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2020 Volume 36 Issue 2
2020, 36(2): 190303
doi: 10.3866/PKU.WHXB201903034
Abstract:
Compressible supercapacitor is a promising flexible energy storage device in view of its excellent capacitive performance, which is recoverable at different compression states. The compressible electrode constitutes the core component that largely determines the performance of a compressible supercapacitor. Commercial polymer sponges are highly compressible materials because most of them are composed of elastic and interconnected polyurethane fibers. However, polymer sponges cannot be directly used as supercapacitor electrodes due to their non-conductive polymer framework. In contrast, carbon sponge (CS) derived from melamine sponge has superior compressible property and exhibits substantially improved conductivity compared to commercial polymer sponge. However, the low specific surface area of CS leads to low specific capacitance, which severely limits its application as compressible supercapacitor electrodes. Currently, pseudocapacitive materials are grown on the conductive CS framework to form hybrid electrodes with improved specific capacitance. Among various pseudocapacitive electrode, iron oxides have attracted considerable attentions due to their natural abundance, high theoretical specific capacitance, and negative working potential. Moreover, the much higher specific capacitance than that of carbon electrodes makes iron oxides one of promising negative candidates for configuring an asymmetric supercapacitor. Herein we report the successful growth of α-Fe2O3 nanosheets on CS by electrodeposition followed by low-temperature thermal annealing. The α-Fe2O3 on CS displays typical nanosheet morphology with mass loading ranging from 3.4 to 6.7 mg·cm-3 that can be facilely controlled by extending the deposition time from 4 to 16 h. The CS-Fe2O3 electrode retains 90% of its geometric height even after manual compression for 100 cycles. Moreover, the CS-Fe2O3 can withstand 60% strain even at Fe2O3 mass loading as high as 6.5 mg·cm-3. The performance of the CS-Fe2O3 electrode at different strains was systematically investigated in 3.0 mol·L-1 KOH aqueous electrolyte by cyclic voltammetry (CV), galvanostatic charge-discharge, and electrochemical impedance spectroscopy (EIS) in a three-electrode system. Our results show that the CS-Fe2O3 composite electrode produces lower specific capacitance at lower strain. The EIS characterization and IR drop results indicate that this is due to the larger internal resistance arising from looser contact of electrode with the current collector and longer ion diffusion length. Particularly, the CS-Fe2O3-12 electrode delivers a maximum specific capacitance of 294 F·g-1 at a current density of 1.0 A·g-1, 1.7-times higher than that of CS substrate. Assuming that the specific capacitance of CS-Fe2O3-12 is derived from the double-layer capacitance of CS and the pseudocapacitance of Fe2O3, the capacitance of Fe2O3 nanosheets in the hybrid is calculated to be as high as 421 F·g-1, much higher than most of recently reported results, showing that the sheet-like structure with more exposed active sites and short ion pathways could dramatically improve the utilization efficiency of the electrode for reversible faradaic reactions. More importantly, the CS-Fe2O3-12 electrode retains 87% of its initial capacitance after continuous charge-discharge at 5.0 A·g-1 for 10000 cycles, showing promising application as a stable and compressible supercapacitor electrode. ![]()
Compressible supercapacitor is a promising flexible energy storage device in view of its excellent capacitive performance, which is recoverable at different compression states. The compressible electrode constitutes the core component that largely determines the performance of a compressible supercapacitor. Commercial polymer sponges are highly compressible materials because most of them are composed of elastic and interconnected polyurethane fibers. However, polymer sponges cannot be directly used as supercapacitor electrodes due to their non-conductive polymer framework. In contrast, carbon sponge (CS) derived from melamine sponge has superior compressible property and exhibits substantially improved conductivity compared to commercial polymer sponge. However, the low specific surface area of CS leads to low specific capacitance, which severely limits its application as compressible supercapacitor electrodes. Currently, pseudocapacitive materials are grown on the conductive CS framework to form hybrid electrodes with improved specific capacitance. Among various pseudocapacitive electrode, iron oxides have attracted considerable attentions due to their natural abundance, high theoretical specific capacitance, and negative working potential. Moreover, the much higher specific capacitance than that of carbon electrodes makes iron oxides one of promising negative candidates for configuring an asymmetric supercapacitor. Herein we report the successful growth of α-Fe2O3 nanosheets on CS by electrodeposition followed by low-temperature thermal annealing. The α-Fe2O3 on CS displays typical nanosheet morphology with mass loading ranging from 3.4 to 6.7 mg·cm-3 that can be facilely controlled by extending the deposition time from 4 to 16 h. The CS-Fe2O3 electrode retains 90% of its geometric height even after manual compression for 100 cycles. Moreover, the CS-Fe2O3 can withstand 60% strain even at Fe2O3 mass loading as high as 6.5 mg·cm-3. The performance of the CS-Fe2O3 electrode at different strains was systematically investigated in 3.0 mol·L-1 KOH aqueous electrolyte by cyclic voltammetry (CV), galvanostatic charge-discharge, and electrochemical impedance spectroscopy (EIS) in a three-electrode system. Our results show that the CS-Fe2O3 composite electrode produces lower specific capacitance at lower strain. The EIS characterization and IR drop results indicate that this is due to the larger internal resistance arising from looser contact of electrode with the current collector and longer ion diffusion length. Particularly, the CS-Fe2O3-12 electrode delivers a maximum specific capacitance of 294 F·g-1 at a current density of 1.0 A·g-1, 1.7-times higher than that of CS substrate. Assuming that the specific capacitance of CS-Fe2O3-12 is derived from the double-layer capacitance of CS and the pseudocapacitance of Fe2O3, the capacitance of Fe2O3 nanosheets in the hybrid is calculated to be as high as 421 F·g-1, much higher than most of recently reported results, showing that the sheet-like structure with more exposed active sites and short ion pathways could dramatically improve the utilization efficiency of the electrode for reversible faradaic reactions. More importantly, the CS-Fe2O3-12 electrode retains 87% of its initial capacitance after continuous charge-discharge at 5.0 A·g-1 for 10000 cycles, showing promising application as a stable and compressible supercapacitor electrode.
