g?1. With a cutoff capacity of 1000 mAh g?1, the Li‐O2 batteries exhibit excellent charge–discharge cycling stability for over 300 cycles. The average potential polarization of discharge/charge gaps is only ≈0.9 V, demonstrating the high ORR and OER activities of these Mo2C nanoparticles. The excellent cycling stability and low potential polarization provide new insights into the design of highly reversible and efficient cathode materials for Li‐O2 batteries.  相似文献   

15.
Si‐based anodes with a stiff diamond structure usually suffer from sluggish lithiation/delithiation reaction due to low Li‐ion and electronic conductivity. Here, a novel ternary compound ZnSi2P3 with a cation‐disordered sphalerite structure, prepared by a facile mechanochemical method, is reported, demonstrating faster Li‐ion and electron transport and greater tolerance to volume change during cycling than the existing Si‐based anodes. A composite electrode consisting of ZnSi2P3 and carbon achieves a high initial Coulombic efficiency (92%) and excellent rate capability (950 mAh g?1 at 10 A g?1) while maintaining superior cycling stability (1955 mAh g?1 after 500 cycles at 300 mA g?1), surpassing the performance of most Si‐ and P‐based anodes ever reported. The remarkable electrochemical performance is attributed to the sphalerite structure that allows fast ion and electron transport and the reversible Li‐storage mechanism involving intercalation and conversion reactions. Moreover, the cation‐disordered sphalerite structure is flexible to ionic substitutions, allowing extension to a family of Zn(Cu)Si2+xP3 solid solution anodes (x = 0, 2, 5, 10) with large capacity, high initial Coulombic efficiency, and tunable working potentials, representing attractive anode candidates for next‐generation, high‐performance, and low‐cost Li‐ion batteries.  相似文献   

16.
All‐solid‐state lithium metal batteries (ASSLMBs) have attracted significant attention due to their superior safety and high energy density. However, little success has been made in adopting Li metal anodes in sulfide electrolyte (SE)‐based ASSLMBs. The main challenges are the remarkable interfacial reactions and Li dendrite formation between Li metal and SEs. In this work, a solid‐state plastic crystal electrolyte (PCE) is engineered as an interlayer in SE‐based ASSLMBs. It is demonstrated that the PCE interlayer can prevent the interfacial reactions and lithium dendrite formation between SEs and Li metal. As a result, ASSLMBs with LiFePO4 exhibit a high initial capacity of 148 mAh g?1 at 0.1 C and 131 mAh g?1 at 0.5 C (1 C = 170 mA g?1), which remains at 122 mAh g?1 after 120 cycles at 0.5 C. All‐solid‐state Li‐S batteries based on the polyacrylonitrile‐sulfur composite are also demonstrated, showing an initial capacity of 1682 mAh g?1. The second discharge capacity of 890 mAh g?1 keeps at 775 mAh g?1 after 100 cycles. This work provides a new avenue to address the interfacial challenges between Li metal and SEs, enabling the successful adoption of Li metal in SE‐based ASSLMBs with high energy density.  相似文献   

17.
The cycling stability of high‐sulfur‐loading lithium–sulfur (Li–S) batteries remains a great challenge owing to the exaggerated shuttle problem and interface instability. Despite enormous efforts on design of advanced electrodes and electrolytes, the stability issue raised from current collectors has been rarely concerned. This study demonstrates that rationally designing a 3D carbonaceous macroporous current collector is an efficient and effective “two‐in‐one” strategy to improve the cycling stability of high‐sulfur‐loading Li–S batteries, which is highly versatile to enable various composite cathodes with sulfur loading >3.7 mAh cm?2. The best cycling performance can be achieved upon 950 cycles with a very low decay rate of 0.029%. Moreover, the origin of such a huge enhancement in cycling stability is ascribed to (1) the inhibition of electrochemical corrosion, which severely occurs on the typical Al foil and disables its long‐term sustainability for charge transfer, and (2) the passivation of cathode surface. The role of the chemical resistivity against corrosion and favorable macroscopic porous structure is highlighted for exploiting novel current collectors toward exceptional cycling stability of high‐sulfur‐loading Li–S batteries.  相似文献   

18.
The application of Li‐S batteries is hindered by low sulfur utilization and rapid capacity decay originating from slow electrochemical kinetics of polysulfide transformation to Li2S at the second discharge plateau around 2.1 V and harsh shuttling effects for high‐S‐loading cathodes. Herein, a cobalt‐doped SnS2 anchored on N‐doped carbon nanotube (NCNT@Co‐SnS2) substrate is rationally designed as both a polysulfide shield to mitigate the shuttling effects and an electrocatalyst to improve the interconversion kinetics from polysulfides to Li2S. As a result, high‐S‐loading cathodes are demonstrated to achieve good cycling stability with high sulfur utilization. It is shown that Co‐doping plays an important role in realizing high initial capacity and good capacity retention for Li‐S batteries. The S/NCNT@Co‐SnS2 cell (3 mg cm?2 sulfur loading) delivers a high initial specific capacity of 1337.1 mA h g?1 (excluding the Co‐SnS2 capacity contribution) and 1004.3 mA h g?1 after 100 cycles at a current density of 1.3 mA cm?2, while the counterpart cell (S/NCNT@SnS2) only shows an initial capacity of 1074.7 and 843 mA h g?1 at the 100th cycle. The synergy effect of polysulfide confinement and catalyzed polysulfide conversion provides an effective strategy in improving the electrochemical performance for high‐sulfur‐loading Li‐S batteries.  相似文献   

19.
The sluggish conversion kinetics and shuttling behavior of lithium polysulfides (LiPSs) seriously deteriorate the practical application of lithium–sulfur (Li–S) batteries. Herein, Ni single atoms on hollow carbon nanosheet-assembled flowers (Ni-NC) are synthesized via a facile pyrolysis-adsorption process to address these challenges. The as-designed Ni-NC with enhanced mesoporosity and accessible surface area can expose more catalytic sites and facilitate electron/ion transfer. These advantages enable the Ni-NC-modified separator to exhibit both enhanced confinement-catalysis ability and suppressed shuttling of LiPSs. Consequently, the Li−S battery with Ni-NC-modified separator shows an initial capacity of 1167 mAh g−1 with a low capacity decay ratio (0.033% per cycle) over 700 cycles at 1 C. Even at the sulfur loading of 6.17 mg cm−2, a high areal capacity of 5.17 mAh cm−2 is realized at 0.1 C, together with superior cycling stability over 300 cycles. This work provides a facile catalyst design strategy for the development of high-performance Li−S batteries.  相似文献   

20.
Sodium‐ion batteries have been considered one of the most promising power sources beyond Li‐ion batteries. Although the Na metal anode exhibits a high theoretical capacity of 1165 mAh g?1, its application in Na batteries is largely hindered by dendrite growth and low coulombic efficiency. Herein, it is demonstrated that an electrolyte consisting of 1 m sodium tetrafluoroborate in tetraglyme can enable excellent cycling efficiency (99.9%) of a Na metal anode for more than 1000 cycles. This high reversibility of a Na anode can be attributed to a stable solid electrolyte interphase formed on the Na surface, as revealed by cryogenic transmission electron microscopy and X‐ray photoelectron spectroscopy (XPS). These electrolytes also enable excellent cycling stability of Na||hard‐carbon cells and Na||Na2/3Co1/3Mn2/3O2 cells at high rates with very high coulombic efficiencies.  相似文献   

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