Pseudocapacitance of TiO2−x/CNT Anodes for High‐Performance Quasi‐Solid‐State Li‐Ion and Na‐Ion Capacitors

It is challenging for flexible solid‐state hybrid capacitors to achieve high‐energy‐high‐power densities in both Li‐ion and Na‐ion systems, and the kinetics discrepancy between the sluggish faradaic anode and the rapid capacitive cathode is the most critical issue needs to be addressed. To improve Li‐ion/Na‐ion diffusion kinetics, flexible oxygen‐deficient TiO_2?x/CNT composite film with ultrafast electron/ion transport network is constructed as self‐supported and light‐weight anode for a quasi‐solid‐state hybrid capacitor. It is found that the designed porous yolk–shell structure endows large surface area and provides short diffusion length, the oxygen‐deficient composite film can improve electrical conductivity, and enhance ion diffusion kinetic by introducing intercalation pseudocapacitance, therefore resulting in advance electrochemical properties. It exhibits high capacity, excellent rate performance, and long cycle life when utilized as self‐supported anodes for Li‐ion and Na‐ion batteries. When assembled with activated carbon/carbon nanotube (AC/CNT) flexible cathode, using ion conducting gel polymer as the electrolyte, high energy densities of 104 and 109 Wh kg^?1 are achieved at 250 W kg^?1 in quasi‐solid‐state Li‐ion and Na‐ion capacitors (LICs and SICs), respectively. Still, energy densities of 32 and 36 Wh kg^?1 can be maintained at high power densities of 5000 W kg^?1 in LICs and SICs.     

Etching‐Assisted Crumpled Graphene Wrapped Spiky Iron Oxide Particles for High‐Performance Li‐Ion Hybrid Supercapacitor

From graphene oxide wrapped iron oxide particles with etching/reduction process, high‐performance anode and cathode materials of lithium‐ion hybrid supercapacitors are obtained in the same process with different etching conditions, which consist of partially etched crumpled graphene (CG) wrapped spiky iron oxide particles (CG@SF) for a battery‐type anode, and fully etched CG for a capacitive‐type cathode. The CG is formed along the shape of spikily etched particles, resulting in high specific surface area and electrical conductivity, thus the CG‐based cathode exhibits remarkable capacitive performance of 210 F g^?1 and excellent rate capabilities. The CG@SF can also be ideal anode materials owing to spiky and porous morphology of the particles and tightly attached crumpled graphene onto the spiky particles, which provides structural stability and low contact resistance during repetitive lithiation/delithiation processes. The CG@SF anode shows a particularly high capacitive performance of 1420 mAh g^?1 after 270 cycles, continuously increases capacity beyond the 270th cycle, and also maintains a high capacity of 170 mAh g^?1 at extremely high speeds of 100 C. The full‐cell exhibits a higher energy density up to 121 Wh kg^?1 and maintains high energy density of 60.1 Wh kg^?1 at 18.0 kW kg^?1. This system could thus be a practical energy storage system to fill the gap between batteries and supercapacitors.     

Boosting Zn‐Ion Energy Storage Capability of Hierarchically Porous Carbon by Promoting Chemical Adsorption

The construction of advanced Zn‐ion hybrid supercapacitors (ZHSCs) with high energy density is promising but still challenging, especially at high current densities. In this work, a high‐energy and ultrastable aqueous ZHSC is demonstrated by introducing N dopants into a hierarchically porous carbon cathode for the purpose of enhancing its chemical adsorption of Zn ions. Experimental results and theoretical simulations reveal that N doping not only significantly facilitates the chemical adsorption process of Zn ions, but also greatly increases its conductivity, surface wettability, and active sites. Consequently, the as‐fabricated aqueous ZHSC based on this N‐doped porous carbon cathode displays an exceptionally high energy density of 107.3 Wh kg^?1 at a high current density of 4.2 A g^?1, a superb power density of 24.9 kW kg^?1, and an ultralong‐term lifespan (99.7% retention after 20 000 cycles), substantially superior to state‐of‐the‐art ZHSCs. Particularly, such a cathode also leads to a quasi‐solid‐state device with satisfactory energy storage performance, delivering a remarkable energy density of 91.8 Wh kg^?1. The boosted energy storage strategy by tuning the chemical adsorption capability is also applicable to other carbon materials.     

