Asymmetric Supercapacitor Electrodes and Devices

The world is recently witnessing an explosive development of novel electronic and optoelectronic devices that demand more‐reliable power sources that combine higher energy density and longer‐term durability. Supercapacitors have become one of the most promising energy‐storage systems, as they present multifold advantages of high power density, fast charging–discharging, and long cyclic stability. However, the intrinsically low energy density inherent to traditional supercapacitors severely limits their widespread applications, triggering researchers to explore new types of supercapacitors with improved performance. Asymmetric supercapacitors (ASCs) assembled using two dissimilar electrode materials offer a distinct advantage of wide operational voltage window, and thereby significantly enhance the energy density. Recent progress made in the field of ASCs is critically reviewed, with the main focus on an extensive survey of the materials developed for ASC electrodes, as well as covering the progress made in the fabrication of ASC devices over the last few decades. Current challenges and a future outlook of the field of ASCs are also discussed.     

Flexible,Stretchable, and Transparent Planar Microsupercapacitors Based on 3D Porous Laser‐Induced Graphene

The graphene with 3D porous network structure is directly laser‐induced on polyimide sheets at room temperature in ambient environment by an inexpensive and one‐step method, then transferred to silicon rubber substrate to obtain highly stretchable, transparent, and flexible electrode of the all‐solid‐state planar microsupercapacitors. The electrochemical capacitance properties of the graphene electrodes are further enhanced by nitrogen doping and with conductive poly(3,4‐ethylenedioxythiophene) coating. With excellent flexibility, stretchability, and capacitance properties, the planar microsupercapacitors present a great potential in fashionable and comfortable designs for wearable electronics.     

A Novel Aqueous Asymmetric Supercapacitor based on Pyrene-4,5,9,10-Tetraone Functionalized Graphene as the Cathode and Annealed Ti3C2Tx MXene as the Anode

Asymmetric supercapacitors (ASCs), employing two dissimilar electrode materials with a large redox peak position difference as cathode and anode, have been designed to further broaden the voltage window and improve the energy density of supercapacitors. Organic molecule based electrodes can be constructed by combining redox-active organic molecules with conductive carbon-based materials such as graphene. Herein, pyrene-4,5,9,10-tetraone (PYT), a redox-active molecule with four carbonyl groups, exhibits a four-electron transfer process and can potentially deliver a high capacity. PYT is noncovalently combined with two different kinds of graphene (Graphenea [GN] and LayerOne [LO]) at different mass ratios. The PYT-functionalized GN electrode (PYT/GN 4–5) possesses a high capacity of 711 F g⁻¹ at 1 A g⁻¹ in 1 M H₂SO₄. To match with the PYT/GN 4–5 cathode, an annealed-Ti₃C₂T_x (A-Ti₃C₂T_x) MXene anode with a pseudocapacitive character is prepared by pyrolysis of pure Ti₃C₂T_x. The assembled PYT/GN 4–5//A-Ti₃C₂T_x ASC delivers an outstanding energy density of 18.4 Wh kg⁻¹ at a power density of 700 W kg⁻¹. The PYT-functionalized graphene holds great potential for high-performance energy storage devices.     

High‐Stability MnOx Nanowires@C@MnOx Nanosheet Core–Shell Heterostructure Pseudocapacitance Electrode Based on Reversible Phase Transition Mechanism

A stable MnO_x@C@MnO_x core–shell heterostructure consisting of vertical MnO_x nanosheets grown evenly on the surface of the MnO_x@carbon nanowires are obtained by simple liquid phase method combined with thermal treatment. The hierarchical MnO_x@C@MnO_x heterostructure electrode possesses a high specific capacitance of 350 F g^?1 and an excellent cycle performance owing to the existence of the pore structure among the ultrasmall MnO_x nanoparticles and the rapid transmission of electrons between the active material and carbon coating layer. Particularly, according to the in situ Raman spectra analysis, no characteristic peaks corresponding to MnOOH are found during charging/discharging, indicating that pseudocapacitive behavior of the MnO_x electrode have no relevance to the intercalation/deintercalation of protons (H⁺) in the electrolyte. Further combining in situ X‐ray powder diffraction analysis, the diffraction peak of α‐MnO₂ can be detected in the process of charging, while Mn₃O₄ phase is found in discharge products. Therefore, these results demonstrate that the MnO_x undergoes a reversible phase transformation reaction of Mn₃O₄?α‐MnO₂. Moreover, the assembled all‐solid‐state asymmetric supercapacitor with a MnO_x@C@MnO_x electrode delivers a high energy density of 23 Wh kg^?1, an acceptable power density of 2500 W kg^?1, and an excellent cyclic stability performance of 94% after 2000 cycles, showing the potential for practical application.     

