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1.
2D transition metal‐dichalcogenides are emerging as efficient and cost‐effective electrocatalysts for the hydrogen evolution reaction (HER). However, only the edge sites of their trigonal prismatic phase show HER‐electrocatalytic properties, while the basal plane, which is absent of defective/unsaturated sites, is inactive. Herein, the authors tackle the key challenge of increasing the number of electrocatalytic sites by designing and engineering heterostructures composed of single‐/few‐layer MoSe2 flakes and carbon nanomaterials (graphene or single‐wall carbon nanotubes) produced by solution processing. The electrochemical coupling between the materials that comprise the heterostructure effectively enhances the HER‐electrocatalytic activity of the native MoSe2 flakes. The optimization of the mass loading of MoSe2 flakes and their electrode assembly via monolithic heterostructure stacking provides a cathodic current density of 10 mA cm?2 at overpotential of 100 mV, a Tafel slope of 63 mV dec?1, and an exchange current density (j0) of 0.203 µA cm?2. In addition, thermal and chemical treatments are exploited to texturize the basal planes of the MoSe2 flakes (through Se‐vacancies creation) and to achieve in situ semiconducting‐to‐metallic phase conversion, respectively, thus they activate new HER‐electrocatalytic sites. The as‐engineered electrodes show a 4.8‐fold enhancement of j0 and a decrease in the Tafel slope to 54 mV dec?1.  相似文献   

2.
Developing advanced supercapacitors with both high areal and volumetric energy densities remains challenging. In this work, self‐supported, compact carbon composite electrodes are designed with tunable thickness using 3D printing technology for high‐energy‐density supercapacitors. The 3D carbon composite electrodes are composed of the closely stacked and aligned active carbon/carbon nanotube/reduced graphene oxide (AC/CNT/rGO) composite filaments. The AC microparticles are uniformly embedded in the wrinkled CNT/rGO conductive networks without using polymer binders, which contributes to the formation of abundant open and hierarchical pores. The 3D‐printed ultrathick AC/CNT/rGO composite electrode (ten layers) features high areal and volumetric mass loadings of 56.9 mg cm?2 and 256.3 mg cm?3, respectively. The symmetric cell assembled with the 3D‐printed thin GO separator and ultrathick AC/CNT/rGO electrodes can possess both high areal and volumetric capacitances of 4.56 F cm?2 and 10.28 F cm?3, respectively. Correspondingly, the assembled ultrathick and compact symmetric cell achieves high areal and volumetric energy densities of 0.63 mWh cm?2 and 1.43 mWh cm?3, respectively. The all‐component extrusion‐based 3D printing offers a promising strategy for the fabrication of multiscale and multidimensional structures of various high‐energy‐density electrochemical energy storage devices.  相似文献   

3.
Lithium‐sulfur batteries (LSBs) have been regarded as a competitive candidate for next‐generation electrochemical energy‐storage technologies due to their merits in energy density. The sluggish redox kinetics of the electrochemistry and the high solubility of polysulfides during cycling result in insufficient sulfur utilization, severe polarization, and poor cyclic stability. Herein, sulfiphilic few‐layered MoSe2 nanoflakes decorated rGO (MoSe2@rGO) hybrid has been synthesized through a facile hydrothermal method and for the first time, is used as a conceptually new‐style sulfur host for LSBs. Specifically, MoSe2@rGO not only strongly interacts with polysulfides but also dynamically strengthens polysulfide redox reactions. The polarization problem is effectively alleviated by relying on the sulfiphilic MoSe2. Moreover, MoSe2@rGO is demonstrated to be beneficial for the fast nucleation and uniform deposition of Li2S, contributing to the high discharge capacity and good cyclic stability. A high initial capacity of 1608 mAh g?1 at 0.1 C, a slow decay rate of 0.042% per loop at 0.25 C, and a high reversible capacity of 870 mAh g?1 with areal sulfur loading of 4.2 mg cm?2 at 0.3 C are obtained. The concept of introducing sulfiphilic transition‐metal selenides into the LSBs system can stimulate engineering of novel architectures with enhanced properties for various energy‐storage devices.  相似文献   