A Novel Potassium‐Ion‐Based Dual‐Ion Battery

In this work, combining both advantages of potassium‐ion batteries and dual‐ion batteries, a novel potassium‐ion‐based dual‐ion battery (named as K‐DIB) system is developed based on a potassium‐ion electrolyte, using metal foil (Sn, Pb, K, or Na) as anode and expanded graphite as cathode. When using Sn foil as the anode, the K‐DIB presents a high reversible capacity of 66 mAh g^?1 at a current density of 50 mA g^?1 over the voltage window of 3.0–5.0 V, and exhibits excellent long‐term cycling performance with 93% capacity retention for 300 cycles. Moreover, as the Sn foil simultaneously acts as the anode material and the current collector, dead load and dead volume of the battery can be greatly reduced, thus the energy density of the K‐DIB is further improved. It delivers a high energy density of 155 Wh kg^?1 at a power density of 116 W kg^?1, which is comparable with commercial lithium‐ion batteries. Thus, with the advantages of environmentally friendly, cost effective, and high energy density, this K‐DIB shows attractive potential for future energy storage application.     

A High‐Performance Lithium‐Ion Capacitor Based on 2D Nanosheet Materials

Lithium‐ion capacitors (LICs) are promising electrical energy storage systems for mid‐to‐large‐scale applications due to the high energy and large power output without sacrificing long cycle stability. However, due to the different energy storage mechanisms between anode and cathode, the energy densities of LICs often degrade noticeably at high power density, because of the sluggish kinetics limitation at the battery‐type anode side. Herein, a high‐performance LIC by well‐defined ZnMn₂O₄‐graphene hybrid nanosheets anode and N‐doped carbon nanosheets cathode is presented. The 2D nanomaterials offer high specific surface areas in favor of a fast ion transport and storage with shortened ion diffusion length, enabling fast charge and discharge. The fabricated LIC delivers a high specific energy of 202.8 Wh kg^?1 at specific power of 180 W kg^?1, and the specific energy remains 98 Wh kg^?1 even when the specific power achieves as high as 21 kW kg^?1.     

Confined Amorphous Red Phosphorus in MOF‐Derived N‐Doped Microporous Carbon as a Superior Anode for Sodium‐Ion Battery

Red phosphorus (P) has attracted intense attention as promising anode material for high‐energy density sodium‐ion batteries (NIBs), owing to its high sodium storage theoretical capacity (2595 mAh g^?1). Nevertheless, natural insulating property and large volume variation of red P during cycling result in extremely low electrochemical activity, leading to poor electrochemical performance. Herein, the authors demonstrate a rational strategy to improve sodium storage performance of red P by confining nanosized amorphous red P into zeolitic imidazolate framework‐8 (ZIF‐8) ‐derived nitrogen‐doped microporous carbon matrix (denoted as P@N‐MPC). When used as anode for NIBs, the P@N‐MPC composite displays a high reversible specific capacity of ≈600 mAh g^?1 at 0.15 A g^?1 and improved rate capacity (≈450 mAh g^?1 at 1 A g^?1 after 1000 cycles with an extremely low capacity fading rate of 0.02% per cycle). The superior sodium storage performance of the P@N‐MPC is mainly attributed to the novel structure. The N‐doped porous carbon with sub‐1 nm micropore facilitates the rapid diffusion of organic electrolyte ions and improves the conductivity of the encapsulated red P. Furthermore, the porous carbon matrix can buffer the volume change of red P during repeat sodiation/desodiation process, keeping the structure intact after long cycle life.     

Tin Sulfide‐Based Nanohybrid for High‐Performance Anode of Sodium‐Ion Batteries

Nanohybrid anode materials for Na‐ion batteries (NIBs) based on conversion and/or alloying reactions can provide significantly improved energy and power characteristics, while suffering from low Coulombic efficiency and unfavorable voltage properties. An NIB paper‐type nanohybrid anode (PNA) based on tin sulfide nanoparticles and acid‐treated multiwalled carbon nanotubes is reported. In 1 m NaPF₆ dissolved in diethylene glycol dimethyl ether as an electrolyte, the above PNA shows a high reversible capacity of ≈1200 mAh g^?1 and a large voltage plateau corresponding to a capacity of ≈550 mAh g^?1 in the low‐voltage region of ≈0.1 V versus Na⁺/Na, exhibiting high rate capabilities at a current rate of 1 A g^?1 and good cycling performance over 250 cycles. In addition, the PNA exhibits a high first Coulombic efficiency of ≈90%, achieving values above 99% during subsequent cycles. Furthermore, the feasibility of PNA usage is demonstrated by full‐cell tests with a reported cathode, which results in high specific energy and power values of ≈256 Wh kg^?1 and 471 W kg^?1, respectively, with stable cycling.     