Design of Novel Wearable,Stretchable, and Waterproof Cable‐Type Supercapacitors Based on High‐Performance Nickel Cobalt Sulfide‐Coated Etching‐Annealed Yarn Electrodes

Rapid advances in functional electronics bring tremendous demands on innovation toward effective designs of device structures. Yarn supercapacitors (SCs) show advantages of flexibility, knittability, and small size, and can be integrated into various electronic devices with low cost and high efficiency for energy storage. In this work, functionalized stainless steel yarns are developed to support active materials of positive and negative electrodes, which not only enhance capacitance of both electrodes but can also be designed into stretchable configurations. The as‐made asymmetric yarn SCs show a high energy density of 0.0487 mWh cm^?2 (10.19 mWh cm^?3) at a power density of 0.553 mW cm^?2 (129.1 mW cm^?3) and a specific capacitance of 127.2 mF cm^?2 under an operating voltage window of 1.7 V. The fabricated SC is then made into a stretchable configuration by a prestraining‐then‐releasing approach using polydimethylsiloxane (PDMS) tube, and its electrochemical performance can be well maintained when stretching up to a high strain of 100%. Moreover, the stretchable cable‐type SCs are stably workable under water‐immersed condition. The method opens up new ways for fabricating flexible, stretchable, and waterproof devices.     

Novel Skutterudite CoP3–Based Asymmetric Supercapacitor with Super High Energy Density

Skutterudite CoP₃ holds a unique structural formation that exhibits much better electronic properties for obtaining high energy density supercapacitors. Herein, novel skutterudite Ni–CoP₃ nanosheets are constructed by etching and coprecipitating at room temperature and subsequent low‐temperature phosphorization reaction. Benefiting from the enhanced electrical conductivity and more electroactive sites brought about by adjusting the electronic structure with Ni incorporating the Ni–CoP₃ electrode with a battery‐type demonstrates an ultrahigh specific capacity of 0.7 mA h cm^?2 and exceptional cycling stability. The asymmetric supercapacitor (ASC) device fabricated by employing Ni–CoP₃ and activated carbon (AC) as positive and negative electrodes, resepectively, exhibits a remarkable high energy density of 89.6 Wh kg^?1 at 796 W kg^?1 and excellent stability of 93% after 10 000 cycles, due to the skutterudite structure. The skutterudite Ni–CoP₃ shows a great potential to be an excellent next‐generation electrode candidate for supercapacitors and other energy storage devices.     

Self‐Assembled Nickel Pyrophosphate‐Decorated Amorphous Bimetal Hydroxides 2D‐on‐2D Nanostructure for High‐Energy Solid‐State Asymmetric Supercapacitor

To obtain a supercapacitor with a remarkable specific capacitance and rate performance, a cogent design and synthesis of the electrode material containing abundant active sites is necessary. In present work, a scalable strategy is developed for preparing 2D‐on‐2D nanostructures for high‐energy solid‐state asymmetric supercapacitors (ASCs). The self‐assembled vertically aligned microsheet‐structured 2D nickel pyrophosphate (Ni₂P₂O₇) is decorated with amorphous bimetallic nickel cobalt hydroxide (NiCo‐OH) to form a 2D‐on‐2D nanostructure arrays electrode. The resulting Ni₂P₂O₇/NiCo‐OH 2D‐on‐2D array electrode exhibits peak specific capacity of 281 mA hg^?1 (4.3 F cm^?2), excellent rate capacity, and cycling stability over 10 000 charge–discharge cycles in the positive potential range. The excellent electrochemical features can be attributed to the high electrical conductivity and 2D layered structure of Ni₂P₂O₇ along with the Faradic capacitance of the amorphous NiCo‐OH nanosheets. The constructed Ni₂P₂O₇/NiCo‐OH//activated carbon based solid‐state ASC cell operates in a high voltage window of 1.8 V with an energy density of 78 Wh kg^?1 (1.065 mWh cm^?3) and extraordinary cyclic stability over 10 000 charge–discharge cycles with excellent energy efficiency (75%–80%) over all current densities. The excellent electrochemical performance of the prepared electrode and solid‐state ASC device offers a favorable and scalable pathway for developing advanced electrodes.     