4.
Sodium‐ion batteries (SIBs) are considered to be promising energy storage devices for large‐scale grid storage application due to the vast earth‐abundance and low cost of sodium‐containing precursors. Designing and fabricating a highly efficient anode is one of the keys to improve the electrochemical performance of SIBs. Recently, fluoride‐based materials are found to show an exceptional anode function with high theoretical specific capacity, based on open‐framework structure enabling Na insertion and also exhibiting improved safety. However, fluoride‐based materials suffer from sluggish kinetics and poor capacity retention essentially due to low electric conductivity. Here, an efficient mixed‐conducting network offering fast pathways is proposed to address these issues. This network relies on titanium fluoride?carbon (TiF3?C) core/sheath nanofibers that are prepared via electrospinning. Such highly interconnected electrodes exhibit an enhanced and faster sodium storage performance. Carbon sheath nanofibers are key to an efficient ion‐ and electron‐conducting network that enable Na+/e? transfer to reach the nanosized TiF3. In addition, in‐situ‐converted Ti and NaF particles embedded in the carbon matrix allow high reversible interfacial storage. As a result, the TiF3?C core/sheath electrode exhibits a high capacity of 161 mAh g?1 at a high current density of 1000 mA g?1 over 2000 cycles.  相似文献   

5.
Transition metal oxides hold great promise as high‐energy anodes in next‐generation lithium‐ion batteries. However, owing to the inherent limitations of low electronic/ionic conductivities and dramatic volume change during charge/discharge, it is still challenging to fabricate practically viable compacted and thick TMO anodes with satisfactory electrochemical performance. Herein, with mesoporous cobalt–boride nanoflakes serving as multifunctional bridges in ZnCo2O4 micro‐/nanospheres, a compacted ZnCo2O4/Co–B hybrid structure is constructed. Co–B nanoflakes not only bridge ZnCo2O4 nanoparticles and function as anchors for ZnCo2O4 micro‐/nanospheres to suppress the severe volume fluctuation, they also work as effective electron conduction bridges to promote fast electron transportation. More importantly, they serve as Li+ transfer bridges to provide significantly boosted Li+ diffusivity, evidenced from both experimental kinetics analysis and density functional theory calculations. The mesopores within Co–B nanoflakes help overcome the large Li+ diffusion barriers across 2D interfaces. As a result, the ZnCo2O4/Co–B electrode delivers high gravimetric/volumetric/areal capacities of 995 mAh g?1/1450 mAh cm?3/5.10 mAh cm?2, respectively, with robust rate capability and long‐term cyclability. The distinct interfacial design strategy provides a new direction for designing compacted conversion‐type anodes with superior lithium storage kinetics and stability for practical applications.  相似文献   

6.
ReS2 (rhenium disulfide) is a new transition‐metal dichalcogenide that exhibits 1T′ phase and extremely weak interlayer van der Waals interactions. This makes it promising as an anode material for sodium‐ion batteries. However, achieving both a high‐rate capability and a long‐life has remained a major research challenge. Here, a new composite is reported, in which both are realized for the first time. 1T′‐ReS2 is confined through strong interfacial interaction in a 2D‐honeycombed carbon nanosheets that comprise an rGO inter‐layer and a N‐doped carbon coating‐layer (rGO@ReS2@N‐C). The strong interfacial interaction between carbon and ReS2 increases overall conductivity and decreases Na+ diffusion resistance, whilst the intended 2D‐honeycombed carbon protective layer maintains structural morphology and electrochemical activity during long‐term cycling. These findings are confirmed by advanced characterization techniques, electrochemical measurement, and density functional theory calculation. The new rGO@ReS2@N‐C exhibits the greatest rate performance reported so far for ReS2 of 231 mAh g?1 at 10 A g?1. Significantly, this is together with ultra‐stable long‐term cycling of 192 mAh g?1 at 2 A g?1 after 4000 cycles.  相似文献   