2020, 36(2): 190304
doi: 10.3866/PKU.WHXB201903043
Abstract:
The rapid economic development has necessitated increased environmental protection and tremendous efforts have been devoted to designing and preparing environmentally friendly energy storage and conversion devices, including batteries, supercapacitors (SCs), and solar cells. As useful energy storage and conversion devices, SCs have received significant attention due to their high power density, long cycle stability, and rapid charging rate. The performance of SCs largely depends on the electrode materials, which can be composed of metal oxides, conducting polymers, carbon materials, and their composites. Carbon materials, including carbon nanotubes, carbon fibers, porous carbons, template carbons, and graphene-like carbon nanosheets (GCNSs), have attracted significant attention owing to their tailorable pore size and excellent physiochemical stability. GCNSs are considered to be outstanding carbon materials for use in high-performance SC because of their large specific surface area and high electrical conductivity. To date, many carbon precursors have been used to synthesize GCNSs for SCs such as coal, biomass, and chemical by-products. In particular, cheap and abundant chemical by-products for the synthesis of carbon materials can reduce preparation costs and environmental pollution as well as achieve high value-added chemicals. Coal tar, a by-product of the coal coking process, is rich in aromatic polycyclic hydrocarbon molecules, which can be polymerized, carbonized, and activated to synthesize GCNSs for SCs. In addition, MgO particles can be used as templates due to their stable properties and low-cost compared with other metal oxide templates (e.g. Fe2O3, NiO, or CuO), imparting space confinement and structure guidance during the preparation of GCNSs. Herein, we report a facile method for the preparation of interconnected graphene-like nanosheets (IGNSs) from coal tar by MgO templating combined with in-situ KOH activation. The IGNSs were obtained after the impurity removal by repeated washing with dilute acid. The as-synthesized IGNSs feature high specific surface area of up to 2887 m2∙g−1 and abundant hierarchical short pores, which provide abundant active sites for ion adsorption, supply plentiful channels for fast ion transport and boost electrical conductivity. As electrodes for SCs, IGNSs manifest high specific capacitance value of up to 313 F∙g−1 at 0.05 A∙g−1, good rate capability of 261 F∙g−1 at 20 A∙g−1, and excellent cycle stability with 92.7% of initial capacitance retained after 10000 cycles in 6 mol∙L−1 KOH aqueous electrolyte. This study provides a facile method for large-scale production of IGNSs from aromatic hydrocarbon molecules for use in high-performance energy storage devices. ![]()
The rapid economic development has necessitated increased environmental protection and tremendous efforts have been devoted to designing and preparing environmentally friendly energy storage and conversion devices, including batteries, supercapacitors (SCs), and solar cells. As useful energy storage and conversion devices, SCs have received significant attention due to their high power density, long cycle stability, and rapid charging rate. The performance of SCs largely depends on the electrode materials, which can be composed of metal oxides, conducting polymers, carbon materials, and their composites. Carbon materials, including carbon nanotubes, carbon fibers, porous carbons, template carbons, and graphene-like carbon nanosheets (GCNSs), have attracted significant attention owing to their tailorable pore size and excellent physiochemical stability. GCNSs are considered to be outstanding carbon materials for use in high-performance SC because of their large specific surface area and high electrical conductivity. To date, many carbon precursors have been used to synthesize GCNSs for SCs such as coal, biomass, and chemical by-products. In particular, cheap and abundant chemical by-products for the synthesis of carbon materials can reduce preparation costs and environmental pollution as well as achieve high value-added chemicals. Coal tar, a by-product of the coal coking process, is rich in aromatic polycyclic hydrocarbon molecules, which can be polymerized, carbonized, and activated to synthesize GCNSs for SCs. In addition, MgO particles can be used as templates due to their stable properties and low-cost compared with other metal oxide templates (e.g. Fe2O3, NiO, or CuO), imparting space confinement and structure guidance during the preparation of GCNSs. Herein, we report a facile method for the preparation of interconnected graphene-like nanosheets (IGNSs) from coal tar by MgO templating combined with in-situ KOH activation. The IGNSs were obtained after the impurity removal by repeated washing with dilute acid. The as-synthesized IGNSs feature high specific surface area of up to 2887 m2∙g−1 and abundant hierarchical short pores, which provide abundant active sites for ion adsorption, supply plentiful channels for fast ion transport and boost electrical conductivity. As electrodes for SCs, IGNSs manifest high specific capacitance value of up to 313 F∙g−1 at 0.05 A∙g−1, good rate capability of 261 F∙g−1 at 20 A∙g−1, and excellent cycle stability with 92.7% of initial capacitance retained after 10000 cycles in 6 mol∙L−1 KOH aqueous electrolyte. This study provides a facile method for large-scale production of IGNSs from aromatic hydrocarbon molecules for use in high-performance energy storage devices.
2020, 36(2): 190405
doi: 10.3866/PKU.WHXB201904050
Abstract:
The rapid development of electronic products has increased the demand for safe, low-cost, and high-performance energy storage devices. Lithium-ion batteries have been commercialized owing to their high energy density. However, the limited lithium resources and their uneven distribution have triggered the search for alternative energy storage systems. In this context, rechargeable aqueous zinc-ion batteries have gained immense attention owing to their low cost and environmental friendliness. Nevertheless, it is highly challenging to develop zinc-ion battery cathode materials with both high capacity and long cycle life. Hence, in this study, we prepared three-dimensional porous activated carbon (3DAC) with high specific surface area by using ethylenediaminetetraacetic acid (EDTA) tetrasodium salt hydrate as the raw material. We developed a zinc-ion hybrid capacitor (ZIHC) in 1 mol∙L−1 ZnSO4 using 3DAC as the cathode and a zinc foil as the anode. The ZIHC stored charge by the reversible deposition/dissolution of Zn2+ on the zinc anode and rapid reversible adsorption/desorption of ions on the 3DAC cathode. Owing to the large specific surface area and highly porous structure of the 3DAC cathode, the assembled ZIHC exhibited excellent electrochemical performance. It worked well over the voltage range of 0.1–1.7 V, providing a high specific capacitance of 213 mAh·g−1 at the current density of 0.5 A·g−1 (the highest value reported till date). The ZIHC showed specific capacities of 182, 160, 139, 130, 127, 122, and 116 mAh·g−1 at the current densities of 1, 2, 4, 6, 8, 10, and 20 A·g−1, respectively. Meanwhile, it exhibited the highest energy density of 164 Wh·kg−1 (at a power density of 390 W·kg−1) and still delivered the highest power density of 9.3 kW·kg−1 with a high energy density of 74 Wh·kg−1. In addition, our ZIHC also exhibited excellent cycling stability. After 20000 cycles at 10 A·g−1, it retained 90% of its initial capacity and exhibited high Coulombic efficiency (≈100%). In order to investigate the causes of capacity decay, we examined the cycled zinc foil by scanning electron microscopy and X-ray diffraction. The results showed that a large number of Zn4SO4(OH)6⋅3H2O disordered dendrites were formed on the surface of the zinc foil. These dendrites inhibited the reversible deposition/dissolution of zinc ions, resulting in the capacity decay of the ZIHC during the cycling process. This study will be helpful for developing next-generation high-performance energy storage devices. ![]()
