Recently, hybrid supercapacitors (HSCs), which combine the use of battery and supercapacitor, have been extensively studied in order to satisfy increasing demands for large energy density and high power capability in energy-storage devices. For this purpose, the requirement for anode materials that provide enhanced charge storage sites (high capacity) and accommodate fast charge transport (high rate capability) has increased. Herein, therefore, a preparation of nanocomposite as anode material is presented and an advanced HSC using it is thoroughly analyzed. The HSC comprises a mesoporous Nb2O5/carbon (m-Nb2O5-C) nanocomposite anode synthesized by a simple one-pot method using a block copolymer assisted self-assembly and commercial activated carbon (MSP-20) cathode under organic electrolyte. The m-Nb2O5-C anode provides high specific capacity with outstanding rate performance and cyclability, mainly stemming from its enhanced pseudocapacitive behavior through introduction of a carbon-coated mesostructure within a voltage range from 3.0 to 1.1 V (vs Li/Li(+)). The HSC using the m-Nb2O5-C anode and MSP-20 cathode exhibits excellent energy and power densities (74 W h kg(-1) and 18,510 W kg(-1)), with advanced cycle life (capacity retention: ∼90% at 1000 mA g(-1) after 1000 cycles) within potential range from 1.0 to 3.5 V. In particular, we note that the highest power density (18,510 W kg(-1)) of HSC is achieved at 15 W h kg(-1), which is the highest level among similar HSC systems previously reported. With further study, the HSCs developed in this work could be a next-generation energy-storage device, bridging the performance gap between conventional batteries and supercapacitors.
Hybrid supercapacitors (battery-supercapacitor hybrid devices, HSCs) deliver high energy within seconds (excellent rate capability) with stable cyclability. One of the key limitations in developing high-performance HSCs is imbalance in power capability between the sluggish Faradaic lithium-intercalation anode and rapid non-Faradaic capacitive cathode. To solve this problem, we synthesize Nb2O5@carbon core-shell nanocyrstals (Nb2O5@C NCs) as high-power anode materials with controlled crystalline phases (orthorhombic (T) and pseudohexagonal (TT)) via a facile one-pot synthesis method based on a water-in-oil microemulsion system. The synthesis of ideal T-Nb2O5 for fast Li(+) diffusion is simply achieved by controlling the microemulsion parameter (e.g., pH control). The T-Nb2O5@C NCs shows a reversible specific capacity of ∼180 mA h g(-1) at 0.05 A g(-1) (1.1-3.0 V vs Li/Li(+)) with rapid rate capability compared to that of TT-Nb2O5@C and carbon shell-free Nb2O5 NCs, mainly due to synergistic effects of (i) the structural merit of T-Nb2O5 and (ii) the conductive carbon shell for high electron mobility. The highest energy (∼63 W h kg(-1)) and power (16 528 W kg(-1) achieved at ∼5 W h kg(-1)) densities within the voltage range of 1.0-3.5 V of the HSC using T-Nb2O5@C anode and MSP-20 cathode are remarkable.
Lithium–sulfur batteries (LSBs) are cost‐effective and high‐energy‐density batteries. However, the insulating nature of active materials, the shuttle effect, and slow redox kinetics lead to severe capacity decay and low rate capabilities. Numerous multimodal approaches have been attempted to tackle these issues and have pushed the cycle stability and energy density to higher levels. Recently, accelerating the redox kinetics using catalytic materials has been considered as a means to realize high‐performance LSBs. In this Minireview, we provide an insightful overview of the advances in the design of LSB catalytic materials and mechanistic descriptions of their catalytic activities.
Sodium‐ion hybrid supercapacitors (Na‐HSCs) have potential for mid‐ to large‐scale energy storage applications because of their high energy/power densities, long cycle life, and the low cost of sodium. However, one of the obstacles to developing Na‐HSCs is the imbalance of kinetics from different charge storage mechanisms between the sluggish faradaic anode and the rapid non‐faradaic capacitive cathode. Thus, to develop high‐power Na‐HSC anode materials, this paper presents the facile synthesis of nanocomposites comprising Nb2O5@Carbon core–shell nanoparticles (Nb2O5@C NPs) and reduced graphene oxide (rGO), and an analysis of their electrochemical performance with respect to various weight ratios of Nb2O5@C NPs to rGO (e.g., Nb2O5@C, Nb2O5@C/rGO‐70, ‐50, and ‐30). In a Na half‐cell configuration, the Nb2O5@C/rGO‐50 shows highly reversible capacity of ≈285 mA h g−1 at 0.025 A g−1 in the potential range of 0.01–3.0 V (vs Na/Na+). In addition, the Na‐HSC using the Nb2O5@C/rGO‐50 anode and activated carbon (MSP‐20) cathode delivers high energy/power densities (≈76 W h kg−1 and ≈20 800 W kg−1) with a stable cycle life in the potential range of 1.0–4.3 V. The energy and power densities of the Na‐HSC developed in this study are higher than those of similar Li‐ and Na‐HSCs previously reported.