A Nonaqueous Potassium‐Based Battery–Supercapacitor Hybrid Device

A low cost nonaqueous potassium‐based battery–supercapacitor hybrid device (BSH) is successfully established for the first time with soft carbon as the anode, commercialized activated carbon as the cathode, and potassium bis(fluoro‐slufonyl)imide in dimethyl ether as the electrolyte. This BSH reconciles the advantages of potassium ion batteries and supercapacitors, achieving a high energy density of 120 W h kg^?1, a high power density of 599 W kg^?1, a long cycle life of 1500 cycles, and an ultrafast charge/slow discharge performance (energy density and power density are calculated based on the total mass of active materials in the anode and cathode). This work demonstrates a great potential of applying the nonaqueous BSH for low cost electric energy storage systems.     

Beyond Activated Carbon: Graphite‐Cathode‐Derived Li‐Ion Pseudocapacitors with High Energy and High Power Densities

Supercapacitors have aroused considerable attention due to their high power capability, which enables charge storage/output in minutes or even seconds. However, to achieve a high energy density in a supercapacitor has been a long‐standing challenge. Here, graphite is reported as a high‐energy alternative to the frequently used activated carbon (AC) cathode for supercapacitor application due to its unique Faradaic pseudocapacitive anion intercalation behavior. The graphite cathode manifests both higher gravimetric and volumetric energy density (498 Wh kg^?1 and 431.2 Wh l^?1) than an AC cathode (234 Wh kg^?1 and 83.5 Wh l^?1) with peak power densities of 43.6 kW kg^?1 and 37.75 kW l^?1. A new type of Li‐ion pseudocapacitor (LIpC) is thus proposed and demonstrated with graphite as cathode and prelithiated graphite or Li₄Ti₅O₁₂ (LTO) as anode. The resultant graphite–graphite LIpCs deliver high energy densities of 167–233 Wh kg^?1 at power densities of 0.22–21.0 kW kg^?1 (based on active mass in both electrodes), much higher than 20–146 Wh kg^?1 of AC‐derived Li‐ion capacitors and 23–67 Wh kg^?1 of state‐of‐the‐art metal oxide pseudocapacitors. Excellent rate capability and cycling stability are further demonstrated for LTO‐graphite LIpCs.     

A Flexible Sulfur‐Enriched Nitrogen Doped Multichannel Hollow Carbon Nanofibers Film for High Performance Sodium Storage

Heteroatom doping is regarded as a promising method to enhance the sodium storage performance of carbon materials. In this work, a sulfur‐enriched N‐doped multichannel hollow carbon nanofiber (denoted as S‐NCNF) film is prepared through electrospinning technology and heat treatment with sublimed sulfur as the flexible anode for sodium ion batteries (NIBs). The S‐NCNF film displays outstanding electrochemical performance, particularly with a high rate capacity (132 mA h g^?1 at the current density of 10 A g^?1) and remarkable long cycling stability (reversible specific capacity of 187 mA h g^?1 at 2 A g^?1 over 2000 cycles). The improved sodium storage performance results from the unique 3D structure, abundant defects, and increased interlayer spacing of S‐NCNFs. The density functional theory calculations demonstrate that nitrogenous carbon nanofibers doping with sulfur could not only promote the adsorption of sodium but also favor electrons' transfer. This strategy has been demonstrated as a general process to design free‐standing carbon‐based thin film with other heteroatom doping.     