7.
3D CoNi2S4‐graphene‐2D‐MoSe2 (CoNi2S4‐G‐MoSe2) nanocomposite is designed and prepared using a facile ultrasonication and hydrothermal method for supercapacitor (SC) applications. Because of the novel nanocomposite structures and resultant maximized synergistic effect among ultrathin MoSe2 nanosheets, highly conductive graphene and CoNi2S4 nanoparticles, the electrode exhibits rapid electron and ion transport rate and large electroactive surface area, resulting in its amazing electrochemical properties. The CoNi2S4‐G‐MoSe2 electrode demonstrates a maximum specific capacitance of 1141 F g?1, with capacitance retention of ≈108% after 2000 cycles at a high charge–discharge current density of 20 A g?1. As to its symmetric device, 109 F g?1 at a scan rate of 5 mV s?1 is exhibited. This pioneering work should be helpful in enhancing the capacitive performance of SC materials by designing nanostructures with efficient synergetic effects.  相似文献   

8.
Smart hybridization of active materials into tailored electrode structure is highly important for developing advanced electrochemical energy storage devices. With the help of sandwiched design, herein a powerful strategy is developed to fabricate three‐layer sandwiched composite core/shell arrays via combined hydrothermal and polymerization approaches. In such a unique architecture, wrinkled MoSe2 nanosheets are sandwiched by vertical graphene (VG) core and N‐doped carbon (N‐C) shell forming sandwiched core/shell arrays. Interesting advantages including high electrical conductivity, strong mechanical stability, and large porosity are combined in the self‐supported VG/MoSe2/N‐C sandwiched arrays. As a preliminary test, the sodium ion storage properties of VG/MoSe2/N‐C sandwiched arrays are characterized and demonstrated with high capacity (540 mA h g?1), enhanced high rate capability, and long‐term cycling stability (298 mA h g?1 at 2.0 A g?1 after 1000 cycles). The sandwiched core/shell structure plays positive roles in the enhancement of electrochemical performances due to dual conductive carbon networks, good volume accommodation, and highly porous structure with fast ion diffusion. The directional electrode design protocol provides a general method for synthesis of high‐performance ternary core/shell electrodes.  相似文献   

9.
Achieving high areal capacity is a challenge for current lithium‐ion batteries (LIBs). To address this issue, nickel foam (NF), as a free‐standing skeleton suffers from long‐term poor anchor ability for active materials, resulting in detachment from conductive substrates. In addition, the weighty NF damages the overall energy density of the electrode. Herein, an in situ fabrication of interlayer strategy is proposed to effectively address these issues through constructing layer‐by‐layer a 3D structure composed of an inner conductive framework, medial NiO layer, and outer few‐layer NiO nanoflowers in turn (NiO@NiO/NF). The interlayer derived from partial oxidation of NF not only reinforces the attachment of the active layer on NF but also contributes capacity to the whole electrode, leading to excellent stability and areal capacity. When used as the anode of LIBs, ultrahigh reversible capacity of 1.98 mAh cm?2 is delivered at 1.20 mA cm?2. The electrode still maintains good integrity and flexibility after 1000 cycles, showing good structure stability. Compared with previous reports, NiO@NiO/NF is one of the most outstanding NiO‐based electrodes. This work proposes a feasible strategy to enhance the capacity and stability of self‐supporting electrodes, and opens a new avenue for high‐areal‐capacity anode of LIBs.  相似文献   

10.
Rechargeable aqueous zinc‐ion batteries (ZIBs) are appealing due to their high safety, zinc abundance, and low cost. However, developing suitable cathode materials remains a great challenge. Herein, a novel 2D heterostructure of ultrathin amorphous vanadium pentoxide uniformly grown on graphene (A‐V2O5/G) with a very short ion diffusion pathway, abundant active sites, high electrical conductivity, and exceptional structural stability, is demonstrated for highly reversible aqueous ZIBs (A‐V2O5/G‐ZIBs), coupling with unprecedented high capacity, rate capability, long‐term cyclability, and excellent safety. As a result, 2D A‐V2O5/G heterostructures for stacked ZIBs at 0.1 A g?1 display an ultrahigh capacity of 489 mAh g?1, outperforming all reported ZIBs, with an admirable rate capability of 123 mAh g?1 even at 70 A g?1. Furthermore, the new‐concept prototype planar miniaturized zinc‐ion microbatteries (A‐V2O5/G‐ZIMBs), demonstrate a high volumetric capacity of 20 mAh cm?3 at 1 mA cm?2, long cyclability; holding high capacity retention of 80% after 3500 cycles, and in‐series integration, demonstrative of great potential for highly‐safe microsized power sources. Therefore, the exploration of such 2D heterostructure materials with strong synergy is a reliable strategy for developing safe and high‐performance energy storage devices.  相似文献   