In order to achieve high-power and -energy anodes operating above 1.0 V (vs Li/Li + ), titanium-based materials have been investigated for a long time. However, theoretically low lithium charge capacities of titanium-anodes have required new types of high-capacity anode materials. As a candidate, TiNb 2 O 7 has attracted much attention due to the high theoretical capacity of 387.6 mA h g −1 . However, the high formation temperature of the TiNb 2 O 7 phase resulted in large-sized TiNb 2 O 7 crystals, thus resulting in poor rate capability. Herein, ordered mesoporous TiNb 2 O 7 (denoted as m-TNO) was synthesized by block copolymer assisted self-assembly, and the resulting binary metal oxide was applied as an anode in a lithium ion battery. The nanocrystals (∼15 nm) developed inside the confined pore walls and large pores (∼40 nm) of m-TNO resulted in a short diffusion length for lithium ions/electrons and fast penetration of electrolyte. As a stable anode, the m-TNO electrode exhibited a high capacity of 289 mA h g −1 (at 0.1 C) and an excellent rate performance of 162 mA h g −1 at 20 C and 116 mA h g −1 at 50 C (= 19.35 A g −1 ) within a potential range of 1.0−3.0 V (vs Li/Li + ), which clearly surpasses other Ti-and Nb-based anode materials (TiO 2 , Li 4 Ti 5 O 12 , Nb 2 O 5 , etc.) and previously reported TiNb 2 O 7 materials. The m-TNO and carbon coated m-TNO electrodes also demonstrated stable cycle performances of 48 and 81% retention during 2,000 cycles at 10 C rate, respectively.
An ordered mesoporous WO(3-X) with high electrical conductivity (m-WO(3-X)) was prepared and evaluated as an anode material for lithium ion batteries (LIBs). Ordered mesoporous tungsten trioxide (m-WO(3)) with an identical pore structure to that of m-WO(3-X) and bulk WO(3-X) (b-WO(3-X)) was prepared for the comparison purpose. An m-WO(3-X) electrode exhibited a high reversible capacity (748 mAh g(-1), 6.5 Li/W) and a high volumetric capacity (∼1500 mAh cm(-3)), which is comparable to the Li metal itself (ca. 2000 mAh cm(-3)). Also, an improved rate capability and a good cyclability were observed in the m-WO(3-X) electrode when compared with m-WO(3) and b-WO(3-X) electrodes. From electrochemical impedance spectroscopy (EIS) analysis, the advanced anode performance of the m-WO(3-X) electrode was probably attributed to large ordered mesopores and a high electrical conductivity. Differential scanning calorimetry (DSC) result displayed that the safety of m-WO(3-X) was more improved than those of graphite and Si anode materials.
Hierarchically porous oxide materials have immense potential for applications in catalysis, separation, and energy devices, but the synthesis of these materials is hampered by the need to use multiple templates and the associated complicated steps and uncontrollable mixing behavior. Here we report a simple one-pot strategy for the synthesis of inorganic oxide materials with multiscale porosity. The inorganic precursor and block copolymer are coassembled into an ordered mesostructure (microphase separation), while the in situ-polymerized organic precursor forms organic-rich macrodomains (macrophase separation) around which the mesostructure grows. Calcination generates hierarchical meso/macroporous SiO2 and TiO2 with three-dimensionally interconnected pore networks. The continuous 3D macrostructures were clearly visualized by nanoscale X-ray computed tomography. The resulting TiO2 was used as the anode in a lithium ion battery and showed excellent rate capability compared with mesoporous TiO2. This work is of particular importance because it (i) expands the base of BCP self-assembly from mesostructures to complex porous structures, (ii) shows that the interplay of micro- and macrophase separation can be fully exploited for the design of hierarchically porous inorganic materials, and therefore (iii) provides strategies for researchers in materials science and polymer science.
Off-grid energy storage devices are becoming increasingly important to power distributed applications, such as the Internet of things, and smart city ubiquitous sensor systems. To date, this has been achieved by combining an energy storage device, e.g., a battery or capacitor with an energy harvester, e.g., a solar cell. However, this approach inherently increases the device footprint and the output voltages of energy harvesters often do not match those required by energy storage device. Here we propose the first photorechargeable zinc-ion capacitors, where graphitic carbon nitride acts simultaneously as the capacitor electrode and light harvesting material. This approach allows light to be used to recharge the capacitor directly and they can be operated in a continuous light powered mode. These capacitors show a photo-rechargeable specific capacitance of ∼11377 mF g −1 , a photo-charging voltage response of ∼850 mV, and a cyclability with ∼90% capacitance retention over 1000 cycles.
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