High Performance Lithium‐Ion Batteries Using Layered 2H‐MoTe2 as Anode

The major challenges faced by candidate electrode materials in lithium‐ion batteries (LIBs) include their low electronic and ionic conductivities. 2D van der Waals materials with good electronic conductivity and weak interlayer interaction have been intensively studied in the electrochemical processes involving ion migrations. In particular, molybdenum ditelluride (MoTe₂) has emerged as a new material for energy storage applications. Though 2H‐MoTe₂ with hexagonal semiconducting phase is expected to facilitate more efficient ion insertion/deinsertion than the monoclinic semi‐metallic phase, its application as an anode in LIB has been elusive. Here, 2H‐MoTe₂, prepared by a solid‐state synthesis route, has been employed as an efficient anode with remarkable Li⁺ storage capacity. The as‐prepared 2H‐MoTe₂ electrodes exhibit an initial specific capacity of 432 mAh g^?1 and retain a high reversible specific capacity of 291 mAh g^?1 after 260 cycles at 1.0 A g^?1. Further, a full‐cell prototype is demonstrated by using 2H‐MoTe₂ anode with lithium cobalt oxide cathode, showing a high energy density of 454 Wh kg^?1 (based on the MoTe₂ mass) and capacity retention of 80% over 100 cycles. Synchrotron‐based in situ X‐ray absorption near‐edge structures have revealed the unique lithium reaction pathway and storage mechanism, which is supported by density functional theory based calculations.     

Peapod‐like Li3VO4/N‐Doped Carbon Nanowires with Pseudocapacitive Properties as Advanced Materials for High‐Energy Lithium‐Ion Capacitors

Lithium ion capacitors are new energy storage devices combining the complementary features of both electric double‐layer capacitors and lithium ion batteries. A key limitation to this technology is the kinetic imbalance between the Faradaic insertion electrode and capacitive electrode. Here, we demonstrate that the Li₃VO₄ with low Li‐ion insertion voltage and fast kinetics can be favorably used for lithium ion capacitors. N‐doped carbon‐encapsulated Li₃VO₄ nanowires are synthesized through a morphology‐inheritance route, displaying a low insertion voltage between 0.2 and 1.0 V, a high reversible capacity of ≈400 mAh g^?1 at 0.1 A g^?1, excellent rate capability, and long‐term cycling stability. Benefiting from the small nanoparticles, low energy diffusion barrier and highly localized charge‐transfer, the Li₃VO₄/N‐doped carbon nanowires exhibit a high‐rate pseudocapacitive behavior. A lithium ion capacitor device based on these Li₃VO₄/N‐doped carbon nanowires delivers a high energy density of 136.4 Wh kg^?1 at a power density of 532 W kg^?1, revealing the potential for application in high‐performance and long life energy storage devices.     

Graphene Caging Silicon Particles for High‐Performance Lithium‐Ion Batteries

Silicon holds great promise as an anode material for lithium‐ion batteries with higher energy density; its implication, however, is limited by rapid capacity fading. A catalytic growth of graphene cages on composite particles of magnesium oxide and silicon, which are made by magnesiothermic reduction reaction of silica particles, is reported herein. Catalyzed by the magnesium oxide, graphene cages can be conformally grown onto the composite particles, leading to the formation of hollow graphene‐encapsulated Si particles. Such materials exhibit excellent lithium storage properties in terms of high specific capacity, remarkable rate capability (890 mAh g^?1 at 5 A g^?1), and good cycling retention over 200 cycles with consistently high coulombic efficiency at a current density of 1 A g^?1. A full battery test using LiCoO₂ as the cathode demonstrates a high energy density of 329 Wh kg^?1.     

Ultra‐High Pyridinic N‐Doped Porous Carbon Monolith Enabling High‐Capacity K‐Ion Battery Anodes for Both Half‐Cell and Full‐Cell Applications

An ultrahigh pyridinic N‐content‐doped porous carbon monolith is reported, and the content of pyridinic N reaches up to 10.1% in overall material (53.4 ± 0.9% out of 18.9 ± 0.4% N content), being higher than most of previously reported N‐doping carbonaceous materials, which exhibit greatly improved electrochemical performance for potassium storage, especially in term of the high reversible capacity. Remarkably, the pyridinic N‐doped porous carbon monolith (PNCM) electrode exhibits high initial charge capacity of 487 mAh g^?1 at a current density of 20 mA g^?1, which is one of the highest reversible capacities among all carbonaceous anodes for K‐ion batteries. Moreover, the K‐ion full cell is successfully assembled, demonstrating a high practical energy density of 153.5 Wh kg^?1. These results make PNCM promising for practical application in energy storage devices and encourage more investigations on a similar potassium storage system.     