11.
The fabrication of ultrasmall and high‐content SnO2 nanocrystals anchored on doped graphene can endow SnO2 with superior electrochemical properties. Herein, an effective strategy, involving molecular engineering of a layer‐by‐layer assembly technique, is proposed to homogeneously anchor SnO2 nanocrystals on nitrogen/sulfur codoped graphene (NSGS), which serves as an advanced anode material in lithium/sodium‐ion batteries (LIBs/SIBs). Benefiting from novel design and specific structure, the optimized NSGS for LIBs displays high initial capacity (2123.9 mAh g?1 at 0.1 A g?1), long‐term cycling performance (only 0.8% loss after 500 cycles), and good rate capability (477.4 mAh g?1 at 5 A g?1). In addition, the optimized NSGS for SIBs also delivers high initial capacity (791.7 mAh g?1 at 0.1 A g?1) and high reversible capacity (180.2 mAh g?1 after 500 cycles at 0.5 A g?1). Meanwhile, based on the detailed analysis of phase transition and electrochemical reaction kinetics, the reaction mechanisms of NSGS in LIBs and SIBs as well as the distinction in LIBs/SIBs are clearly articulated. Notably, to further explore the practical application, Li/Na+ full cells are also assembled by coupling the optimized NSGS anode with LiCoO2 and Na3V2(PO4)3/C cathodes, respectively.  相似文献   

12.
Achieving a high areal capacity is essential for the transfer of outstanding laboratory electrode results to commercial applications and also to ensure there exists a capacity matched cathode and anode for a properly tuned battery. Despite intensive efforts, most electrode materials exhibit areal capacities lower than that of the graphite anodes (4 mA h cm?2). An effective and low‐cost approach is reported to attain a high areal capacity via an intense densification by compacting a porous carbon nanotube sponge grafted with Co3O4 nanoparticles. The hybrid sponge can be compacted to a large degree (up to a tenfold densification) while still keeping its structural integrity and the 3D porous network. This method allows achieving a mass loading of up ?to 14.3 mg cm?2 and an areal capacity of 12 mA h cm?2 (at a current density of 200 mA g?1) together with a gravimetric capacity of >800 mA h g?1. This densification by compaction approach offers an effective and low‐cost strategy to develop high mass loading and areal capacity electrodes for practical energy storage systems.  相似文献   

13.
Secondary batteries based on earth‐abundant potassium metal anodes are attractive for stationary energy storage. However, suppressing the formation of potassium metal dendrites during cycling is pivotal in the development of future potassium metal‐based battery technology. Herein, a promising artificial solid‐electrolyte interphase (ASEI) design, simply covering a carbon nanotube (CNT) film on the surface of a potassium metal anode, is demonstrated. The results show that the spontaneously potassiated CNT framework with a stable self‐formed solid‐electrolyte interphase layer integrates a quasi‐hosting feature with fast interfacial ion transport, which enables dendrite‐free deposition of potassium at an ultrahigh capacity (20 mAh cm?2). Remarkably, the potassium metal anode exhibits an unprecedented cycle life (over 1000 cycles, over 2000 h) at a high current density of 5 mA cm?2 and a desirable areal capacity of 4 mAh cm?2. Dendrite‐free morphology in carbon‐fiber and carbon‐black‐based ASEI for potassium metal anodes, which indicates a broader promise of this approach, is also observed.  相似文献   