Biomass‐Derived Nitrogen‐Doped Carbon Nanofiber Network: A Facile Template for Decoration of Ultrathin Nickel‐Cobalt Layered Double Hydroxide Nanosheets as High‐Performance Asymmetric Supercapacitor Electrode

The development of biomass‐based energy storage devices is an emerging trend to reduce the ever‐increasing consumption of non‐renewable resources. Here, nitrogen‐doped carbonized bacterial cellulose (CBC‐N) nanofibers are obtained by one‐step carbonization of polyaniline coated bacterial cellulose (BC) nanofibers, which not only display excellent capacitive performance as the supercapacitor electrode, but also act as 3D bio‐template for further deposition of ultrathin nickel‐cobalt layered double hydroxide (Ni‐Co LDH) nanosheets. The as‐obtained CBC‐N@LDH composite electrodes exhibit significantly enhanced specific capacitance (1949.5 F g^?1 at a discharge current density of 1 A g^?1, based on active materials), high capacitance retention of 54.7% even at a high discharge current density of 10 A g^?1 and excellent cycling stability of 74.4% retention after 5000 cycles. Furthermore, asymmetric supercapacitors (ASCs) are constructed using CBC‐N@LDH composites as positive electrode materials and CBC‐N nanofibers as negative electrode materials. By virtue of the intrinsic pseudocapacitive characteristics of CBC‐N@LDH composites and 3D nitrogen‐doped carbon nanofiber networks, the developed ASC exhibits high energy density of 36.3 Wh kg^?1 at the power density of 800.2 W kg^?1. Therefore, this work presents a novel protocol for the large‐scale production of biomass‐derived high‐performance electrode materials in practical supercapacitor applications.     

Tungsten Nitride Nanodots Embedded Phosphorous Modified Carbon Fabric as Flexible and Robust Electrode for Asymmetric Pseudocapacitor

Owing to the excellent physical properties of metal nitrides such as metallic conductivity and pseudocapacitance, they have recently attracted much attention as competitive materials for high‐performance supercapacitors (SCs). However, the voltage window for metal nitride‐based symmetric SCs is limited (0.6–0.8 V) in aqueous electrolyte due to the oxidation at high negative potentials. In this respect, ultra‐small tungsten nitride particles onto the phosphorous modified carbon fabric (W₂N@P‐CF) are engineered as a promising hybrid electrode for pseudocapacitors. Additionally, the fact that the W₂N@P‐CF electrode can operate in the negative potential region is exploited to design asymmetric pseudocapacitors by coupling with a polypyrrole on carbon fabric (PPy@CF) as the positive electrode. Remarkably, the W₂N@P‐CF//PPy@CF asymmetric cell can be cycled in a wide voltage window of 1.6 V that is almost two times higher than that of metal nitrides symmetric SCs. The pseudocapacitive behavior with matching different potential regions of W₂N@P‐CF and PPy@CF, considerably enhance performance of asymmetric device. The device delivers high volumetric capacity (7.1 F cm^?3), high energy (2.54 mWh cm^?3), power densities, and good cycling stability (88%) over 20 000 cycles. Thus, pseudocapacitive metal nitride‐based devices hold a great promise to provide high voltage and improved energy density in aqueous electrolyte.     

Freestanding 1T‐MnxMo1–xS2–ySey and MoFe2S4–zSez Ultrathin Nanosheet‐Structured Electrodes for Highly Efficient Flexible Solid‐State Asymmetric Supercapacitors

Fabrication of hierarchical nanosheet arrays of 1T phase of transition‐metal dichalcogenides is indeed a critical task, but it holds immense potential for energy storage. A single‐step strategy is employed for the fabrication of stable 1T‐Mn_xMo_1–xS_2–ySe_y and MoFe₂S_4–zSe_z hierarchical nanosheet arrays on carbon cloth as positive and negative electrodes, respectively. The flexible asymmetric supercapacitor constructed with these two electrodes exhibits an excellent electrochemical performance (energy density of ≈69 Wh kg^?1 at a power density of 0.985 kW kg^?1) with ultralong cyclic stability of ≈83.5% capacity retention, after 10 000 consecutive cycles. Co‐doping of the metal and nonmetal boosts the charge storage ability of the transition‐metal chalcogenides following enrichment in the metallic 1T phase, improvement in the surface area, and expansion in the interlayer spacing in tandem, which is the key focus of the present study. This study explicitly demonstrates the exponential enhancement of specific capacity of MoS₂ following intercalation and doping of Mn and Se, and Fe₂S₃ following doping of Mo and Se could be an ideal direction for the fabrication of novel energy‐storage materials with high‐energy storage ability.