Rational Construction of Hollow Core‐Branch CoSe2 Nanoarrays for High‐Performance Asymmetric Supercapacitor and Efficient Oxygen Evolution

Metal selenides have great potential for electrochemical energy storage, but are relatively scarce investigated. Herein, a novel hollow core‐branch CoSe₂ nanoarray on carbon cloth is designed by a facile selenization reaction of predesigned CoO nanocones. And the electrochemical reaction mechanism of CoSe₂ in supercapacitor is studied in detail for the first time. Compared with CoO, the hollow core‐branch CoSe₂ has both larger specific surface area and higher electrical conductivity. When tested as a supercapacitor positive electrode, the CoSe₂ delivers a high specific capacitance of 759.5 F g^?1 at 1 mA cm^?2, which is much larger than that of CoO nanocones (319.5 F g^?1). In addition, the CoSe₂ electrode exhibits excellent cycling stability in that a capacitance retention of 94.5% can be maintained after 5000 charge–discharge cycles at 5 mA cm^?2. An asymmetric supercapacitor using the CoSe₂ as cathode and an N‐doped carbon nanowall as anode is further assembled, which show a high energy density of 32.2 Wh kg^?1 at a power density of 1914.7 W kg^?1, and maintains 24.9 Wh kg^?1 when power density increased to 7354.8 W kg^?1. Moreover, the CoSe₂ electrode also exhibits better oxygen evolution reaction activity than that of CoO.     

Hierarchical 3D All‐Carbon Composite Structure Modified with N‐Doped Graphene Quantum Dots for High‐Performance Flexible Supercapacitors

Flexible supercapacitors have shown enormous potential for portable electronic devices. Herein, hierarchical 3D all‐carbon electrode materials are prepared by assembling N‐doped graphene quantum dots (N‐GQDs) on carbonized MOF materials (cZIF‐8) interweaved with carbon nanotubes (CNTs) for flexible all‐solid‐state supercapacitors. In this ternary electrode, cZIF‐8 provides a large accessible surface area, CNTs act as the electrical conductive network, and N‐GQDs serve as highly pseudocapactive materials. Due to the synergistic effect and hierarchical assembly of these components, N‐GQD@cZIF‐8/CNT electrodes exhibit a high specific capacitance of 540 F g^?1 at 0.5 A g^?1 in a 1 m H₂SO₄ electrolyte and excellent cycle stability with 90.9% capacity retention over 8000 cycles. The assembled supercapacitor possesses an energy density of 18.75 Wh kg^?1 with a power density of 108.7 W kg^?1. Meanwhile, three supercapacitors connected in series can power light‐emitting diodes for 20 min. All‐solid‐state N‐GQD@cZIF‐8/CNT flexible supercapacitor exhibits an energy density of 14 Wh kg^?1 with a power density of 89.3 W kg^?1, while the capacitance retention after 5000 cycles reaches 82%. This work provides an effective way to construct novel electrode materials with high energy storage density as well as good cycling performance and power density for high‐performance energy storage devices via the rational design.     

Tailoring Hierarchically Porous Nitrogen‐, Sulfur‐Codoped Carbon for High‐Performance Supercapacitors and Oxygen Reduction

Heteroatom‐doped carbon materials are intensively studied in supercapacitors and fuel cells, because of their great potential for sustainably bearing on the energy crisis and environmental pollution. Although enormous efforts are put in material perfection with a hierarchically porous microstructure, the simultaneous optimization of both porous structures and surface functionalities is hard to achieve due to inevitable concurrent dopant leaching effect and structural collapse under required high pyrolysis temperature. In this study, an in situ dehalogenation polymerization and activation protocol is introduced to synthesize nitrogen‐ and sulfur‐codoped carbon materials (NS‐PCMs) with hierarchical pore distribution and abundant surface doping, which endows them with good conductivity, abundant accessible active sites, and efficient mass transport. As a result, the as‐prepared carbon materials (NS‐a‐PCM‐1000) show an excellent mass specific capacitance of 461.5 F g^?1 at a current density of 0.1 A g^?1, long cycle life (>23 k, 10 A g^?1), and high device energy and power density (17.3 Wh kg^?1, 250 W kg^?1). Significantly, NS‐a‐PCM‐1000 also exhibits one of the highest oxygen reduction reaction activities (onset potential of 1.0 V vs reversible hydrogen electrode) in alkaline media among all reported metal‐free catalysts.     