The rapid development of electronic products has increased the demand for safe, low-cost, and high-performance energy storage devices. Lithium-ion batteries have been commercialized owing to their high energy density. However, the limited lithium resources and their uneven distribution have triggered the search for alternative energy storage systems. In this context, rechargeable aqueous zinc-ion batteries have gained immense attention owing to their low cost and environmental friendliness. Nevertheless, it is highly challenging to develop zinc-ion battery cathode materials with both high capacity and long cycle life. Hence, in this study, we prepared three-dimensional porous activated carbon (3DAC) with high specific surface area by using ethylenediaminetetraacetic acid (EDTA) tetrasodium salt hydrate as the raw material. We developed a zinc-ion hybrid capacitor (ZIHC) in 1 mol∙L−1 ZnSO4 using 3DAC as the cathode and a zinc foil as the anode. The ZIHC stored charge by the reversible deposition/dissolution of Zn2+ on the zinc anode and rapid reversible adsorption/desorption of ions on the 3DAC cathode. Owing to the large specific surface area and highly porous structure of the 3DAC cathode, the assembled ZIHC exhibited excellent electrochemical performance. It worked well over the voltage range of 0.1–1.7 V, providing a high specific capacitance of 213 mAh·g−1 at the current density of 0.5 A·g−1 (the highest value reported till date). The ZIHC showed specific capacities of 182, 160, 139, 130, 127, 122, and 116 mAh·g−1 at the current densities of 1, 2, 4, 6, 8, 10, and 20 A·g−1, respectively. Meanwhile, it exhibited the highest energy density of 164 Wh·kg−1 (at a power density of 390 W·kg−1) and still delivered the highest power density of 9.3 kW·kg−1 with a high energy density of 74 Wh·kg−1. In addition, our ZIHC also exhibited excellent cycling stability. After 20000 cycles at 10 A·g−1, it retained 90% of its initial capacity and exhibited high Coulombic efficiency (≈100%). In order to investigate the causes of capacity decay, we examined the cycled zinc foil by scanning electron microscopy and X-ray diffraction. The results showed that a large number of Zn4SO4(OH)6⋅3H2O disordered dendrites were formed on the surface of the zinc foil. These dendrites inhibited the reversible deposition/dissolution of zinc ions, resulting in the capacity decay of the ZIHC during the cycling process. This study will be helpful for developing next-generation high-performance energy storage devices.
2020, 36(2): 190305
doi: 10.3866/PKU.WHXB201903052
Abstract:
Supercapacitors have attracted considerable attention as new-generation energy storage devices because of their high charge-discharge rate, ultralong lifetime, and high power density. However, the performance of supercapacitors is severely restricted by either the low intrinsic capacitance of porous carbons or the poor conductivity and sluggish electrochemical kinetics of pseudocapacitive components. Therefore, high-performance electrode materials integrated with high gravimetric and volumetric capacitances, high rate capability, and superb cycling stability are urgently needed. As emerging carbon nanomaterials, carbon-/graphene quantum dots (CDs/GQDs) have uniquely small particle sizes, abundant edge sites, and various functional groups, thus endowing them with great potential for developing high-performance electrode materials for supercapacitors. With the purpose of identifying the application advantages and critical problems of CDs/GQDs for supercapacitor electrodes, this review summarizes the development of CDs/GQDs, quantum dots (QDs)/conductive carbon, QDs/metal oxides, QDs/conductive polymer composites, and QD-derived carbon materials in recent years. In each section of this paper, we introduce the typical and updated studies from corresponding fields in terms of novel preparation routes, the crucial roles of CDs/GQDs in composite materials, and the electrochemical performance of electrode materials and assembled devices. Finally, the advantages and limitations of CD/GQD electrode materials are described, and the future development of QD-based materials is discussed. In general, the previous studies have shown that when directly used as electrode materials for micro-supercapacitors, CDs/GQDs performed at an ultrahigh charge-discharge rate of up to 1000 V∙s−1. However, because of the discontinuous conductive network and good dispersibility in electrolytes, they are not suitable for use in common devices because of poor cycle stability. One of the most promising means for fully realizing active ion storage sites for portable devices is to strongly anchor CDs/GQDs onto conductive carbon scaffolds such as activated carbon, graphene nanosheets, and carbon nanofibers. QDs simultaneously improve the capacitive and rate performance owing to the active sites and improved surface wettability of the composite materials. To further improve the capacitance and cycle stability of electrode materials, different types of QDs/pseudocapacitive material composites (metal oxides or conductive polymers) have been developed. QDs have been shown to increase entire conductivity, accelerate ion transport, and depress the volume expansion of metal oxides and conductive polymers. Benefiting from their small-sized structure and outstanding reactivity, CDs/GQDs can also be used as emerging precursors for constructing advanced carbon electrode materials. Several forward-looking studies have shown that QDs can be converted to carbon nanosheets, heteroatom-doped carbon, and dense and porous carbon blocks with high gravimetric/volumetric capacitances and remarkable rate performance for fast and compact energy storage. Although related fields have rapidly developed in recent years, several critical problems including those related to green and effective methods to prepare CDs/GQDs, construction of entire conductive networks without active sites being sacrificed, the synergistic effect, and the underlying mechanism of QDs in composite materials still must be solved. We hope that this review can provide inspiration and references for further investigation in this promising field. ![]()
Supercapacitors have attracted considerable attention as new-generation energy storage devices because of their high charge-discharge rate, ultralong lifetime, and high power density. However, the performance of supercapacitors is severely restricted by either the low intrinsic capacitance of porous carbons or the poor conductivity and sluggish electrochemical kinetics of pseudocapacitive components. Therefore, high-performance electrode materials integrated with high gravimetric and volumetric capacitances, high rate capability, and superb cycling stability are urgently needed. As emerging carbon nanomaterials, carbon-/graphene quantum dots (CDs/GQDs) have uniquely small particle sizes, abundant edge sites, and various functional groups, thus endowing them with great potential for developing high-performance electrode materials for supercapacitors. With the purpose of identifying the application advantages and critical problems of CDs/GQDs for supercapacitor electrodes, this review summarizes the development of CDs/GQDs, quantum dots (QDs)/conductive carbon, QDs/metal oxides, QDs/conductive polymer composites, and QD-derived carbon materials in recent years. In each section of this paper, we introduce the typical and updated studies from corresponding fields in terms of novel preparation routes, the crucial roles of CDs/GQDs in composite materials, and the electrochemical performance of electrode materials and assembled devices. Finally, the advantages and limitations of CD/GQD electrode materials are described, and the future development of QD-based materials is discussed. In general, the previous studies have shown that when directly used as electrode materials for micro-supercapacitors, CDs/GQDs performed at an ultrahigh charge-discharge rate of up to 1000 V∙s−1. However, because of the discontinuous conductive network and good dispersibility in electrolytes, they are not suitable for use in common devices because of poor cycle stability. One of the most promising means for fully realizing active ion storage sites for portable devices is to strongly anchor CDs/GQDs onto conductive carbon scaffolds such as activated carbon, graphene nanosheets, and carbon nanofibers. QDs simultaneously improve the capacitive and rate performance owing to the active sites and improved surface wettability of the composite materials. To further improve the capacitance and cycle stability of electrode materials, different types of QDs/pseudocapacitive material composites (metal oxides or conductive polymers) have been developed. QDs have been shown to increase entire conductivity, accelerate ion transport, and depress the volume expansion of metal oxides and conductive polymers. Benefiting from their small-sized structure and outstanding reactivity, CDs/GQDs can also be used as emerging precursors for constructing advanced carbon electrode materials. Several forward-looking studies have shown that QDs can be converted to carbon nanosheets, heteroatom-doped carbon, and dense and porous carbon blocks with high gravimetric/volumetric capacitances and remarkable rate performance for fast and compact energy storage. Although related fields have rapidly developed in recent years, several critical problems including those related to green and effective methods to prepare CDs/GQDs, construction of entire conductive networks without active sites being sacrificed, the synergistic effect, and the underlying mechanism of QDs in composite materials still must be solved. We hope that this review can provide inspiration and references for further investigation in this promising field.