14.
The critical challenges of Li‐O2 batteries lie in sluggish oxygen redox kinetics and undesirable parasitic reactions during the oxygen reduction reaction and oxygen evolution reaction processes, inducing large overpotential and inferior cycle stability. Herein, an elaborately designed 3D hierarchical heterostructure comprising NiCo2S4@NiO core–shell arrays on conductive carbon paper is first reported as a freestanding cathode for Li‐O2 batteries. The unique hierarchical array structures can build up multidimensional channels for oxygen diffusion and electrolyte impregnation. A built‐in interfacial potential between NiCo2S4 and NiO can drastically enhance interfacial charge transfer kinetics. According to density functional theory calculations, intrinsic LiO2‐affinity characteristics of NiCo2S4 and NiO play an importantly synergistic role in promoting the formation of large peasecod‐like Li2O2, conducive to construct a low‐impedance Li2O2/cathode contact interface. As expected, Li‐O2 cells based on NiCo2S4@NiO electrode exhibit an improved overpotential of 0.88 V, a high discharge capacity of 10 050 mAh g?1 at 200 mA g?1, an excellent rate capability of 6150 mAh g?1 at 1.0 A g?1, and a long‐term cycle stability under a restricted capacity of 1000 mAh g?1 at 200 mA g?1. Notably, the reported strategy about heterostructure accouplement may pave a new avenue for the effective electrocatalyst design for Li‐O2 batteries.  相似文献   

15.
High energy‐density, low‐cost batteries are critically important to a variety of applications ranging from portable electronics to electric vehicles (EVs) and grid‐scale storage. While tremendous research effort has been focused on new materials or chemistries with high energy‐density potential, design innovations such as low‐tortuosity thick electrodes are another promising path toward higher energy density and lower cost. Growing demand for fast‐charging batteries has also highlighted the need for negative electrodes that can accept high rate charging without metal deposition; low tortuosity can be a benefit in this regard. However, a general and scalable fabrication method for low‐tortuosity electrodes is currently lacking. Here an emulsion‐based, magnetic‐alignment approach to producing thick electrodes (>400 µm thickness) with ultrahigh areal capacity (up to ≈14 mAh cm?2 vs 2–4 mAh cm?2 for conventional lithium ion) is reported. The process is demonstrated for LiCoO2 and meso‐carbon microbead graphite. The LiCoO2 cathodes are confirmed to have low tortuosity via DC‐depolarization experiments and deliver high areal capacity (>10 mAh cm?2) in galvanostatic discharge tests at practical C‐rates and model EV drive‐cycle tests. This simple fabrication method can potentially be applied to many other active materials to enable thick, low‐tortuosity electrodes.  相似文献   

16.
Aqueous batteries, particularly those integrating organic active materials functioning in a neutral pH environment, stand out as highly promising contenders in the stationary electrochemical storage domain, owing to their unparalleled safety, sustainability, and low‐cost materials. Herein, a novel di‐block oligomer, serving as the negative electrode of an all‐organic aqueous battery, is shown to offer exceptional output capabilities. The battery's performance is further enhanced by a unique intermixed p/n‐type storage mechanism, which is able to simultaneously exchange light and naturally abundant Na+, Mg2+, and Cl?. Reaching up to 105 mAh g?1, this system shows remarkable capacity retention for several thousand cycles (6500 cycles, ≈40 days) in various neutral electrolytes, including raw ocean water (≈3000 cycles, ≈75 days). The surprisingly fast kinetics of this di‐block oligomer allow to attain an unmatched specific capacity of near to 60 mAh g?1electrode while entirely devoid of conducting additives, and more than 80 mAh g?1electrode with 10% carbon additive, as well as displaying an areal capacity as high as 3.4 mAh cm?2 at C rate. Full cell validation was demonstrated over 1600 cycles by virtue of a commercial 2,2,6,6‐tétraméthylpipéridin‐1‐yl)oxyl (TEMPO) molecule, which permitted an energy density of close to 40 Wh kg?1materials at C rate in a self‐pH‐buffered and inexpensive aqueous electrolyte.  相似文献   