Polyhedral‐Like NiMn‐Layered Double Hydroxide/Porous Carbon as Electrode for Enhanced Electrochemical Performance Supercapacitors

Polyhedral‐like NiMn‐layered double hydroxide/porous carbon (NiMn‐LDH/PC‐x ) composites are successfully synthesized by hydrothermal method (x = 1, 2 means different mass percent of porous carbon (PC) in composites). The NiMn‐LDH/PC‐1 composites possess specific capacitance 1634 F g⁻¹ at a current density of 1 A g⁻¹, and it is much better than that of pure LDH (1095 F g⁻¹ at 1 A g⁻¹). Besides, the sample can retain 84.58% of original capacitance after 3000 cycles at 15 A g⁻¹. An asymmetric supercapacitor with NiMn‐LDH/PC‐1 as anode and activated carbon as cathode is fabricated, and the supercapacitor can achieve an energy density of 18.60 Wh kg⁻¹ at a power density of 225.03 W kg⁻¹. The enhanced electrochemical performance attributes to the high faradaic pseudocapacitance of NiMn‐LDH, the introduction of PC, and the 3D porous structure of LDH/PC‐1 composites. The introduction of PC hinders serious agglomeration of LDH and further accelerates ions transport. The encouraging results indicate that these materials are one of the most potential candidates for energy storage devices.     

A High‐Energy and Long‐Life Aqueous Zn/Birnessite Battery via Reversible Water and Zn2+ Coinsertion

Aqueous rechargeable Zn/birnessite batteries have recently attracted extensive attention for energy storage system because of their low cost and high safety. However, the reaction mechanism of the birnessite cathode in aqueous electrolytes and the cathode structure degradation mechanics still remain elusive and controversial. In this work, it is found that solvation water molecules coordinated to Zn²⁺ are coinserted into birnessite lattice structure contributing to Zn²⁺ diffusion. However, the birnessite will suffer from hydroxylation and Mn dissolution with too much solvated water coinsertion. Through engineering Zn²⁺ primary solvation sheath with strong‐field ligand in aqueous electrolyte, highly reversible [Zn(H₂O)₂]²⁺ complex intercalation/extraction into/from birnessite cathode is obtained. Cathode–electrolyte interface suppressing the Mn dissolution also forms. The Zn metal anode also shows high reversibility without formation of “death‐zinc” and detrimental dendrite. A full cell coupled with birnessite cathode and Zn metal anode delivers a discharge capacity of 270 mAh g^?1, a high energy density of 280 Wh kg^?1 (based on total mass of cathode and anode active materials), and capacity retention of 90% over 5000 cycles.     

Birnessite Nanosheet Arrays with High K Content as a High‐Capacity and Ultrastable Cathode for K‐Ion Batteries

Potassium‐ion batteries (PIBs) are one of the emerging energy‐storage technologies due to the low cost of potassium and theoretically high energy density. However, the development of PIBs is hindered by the poor K⁺ transport kinetics and the structural instability of the cathode materials during K⁺ intercalation/deintercalation. In this work, birnessite nanosheet arrays with high K content (K_0.77MnO₂?0.23H₂O) are prepared by “hydrothermal potassiation” as a potential cathode for PIBs, demonstrating ultrahigh reversible specific capacity of about 134 mAh g^?1 at a current density of 100 mA g^?1, as well as great rate capability (77 mAh g^?1 at 1000 mA g^?1) and superior cycling stability (80.5% capacity retention after 1000 cycles at 1000 mA g^?1). With the introduction of adequate K⁺ ions in the interlayer, the K‐birnessite exhibits highly stabilized layered structure with highly reversible structure variation upon K⁺ intercalation/deintercalation. The practical feasibility of the K‐birnessite cathode in PIBs is further demonstrated by constructing full cells with a hard–soft composite carbon anode. This study highlights effective K⁺‐intercalation for birnessite to achieve superior K‐storage performance for PIBs, making it a general strategy for developing high‐performance cathodes in rechargeable batteries beyond lithium‐ion batteries.