2020, 36(2): 190305
doi: 10.3866/PKU.WHXB201903055
Abstract:
Supercapacitors have been widely used in various fields because of their high power density, long cycle life, and cost-effectiveness. Plant-based porous carbon continues to be the most suitable alternative for manufacturing the commercial electrode materials of supercapacitors because of its good electrochemical performance, simple preparation process, high availability, and low cost. Although plant-based porous carbon prepared using physical activation has been widely used in commercial supercapacitors, its performance is severely restricted because of its low value of specific surface area and highly microporous structure. With a view to achieving high values of specific gravimetric/volumetric capacitances and outstanding rate performance in supercapacitors, this review summarizes the recently developed methods for preparing plant-based ultrahigh specific surface area porous carbon materials, mesoporous carbon materials, hierarchical porous carbon materials, and nitrogen-doped porous carbon materials. The factors affecting the electrochemical performance of plant-based porous carbon are also discussed. We also summarize some novel strategies to improve the volumetric electrochemical performance of plant-based porous carbon materials, such as preparing dense and porous carbon materials, performing heteroatom doping, and combining the carbon with pseudocapacitive materials (conductive polymers or metal oxides). Finally, the challenges and perspectives of using plant-based porous carbon in supercapacitors are also proposed. In brief, when used as the electrode material for supercapacitors, the ultrahigh surface area porous carbon prepared by KOH activation shows high value of specific capacitance at low current densities. However, the tortuous and deep micropores in the plant-based porous carbon result in its sluggish ion-transport kinetics and high value of equivalent series resistance, which, in turn, result in poor rate performance. To improve the rate performance, tremendous efforts have been made to introduce mesopores in the carbon as ion-transport channels. However, this strategy usually involves the coalescence of a large number of micropores, resulting in the reduced surface area as well as energy storage ability of the carbon. Hence, many researchers have utilized the inherent porous structure and inorganic templates of plants to prepare hierarchical porous carbon both with high specific surface area and high mesopore volume for use in devices with high capacitance and power. In addition to altering the surface area and pore structure of the carbon, doping with nitrogen is another promising approach to enhance the capacitance and electronic conductivity of the plant-based porous carbon. Surface nitrogen can be introduced by the direct carbonization/activation of nitrogen-rich plant precursors or by the reaction of the carbon with nitrogen-containing reagents. Porous carbon with large specific area and with developed mesoporous structure may exhibit superior gravimetric capacitance but inferior volumetric capacitance because of the trade-off between its well-developed microporous structure and packing density. To improve the volume performance, some methods, such as preparing dense and porous carbon with reasonably porous structure, using heteroatom-doped carbon, and incorporating the carbon with pseudocapacitive materials, have been developed. Although the electrochemical performance of plant-based porous carbon has been significantly improved using the aforementioned methods, yet issues such as the lack of green methods and low-cost activation methods to prepare large surface area porous carbon, the design and controlled modulation of carbon micro-structures, the influence of heteroatom doping on pseudocapacitance, and weak interaction between pseudocapacitive components and plant-based porous carbon still need to be resolved. We hope that this review may provide the necessary background and ideas to develop more effective preparation methods for high-performance plant-based porous carbon. ![]()
Supercapacitors have been widely used in various fields because of their high power density, long cycle life, and cost-effectiveness. Plant-based porous carbon continues to be the most suitable alternative for manufacturing the commercial electrode materials of supercapacitors because of its good electrochemical performance, simple preparation process, high availability, and low cost. Although plant-based porous carbon prepared using physical activation has been widely used in commercial supercapacitors, its performance is severely restricted because of its low value of specific surface area and highly microporous structure. With a view to achieving high values of specific gravimetric/volumetric capacitances and outstanding rate performance in supercapacitors, this review summarizes the recently developed methods for preparing plant-based ultrahigh specific surface area porous carbon materials, mesoporous carbon materials, hierarchical porous carbon materials, and nitrogen-doped porous carbon materials. The factors affecting the electrochemical performance of plant-based porous carbon are also discussed. We also summarize some novel strategies to improve the volumetric electrochemical performance of plant-based porous carbon materials, such as preparing dense and porous carbon materials, performing heteroatom doping, and combining the carbon with pseudocapacitive materials (conductive polymers or metal oxides). Finally, the challenges and perspectives of using plant-based porous carbon in supercapacitors are also proposed. In brief, when used as the electrode material for supercapacitors, the ultrahigh surface area porous carbon prepared by KOH activation shows high value of specific capacitance at low current densities. However, the tortuous and deep micropores in the plant-based porous carbon result in its sluggish ion-transport kinetics and high value of equivalent series resistance, which, in turn, result in poor rate performance. To improve the rate performance, tremendous efforts have been made to introduce mesopores in the carbon as ion-transport channels. However, this strategy usually involves the coalescence of a large number of micropores, resulting in the reduced surface area as well as energy storage ability of the carbon. Hence, many researchers have utilized the inherent porous structure and inorganic templates of plants to prepare hierarchical porous carbon both with high specific surface area and high mesopore volume for use in devices with high capacitance and power. In addition to altering the surface area and pore structure of the carbon, doping with nitrogen is another promising approach to enhance the capacitance and electronic conductivity of the plant-based porous carbon. Surface nitrogen can be introduced by the direct carbonization/activation of nitrogen-rich plant precursors or by the reaction of the carbon with nitrogen-containing reagents. Porous carbon with large specific area and with developed mesoporous structure may exhibit superior gravimetric capacitance but inferior volumetric capacitance because of the trade-off between its well-developed microporous structure and packing density. To improve the volume performance, some methods, such as preparing dense and porous carbon with reasonably porous structure, using heteroatom-doped carbon, and incorporating the carbon with pseudocapacitive materials, have been developed. Although the electrochemical performance of plant-based porous carbon has been significantly improved using the aforementioned methods, yet issues such as the lack of green methods and low-cost activation methods to prepare large surface area porous carbon, the design and controlled modulation of carbon micro-structures, the influence of heteroatom doping on pseudocapacitance, and weak interaction between pseudocapacitive components and plant-based porous carbon still need to be resolved. We hope that this review may provide the necessary background and ideas to develop more effective preparation methods for high-performance plant-based porous carbon.