17.
Printed batteries are an emerging solution for integrated energy storage using low‐cost, high accuracy fabrication techniques. While several printed batteries have been previously shown, few have designed a battery that can be incorporated into an integrated device. Specifically, a fully printed battery with a small active electrode area (<1 cm2) achieving high areal capacities (>10 mAh cm?2) at high current densities (1–10 mA cm?2) has not been demonstrated, which represents the minimum form‐factor and performance requirements for many low‐power device applications. This work addresses these challenges by investigating the scaling limits of a fully printed Zn–Ag2O battery and determining the electrochemical limitations for a mm2‐scale battery. Processed entirely in air, Zn–Ag2O batteries are well suited for integration in typical semiconductor packaging flows compared to lithium‐based chemistries. Printed cells with electrodes as small as 1 mm2 maintain steady operating voltages above (>1.4 V) at high current densities (1–12 mA cm?2) and achieve the highest reported areal capacity for a fully printed battery at 11 mAh cm?2. The findings represent the first demonstration of a small, packaged, fully printed Zn–Ag2O battery with high areal capacities at high current densities, a crucial step toward realizing chip‐scale energy storage for integrated electronic systems.  相似文献   

18.
The recent trend in zinc (Zn) anode aqueous batteries has been to explore layered structures like manganese dioxides and vanadium oxides as Zn‐ion intercalation hosts. These structures, although novel, face limitations like their layered counterparts in lithium (Li)‐ion batteries, where the capacity is limited to the host's intercalation capacity. In this paper, a new strategy is proposed in enabling new generation of energy dense aqueous‐based batteries, where the conversion reactions of rock salt/spinel manganese oxides and carbon nanotube‐nested nanosized Zn electrodes are exploited to extract significantly higher capacity compared to intercalation systems. Accessing the conversion reactions allows to achieve high capacities of 750 mAh g?1 (≈30 mAh cm?2) from manganese oxide (MnO) and 810 mAh g?1 (≈30 mAh cm?2) from nanoscale Zn anodes, respectively. The high areal capacities help to attain unprecedented energy densities of 210 Wh per L‐cell and 320 Wh per kg‐total (398 Wh per kg‐active) from aqueous MnO|CNT‐Zn batteries, which allows an assessment of its viable use in a small‐scale automobile.  相似文献   

19.
The search for earth‐abundant and high‐performance electrode materials for sodium‐ion batteries represents an important challenge to current battery research. 2D transition metal dichalcogenides, particularly MoS2, have attracted increasing attention recently, but few of them so far have been able to meet expectations. In this study, it is demonstrated that another phase of molybdenum sulfide—amorphous chain‐like MoS3—can be a better choice as the anode material of sodium‐ion batteries. Highly compact MoS3 particles infiltrated with carbon nanotubes are prepared via the facile acid precipitation method in ethylene glycol. Compared to crystalline MoS2, the resultant amorphous MoS3 not only exhibits impressive gravimetric performance—featuring excellent specific capacity (≈615 mA h g?1), rate capability (235 mA h g?1 at 20 A g?1), and cycling stability but also shows exceptional volumetric capacity of ≈1000 mA h cm?3 and an areal capacity of >6.0 mA h cm?2 at very high areal loadings of active materials (up to 12 mg cm?2). The experimental results are supported by density functional theory simulations showing that the 1D chains of MoS3 can facilitate the adsorption and diffusion of Na+ ions. At last, it is demonstrated that the MoS3 anode can be paired with an Na3V2(PO4)3 cathode to afford full cells with great capacity and cycling performance.  相似文献   

20.
In this work, for the first time an in situ electrochemical pretreatment approach to fabricate a highly reversible oxygen electrode with redistributed ultrafine RuO2 catalysts on a carbon nanotube (CNT) matrix is reported. The optimally pretreated RuO2/CNT oxygen electrodes demonstrate an extremely stable cycling life, 800 times with non‐Li metal anode, under a capacity‐limited protocol of 800 mAh g?1 in an ether‐based electrolyte in an O2 environment. The highly stable activity of ultrafine RuO2 catalysts in oxygen reduction and evolution processes originates from the synergetic effect of greatly reduced size of catalyst (<2 nm) and uniform redistribution of catalyst particles after the in situ electrochemical pretreatment process. The pretreatment method discovered in this work can not only significantly enhance the activity/efficiency of the catalysts used for air electrodes but can also be widely applied to other electro‐catalysis systems.  相似文献   

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