2020, 36(2): 190400
doi: 10.3866/PKU.WHXB201904007
Abstract:
The world is currently facing a series of energy-related problems and challenges. In response, scientists are committed to seeking green high-performance energy storage devices to meet the demands of long-term, sustainable, and innovative development in the future. As a new type of green energy storage device, the supercapacitor has the advantages of high power density, high theoretical specific capacitance, fast charge and discharge speed, long cycle life, high safety, environmental friendliness, and economy to help people cope with the energy crisis. In addition, energy storage devices including Li-ion batteries and supercapacitors are being transformed from heavy, rigid, and bulky devices into light, flexible, and small units to fulfill the needs of the next generation. Among these energy storage systems, the electrode material is an important factor affecting the performance of supercapacitors. In recent years, supercapacitors based on manganese dioxide have been widely studied owing to their high theoretical specific capacitance, good chemical stability, and environmental friendliness. At the same time, a variety of two-dimensional materials are also used as supercapacitor electrode materials after graphene. Two-dimensional structural features play an important role in improving the energy density of electric double-layer capacitors and improving the pseudocapacitance of capacitors. To achieve high specific capacitance and high rate of performance, combining manganese dioxide with two-dimensional materials is a promising option. In this paper, we systematically introduce the application of composites that combine two-dimensional materials represented by graphene and manganese dioxide in supercapacitors, and considers the electrochemical properties of these composites. However, there is still a long way to go in order to fabricate a suitable hierarchical structure consisting of two-dimensional materials and manganese dioxide. For example, a suitable two-dimensional material must be chosen and combined with manganese dioxide to form composites that possess excellent electrochemical properties. In addition, the fabrication methods for these composites are a principal factor that affects their performance. Thus, there are reasons for us to strongly believe that if these key issues are resolved, the properties of these composites consisting of manganese dioxide and two-dimensional materials will make great progress. Overall, this paper only points out some general directions for these kinds of composites in the future, such as principles for choosing the two-dimensional materials to combine with manganese dioxide, and the composite methods which have been reported previously. We are pleased that other researchers are being inspired by our work, and we are looking forward to seeing better studies in this field. ![]()
The world is currently facing a series of energy-related problems and challenges. In response, scientists are committed to seeking green high-performance energy storage devices to meet the demands of long-term, sustainable, and innovative development in the future. As a new type of green energy storage device, the supercapacitor has the advantages of high power density, high theoretical specific capacitance, fast charge and discharge speed, long cycle life, high safety, environmental friendliness, and economy to help people cope with the energy crisis. In addition, energy storage devices including Li-ion batteries and supercapacitors are being transformed from heavy, rigid, and bulky devices into light, flexible, and small units to fulfill the needs of the next generation. Among these energy storage systems, the electrode material is an important factor affecting the performance of supercapacitors. In recent years, supercapacitors based on manganese dioxide have been widely studied owing to their high theoretical specific capacitance, good chemical stability, and environmental friendliness. At the same time, a variety of two-dimensional materials are also used as supercapacitor electrode materials after graphene. Two-dimensional structural features play an important role in improving the energy density of electric double-layer capacitors and improving the pseudocapacitance of capacitors. To achieve high specific capacitance and high rate of performance, combining manganese dioxide with two-dimensional materials is a promising option. In this paper, we systematically introduce the application of composites that combine two-dimensional materials represented by graphene and manganese dioxide in supercapacitors, and considers the electrochemical properties of these composites. However, there is still a long way to go in order to fabricate a suitable hierarchical structure consisting of two-dimensional materials and manganese dioxide. For example, a suitable two-dimensional material must be chosen and combined with manganese dioxide to form composites that possess excellent electrochemical properties. In addition, the fabrication methods for these composites are a principal factor that affects their performance. Thus, there are reasons for us to strongly believe that if these key issues are resolved, the properties of these composites consisting of manganese dioxide and two-dimensional materials will make great progress. Overall, this paper only points out some general directions for these kinds of composites in the future, such as principles for choosing the two-dimensional materials to combine with manganese dioxide, and the composite methods which have been reported previously. We are pleased that other researchers are being inspired by our work, and we are looking forward to seeing better studies in this field.
2020, 36(2): 190405
doi: 10.3866/PKU.WHXB201904056
Abstract:
The increased demand for high-performance supercapacitors has fueled the development of electrode materials. As an important part of supercapacitors, the electrochemical performance of the supercapacitor is directly affected by the specific surface area, conductivity, electrochemical activity, and stability of electrode materials. In the traditional manufacturing method, a binder must be added to powdered electrode materials to enhance their combination with the current collector, which could lead to morphology damage, pore blockage, and reduced conductivity of active materials that will adversely affect their electrochemical behavior. Thus, research on binder-free electrode materials has attracted significant interest. Recently, electrospun nanofibers have been widely used as supercapacitor electrode materials because of their advantages such as large specific surface area, high porosity, and easy preparation. The attainable continuity and flexibility endow electrospun nanofiber membranes outstanding performance among large numbers of binder-free materials. This review considers recent studies on electrospun nanofiber-based binder-free electrode materials for supercapacitors, including carbon nanofibers, carbon-based composite nanofibers, conductive polymer-based composite nanofibers, and metal oxide nanofibers. These studies demonstrate that pore structure construction, activation treatment, and nitrogen doping can improve the specific surface area, electrochemical activity, wettability, and graphitization degree of carbon nanofibers to enhance their electrochemical properties. Moreover, combining carbon nanofibers with metal oxides, metal sulfides, metal carbides, and conductive polymers by methods such as blending, chemical deposition, electrochemical deposition, etc., can improve their capacitance, rate performance, and cycling stabilities, which complement the advantages of different materials and proves that the performance of multicomponent materials is better than that of single-component materials. In particular, conductive polymers based on composite nanofibers and metal oxide nanofibers can be used as binder-free materials by electrospinning technology, but their dependence on other substances as well as fragile fiber membrane limit their widespread application. Therefore, in order to ensure the continuity or flexibility of fiber membranes, carbon-based composite nanofibers with multicomponent and hierarchical structure could potentially be used/constructed as binder-free electrode materials. Combinations with new types of electrode materials such as metal-organic frameworks (MOF), covalent organic frameworks (COF), MXenes, metal nitride, metal phosphide, etc., and the preparation of materials with novel structures have also been attempted. In order to realize the practical application of eletrospun nanofiber-based binder-free electrode materials, more attention should be given to improving their mechanical properties, production efficiency, and research on the application of flexible devices. We hope that this review can broaden ideas for improving the development and application of electrospun nanofiber-based binder-free electrode materials for high-performance supercapacitors. ![]()
The increased demand for high-performance supercapacitors has fueled the development of electrode materials. As an important part of supercapacitors, the electrochemical performance of the supercapacitor is directly affected by the specific surface area, conductivity, electrochemical activity, and stability of electrode materials. In the traditional manufacturing method, a binder must be added to powdered electrode materials to enhance their combination with the current collector, which could lead to morphology damage, pore blockage, and reduced conductivity of active materials that will adversely affect their electrochemical behavior. Thus, research on binder-free electrode materials has attracted significant interest. Recently, electrospun nanofibers have been widely used as supercapacitor electrode materials because of their advantages such as large specific surface area, high porosity, and easy preparation. The attainable continuity and flexibility endow electrospun nanofiber membranes outstanding performance among large numbers of binder-free materials. This review considers recent studies on electrospun nanofiber-based binder-free electrode materials for supercapacitors, including carbon nanofibers, carbon-based composite nanofibers, conductive polymer-based composite nanofibers, and metal oxide nanofibers. These studies demonstrate that pore structure construction, activation treatment, and nitrogen doping can improve the specific surface area, electrochemical activity, wettability, and graphitization degree of carbon nanofibers to enhance their electrochemical properties. Moreover, combining carbon nanofibers with metal oxides, metal sulfides, metal carbides, and conductive polymers by methods such as blending, chemical deposition, electrochemical deposition, etc., can improve their capacitance, rate performance, and cycling stabilities, which complement the advantages of different materials and proves that the performance of multicomponent materials is better than that of single-component materials. In particular, conductive polymers based on composite nanofibers and metal oxide nanofibers can be used as binder-free materials by electrospinning technology, but their dependence on other substances as well as fragile fiber membrane limit their widespread application. Therefore, in order to ensure the continuity or flexibility of fiber membranes, carbon-based composite nanofibers with multicomponent and hierarchical structure could potentially be used/constructed as binder-free electrode materials. Combinations with new types of electrode materials such as metal-organic frameworks (MOF), covalent organic frameworks (COF), MXenes, metal nitride, metal phosphide, etc., and the preparation of materials with novel structures have also been attempted. In order to realize the practical application of eletrospun nanofiber-based binder-free electrode materials, more attention should be given to improving their mechanical properties, production efficiency, and research on the application of flexible devices. We hope that this review can broaden ideas for improving the development and application of electrospun nanofiber-based binder-free electrode materials for high-performance supercapacitors.
Two-Dimensional Nanosheet Hole Strategy and Their Assembled Materials for Supercapacitor Application
2020, 36(2): 190503
doi: 10.3866/PKU.WHXB201905032
Abstract:
Owing to their high power density, excellent rate performance, and good cycle performance, supercapacitors are widely used for energy storage applications. Two-dimensional (2D) layered materials are structural compounds having a layered host structure with a layer thickness of nanometers and a lateral dimension of several micrometers. Their layer spacing can be controlled by changing the interaction between the layers. 2D layered materials can be delaminated into nanosheets. Exfoliated nanosheet materials provide a new strategy for improving the performance of supercapacitors. Unlike bulk layered materials, the exfoliated nanosheets not only provide a unique nano-scale reaction space for electrochemical reactions, but also offer the possibility for improving the specific capacitance and storage rate of the supercapacitor. However, in 2D layered materials, the ion or electron transport in the vertical direction is obstructed, despite their fast ion and electron transport in the horizontal direction. As a result, the occurrence of electrode reactions, and hence the realization of rapid storage become difficult. It is detrimental to the power and energy densities and rapid energy storage of supercapacitors. Therefore, it is imperative to develop novel electrode materials in order to fabricate supercapacitors showinghigh energy densities at high power densities. Porous 2D layered electrode materials offer two major advantages. First, the porous structure can alleviate the problems caused by the stacking of nanosheets during the assembly process. Second, the porous structure can effectively promote the electrolyte penetration of the electrode, which alleviates the volume changes of the electrode material during the charging-discharging process and releases the structural strain. Hence, such materials facilitate ion or electron transport, thus increasing the specific capacitance of the supercapacitor. Over the past few years, 2D nanosheet holeization has evolved as a promising approach to improve the energy density of supercapacitors at high power densities. Various porous 2D layered supercapacitor electrode materials have been developed. This paper reviews the exfoliation of 2D layered materials, nanosheet holeization strategy, and the application of assembled porous layered electrode materials in supercapacitors. In this paper, we have reviewed the exfoliation of 2D layered materials with different electric properties and the performance of 2D nanosheets. Different methods used for the preparation of holey 2D nanosheets have also been discussed. We prepared holey MnO2 nanosheets and reduced graphite oxide via redox holeization mechanism, and 2D porous nanomaterials were also prepared by using suitable templates such as hard or self-sustaining templates. These holey 2D nanosheets were used to prepare porous 2D layered electrode materials such as holey graphene/manganese dioxide composite fibers and holey graphene/polypyrrole hybrid aerogels. The capacitance of these electrode materials was investigated systematically. Finally, the prospects for the development of porous 2D layered electrode materials such as the optimization of theirrate performance, flexibility, and energy density were discussed. Novel holeization methods should be developed in order to prepare metal oxide nanosheets with controllable hole sizes. In addition, other 2D materials such as MXene should be explored.
Owing to their high power density, excellent rate performance, and good cycle performance, supercapacitors are widely used for energy storage applications. Two-dimensional (2D) layered materials are structural compounds having a layered host structure with a layer thickness of nanometers and a lateral dimension of several micrometers. Their layer spacing can be controlled by changing the interaction between the layers. 2D layered materials can be delaminated into nanosheets. Exfoliated nanosheet materials provide a new strategy for improving the performance of supercapacitors. Unlike bulk layered materials, the exfoliated nanosheets not only provide a unique nano-scale reaction space for electrochemical reactions, but also offer the possibility for improving the specific capacitance and storage rate of the supercapacitor. However, in 2D layered materials, the ion or electron transport in the vertical direction is obstructed, despite their fast ion and electron transport in the horizontal direction. As a result, the occurrence of electrode reactions, and hence the realization of rapid storage become difficult. It is detrimental to the power and energy densities and rapid energy storage of supercapacitors. Therefore, it is imperative to develop novel electrode materials in order to fabricate supercapacitors showinghigh energy densities at high power densities. Porous 2D layered electrode materials offer two major advantages. First, the porous structure can alleviate the problems caused by the stacking of nanosheets during the assembly process. Second, the porous structure can effectively promote the electrolyte penetration of the electrode, which alleviates the volume changes of the electrode material during the charging-discharging process and releases the structural strain. Hence, such materials facilitate ion or electron transport, thus increasing the specific capacitance of the supercapacitor. Over the past few years, 2D nanosheet holeization has evolved as a promising approach to improve the energy density of supercapacitors at high power densities. Various porous 2D layered supercapacitor electrode materials have been developed. This paper reviews the exfoliation of 2D layered materials, nanosheet holeization strategy, and the application of assembled porous layered electrode materials in supercapacitors. In this paper, we have reviewed the exfoliation of 2D layered materials with different electric properties and the performance of 2D nanosheets. Different methods used for the preparation of holey 2D nanosheets have also been discussed. We prepared holey MnO2 nanosheets and reduced graphite oxide via redox holeization mechanism, and 2D porous nanomaterials were also prepared by using suitable templates such as hard or self-sustaining templates. These holey 2D nanosheets were used to prepare porous 2D layered electrode materials such as holey graphene/manganese dioxide composite fibers and holey graphene/polypyrrole hybrid aerogels. The capacitance of these electrode materials was investigated systematically. Finally, the prospects for the development of porous 2D layered electrode materials such as the optimization of theirrate performance, flexibility, and energy density were discussed. Novel holeization methods should be developed in order to prepare metal oxide nanosheets with controllable hole sizes. In addition, other 2D materials such as MXene should be explored.
2020, 36(2): 190402
doi: 10.3866/PKU.WHXB201904025
Abstract:
Carbon materials can offer various micro- and nanostructures as well as bulk and surface functionalities; hence, they remain the most popular for manufacturing supercapacitors. This article critically reviews recent developments in the preparation of carbon materials from new precursors for supercapacitors. Typical examples are activated carbon (AC) and graphene, which can be prepared from various conventional and new precursors such as biomass, polymers, graphite oxide, CH4, and even CO2 via innovative processes to achieve low-cost and/or high specific capacitance. Specifically, when producing AC from natural biomasses or synthetic polymers, either new, spent, or waste, popular activation agents, such as KOH and ZnCl2, are often used to process the ACs derived from these new precursors while the respective activation mechanisms always attract interest. The traditional two-step calcination process at high temperatures is widely employed to achieve high performance, with or without retaining the morphology of the precursors. The three-step calcination, including a post-vacuum treatment, is also the preferred choice in many cases, but it can increase the cost per capacity (kWh∙g−1). More recently, one-step molecular activation promises a better and more economical approach to the commercial application of AC, although further increase of the yield is necessary. In addition to activation, graphitization, N doping, and template control can further improve ACs in terms of the charging and discharging rates, or pseudocapacitance, or both. Considerations are also given to material structure design, and carbon regeneration during activation. Metal-organic frameworks, which were initially used as templates, have been found to be good direct carbon precursors. Various graphene structures, including powders, films, aerogels, foams, and fibers, can be produced from graphite oxide, CO2, and CH4. Similar to AC, graphene can possess micropores by activation. Self-propagating high-temperature synthesis and molten salt processing are newly-reported methods for fabrication of mesoporous graphene. Macroporous graphene hydrogels can be produced by hydrothermal treatment of graphite oxide suspension, which can also be transferred into films. Hierarchically porous structures can be achieved by H2O2 etching or ZnCl2 activation of the macroporous graphene precursor. Sponges as templates combined with KOH activation are applied to create both micro- and macropores in graphene foams. Graphene can grow on fibers and textiles by electrodeposition, dip-coating, or filtration, which can be woven into clothes with a large area or thick loading, illuminating the potential application in flexible and wearable supercapacitors. The key obstacles in AC and graphene production are high cost, low yield, low packing density, and low working potential range. Most Carbon materials derived from new precursors work very well with aqueous electrolytes. Charge storage occurs not only in the electric double layer (i.e., the "carbon | electrolyte" interface), but also via redox activity in association with the bulk and surface functionalities, and the resulting partial delocalization of valence electrons. The analysis of the capacitive electrode has shown a design defect that prevents the working voltage of a symmetrical supercapacitor from reaching the full potential window of the carbon material. This defect can be avoided in AC-based supercapacitors with unequal electrode capacitances, leading to higher cell voltages and hence higher specific energy than their symmetrical counterparts. There are also emerging ways to raise the energy capacity of AC supercapacitors, such as the use of redox electrolytes to enable the Nernstian charge storage mechanism, and of the three dimensional printing method for a desirable electrode structure. All these developments are promising carbon materials from various precursors of new and waste sources for a more affordable and sustainable supercapacitor technology. ![]()
Carbon materials can offer various micro- and nanostructures as well as bulk and surface functionalities; hence, they remain the most popular for manufacturing supercapacitors. This article critically reviews recent developments in the preparation of carbon materials from new precursors for supercapacitors. Typical examples are activated carbon (AC) and graphene, which can be prepared from various conventional and new precursors such as biomass, polymers, graphite oxide, CH4, and even CO2 via innovative processes to achieve low-cost and/or high specific capacitance. Specifically, when producing AC from natural biomasses or synthetic polymers, either new, spent, or waste, popular activation agents, such as KOH and ZnCl2, are often used to process the ACs derived from these new precursors while the respective activation mechanisms always attract interest. The traditional two-step calcination process at high temperatures is widely employed to achieve high performance, with or without retaining the morphology of the precursors. The three-step calcination, including a post-vacuum treatment, is also the preferred choice in many cases, but it can increase the cost per capacity (kWh∙g−1). More recently, one-step molecular activation promises a better and more economical approach to the commercial application of AC, although further increase of the yield is necessary. In addition to activation, graphitization, N doping, and template control can further improve ACs in terms of the charging and discharging rates, or pseudocapacitance, or both. Considerations are also given to material structure design, and carbon regeneration during activation. Metal-organic frameworks, which were initially used as templates, have been found to be good direct carbon precursors. Various graphene structures, including powders, films, aerogels, foams, and fibers, can be produced from graphite oxide, CO2, and CH4. Similar to AC, graphene can possess micropores by activation. Self-propagating high-temperature synthesis and molten salt processing are newly-reported methods for fabrication of mesoporous graphene. Macroporous graphene hydrogels can be produced by hydrothermal treatment of graphite oxide suspension, which can also be transferred into films. Hierarchically porous structures can be achieved by H2O2 etching or ZnCl2 activation of the macroporous graphene precursor. Sponges as templates combined with KOH activation are applied to create both micro- and macropores in graphene foams. Graphene can grow on fibers and textiles by electrodeposition, dip-coating, or filtration, which can be woven into clothes with a large area or thick loading, illuminating the potential application in flexible and wearable supercapacitors. The key obstacles in AC and graphene production are high cost, low yield, low packing density, and low working potential range. Most Carbon materials derived from new precursors work very well with aqueous electrolytes. Charge storage occurs not only in the electric double layer (i.e., the "carbon | electrolyte" interface), but also via redox activity in association with the bulk and surface functionalities, and the resulting partial delocalization of valence electrons. The analysis of the capacitive electrode has shown a design defect that prevents the working voltage of a symmetrical supercapacitor from reaching the full potential window of the carbon material. This defect can be avoided in AC-based supercapacitors with unequal electrode capacitances, leading to higher cell voltages and hence higher specific energy than their symmetrical counterparts. There are also emerging ways to raise the energy capacity of AC supercapacitors, such as the use of redox electrolytes to enable the Nernstian charge storage mechanism, and of the three dimensional printing method for a desirable electrode structure. All these developments are promising carbon materials from various precursors of new and waste sources for a more affordable and sustainable supercapacitor technology.
2020, 36(2): 190404
doi: 10.3866/PKU.WHXB201904049
Abstract:
With the ongoing depletion of fossil fuels, the exploration of sustainable energy resources and advanced energy technologies is necessary and the development of clean and sustainable energy storage devices has become an important topic worldwide. In this regard, rechargeable batteries and supercapacitors (SCs) are currently considered to be promising electrochemical energy storage systems for widespread applications in electronic devices, electric vehicles, and smart-grid energy storage stations. Batteries typically exhibit high energy densities but are limited by their low power density and relatively poor cycling performance. In contrast, SCs exhibit high power density, stable cyclability, and good safety, but the energy densities of SCs are generally inferior to those of batteries, which hinders their widespread application. A reliable approach to addressing this issue is to fabricate hybrid supercapacitors (HSCs) composed of battery-type and capacitive electrodes. This device configuration enables the direct integration of the high energy densities of batteries and high power densities of SCs, making HSCs a promising class of energy storage devices. However, the mismatch of capacity and rate performance between the battery-type and capacitive electrodes hinders the widespread applications of HSCs. A key challenge for the development of high-performance HSCs is to optimize the balance between both electrodes. Recently, tremendous efforts have been focused on the search for suitable electrodes and considerable progress has been achieved. Nevertheless, in traditional electrodes, binders are commonly used to combine individual active materials with conductive additives. Unfortunately, these binders are generally electrochemically inactive and insulating, reducing the overall specific capacity/capacitance and deteriorating the charge/mass transport. Recently, binder-free nanoarray electrodes have provided a promising opportunity for designing effective HSCs owing to the merits of their direct electron transport pathway, short ion diffusion length, and ordered-structure-enabled abundant reaction sites. This review briefly addresses the energy storage mechanism of HSCs and the advantages of array electrodes, and subsequently reviews the recent advances in emerging HSCs developed by our group. The performance-electrode structure relationship is discussed from the perspective of devices featuring different electrolytes, including organic, aqueous neutral and aqueous alkaline electrolytes. Moreover, some solutions are put forward to solve the existing issues of HSCs, and the potential applications of array electrode-based HSCs in flexible/wearable electronics are envisioned. Finally, the challenges and future development trends of HSCs are proposed. ![]()
With the ongoing depletion of fossil fuels, the exploration of sustainable energy resources and advanced energy technologies is necessary and the development of clean and sustainable energy storage devices has become an important topic worldwide. In this regard, rechargeable batteries and supercapacitors (SCs) are currently considered to be promising electrochemical energy storage systems for widespread applications in electronic devices, electric vehicles, and smart-grid energy storage stations. Batteries typically exhibit high energy densities but are limited by their low power density and relatively poor cycling performance. In contrast, SCs exhibit high power density, stable cyclability, and good safety, but the energy densities of SCs are generally inferior to those of batteries, which hinders their widespread application. A reliable approach to addressing this issue is to fabricate hybrid supercapacitors (HSCs) composed of battery-type and capacitive electrodes. This device configuration enables the direct integration of the high energy densities of batteries and high power densities of SCs, making HSCs a promising class of energy storage devices. However, the mismatch of capacity and rate performance between the battery-type and capacitive electrodes hinders the widespread applications of HSCs. A key challenge for the development of high-performance HSCs is to optimize the balance between both electrodes. Recently, tremendous efforts have been focused on the search for suitable electrodes and considerable progress has been achieved. Nevertheless, in traditional electrodes, binders are commonly used to combine individual active materials with conductive additives. Unfortunately, these binders are generally electrochemically inactive and insulating, reducing the overall specific capacity/capacitance and deteriorating the charge/mass transport. Recently, binder-free nanoarray electrodes have provided a promising opportunity for designing effective HSCs owing to the merits of their direct electron transport pathway, short ion diffusion length, and ordered-structure-enabled abundant reaction sites. This review briefly addresses the energy storage mechanism of HSCs and the advantages of array electrodes, and subsequently reviews the recent advances in emerging HSCs developed by our group. The performance-electrode structure relationship is discussed from the perspective of devices featuring different electrolytes, including organic, aqueous neutral and aqueous alkaline electrolytes. Moreover, some solutions are put forward to solve the existing issues of HSCs, and the potential applications of array electrode-based HSCs in flexible/wearable electronics are envisioned. Finally, the challenges and future development trends of HSCs are proposed.
2020, 36(2): 190904
doi: 10.3866/PKU.WHXB201909042
Abstract:
2020, 36(2): 191003
doi: 10.3866/PKU.WHXB201910030
Abstract:
2020, 36(2): 191003
doi: 10.3866/PKU.WHXB201910033
Abstract:
2020, 36(2): 190701
doi: 10.3866/PKU.WHXB201907017
Abstract:
2020, 36(2): 190701
doi: 10.3866/PKU.WHXB201907018
Abstract:
