Layered Oxide Cathode for Potassium‐Ion Battery: Recent Progress and Prospective

Rechargeable potassium‐ion batteries (KIBs) have demonstrated great potential as alternative technologies to the currently used lithium‐ion batteries on account of the competitive price and low redox potential of potassium which is advantageous to applications in the smart grid. As the critical component determining the energy density, appropriate cathode materials are of vital need for the realization of KIBs. Layered oxide cathodes are promising candidates for KIBs due to high reversible capacity, appropriate operating potential, and most importantly, facile and easily scalable synthesis. In light of this trend, the recent advancements and progress in layered oxides research for KIBs cathodes, covering material design, structural evolution, and electrochemical performance are comprehensively reviewed. The structure–performance correlation and some effective optimization strategies are also discussed. Furthermore, challenges and prospects of these layered cathodes are included, with the purpose of providing fresh impetus for future development of these materials for advanced energy storage systems.     

Pseudocapacitive Sodium Storage by Ferroelectric Sn2P2S6 with Layered Nanostructure

Sodium ion batteries (SIB) are considered promising alternative candidates for lithium ion batteries (LIB) because of the wide availability and low cost of sodium, therefore the development of alternative sodium storage materials with comparable performance to LIB is urgently desired. The sodium ions with larger sizes resist intercalation or alloying because of slow reaction kinetics. Most pseudocapacitive sodium storage materials are based on subtle nanomaterial engineering, which is difficult for large‐scale production. Here, ferroelectric Sn₂P₂S₆ with layered nanostructure is developed as sodium ion storage material. The ferroelectricity‐enhanced pseudocapacitance of sodium ion in the interlayer spacing makes the electrochemical reaction easier and faster, endowing the Sn₂P₂S₆ electrode with excellent rate capability and cycle stability. Furthermore, the facile solid state reaction synthesis and common electrode fabrication make the Sn₂P₂S₆ that becomes a promising anode material of SIB.     

Layered Ca0.28MnO2·0.5H2O as a High Performance Cathode for Aqueous Zinc‐Ion Battery

Aqueous zinc‐ion batteries are promising candidates for grid‐scale energy storage because of their intrinsic safety, low cost, and high energy intensity. However, lack of suitable cathode materials with both excellent rate performance and cycling stability hinders further practical application of aqueous zinc‐ion batteries. Here, a nanoflake‐self‐assembled nanorod structure of Ca_0.28MnO₂·0.5H₂O as Zn‐insertion cathode material is designed. The Ca_0.28MnO₂·0.5H₂O exhibits a reversible capacity of 298 mAh g^?1 at 175 mA g^?1 and long‐term cycling stability over 5000 cycles with no obvious capacity fading, which indicates that the per‐insertion of Ca ions and water can significantly improve reversible insertion/extraction stability of Zn²⁺ in Mn‐based layered type material. Further, its charge storage mechanism, especially hydrogen ions, is elucidated. A comprehensive study suggests that the intercalation of hydrogen ions in the first discharge plat is controled by both pH value and type of anion of electrolyte. Further, it can stabilize the Ca_0.28MnO₂·0.5H₂O cathode and facilitate the following insertion of Zn²⁺ in 1 m ZnSO₄/0.1 m MnSO₄ electrolyte. This work can enlighten and promote the development of high‐performance rechargeable aqueous zinc‐ion batteries.     

A High‐Capacity O2‐Type Li‐Rich Cathode Material with a Single‐Layer Li2MnO3 Superstructure

A high capacity cathode is the key to the realization of high‐energy‐density lithium‐ion batteries. The anionic oxygen redox induced by activation of the Li₂MnO₃ domain has previously afforded an O3‐type layered Li‐rich material used as the cathode for lithium‐ion batteries with a notably high capacity of 250–300 mAh g^?1. However, its practical application in lithium‐ion batteries has been limited due to electrodes made from this material suffering severe voltage fading and capacity decay during cycling. Here, it is shown that an O2‐type Li‐rich material with a single‐layer Li₂MnO₃ superstructure can deliver an extraordinary reversible capacity of 400 mAh g^?1 (energy density: ≈1360 Wh kg^?1). The activation of a single‐layer Li₂MnO₃ enables stable anionic oxygen redox reactions and leads to a highly reversible charge–discharge cycle. Understanding the high performance will further the development of high‐capacity cathode materials that utilize anionic oxygen redox processes.     

Layered Transition Metal Dichalcogenide-Based Nanomaterials for Electrochemical Energy Storage

The rapid development of electrochemical energy storage (EES) systems requires novel electrode materials with high performance. A typical 2D nanomaterial, layered transition metal dichalcogenides (TMDs) are regarded as promising materials used for EES systems due to their large specific surface areas and layer structures benefiting fast ion transport. The typical methods for the preparation of TMDs and TMD-based nanohybrids are first summarized. Then, in order to improve the electrochemical performance of various kinds of rechargeable batteries, such as lithium-ion batteries, lithium–sulfur batteries, sodium-ion batteries, and other types of emerging batteries, the strategies for the design and fabrication of layered TMD-based electrode materials are discussed. Furthermore, the applications of layered TMD-based nanomaterials in supercapacitors, especially in untraditional supercapacitors, are presented. Finally, the existing challenges and promising future research directions in this field are proposed.     

Insight into Ca‐Substitution Effects on O3‐Type NaNi1/3Fe1/3Mn1/3O2 Cathode Materials for Sodium‐Ion Batteries Application

O3‐type NaNi_1/3Fe_1/3Mn_1/3O₂ (NaNFM) is well investigated as a promising cathode material for sodium‐ion batteries (SIBs), but the cycling stability of NaNFM still needs to be improved by using novel electrolytes or optimizing their structure with the substitution of different elements sites. To enlarge the alkali‐layer distance inside the layer structure of NaNFM may benefit Na⁺ diffusion. Herein, the effect of Ca‐substitution is reported in Na sites on the structural and electrochemical properties of Na_1?xCa_x/2NFM (x = 0, 0.05, 0.1). X‐ray diffraction (XRD) patterns of the prepared Na_1?xCa_x/2NFM samples show single α‐NaFeO₂ type phase with slightly increased alkali‐layer distance as Ca content increases. The cycling stabilities of Ca‐substituted samples are remarkably improved. The Na_0.9Ca_0.05Ni_1/3Fe_1/3Mn_1/3O₂ (Na_0.9Ca_0.05NFM) cathode delivers a capacity of 116.3 mAh g^?1 with capacity retention of 92% after 200 cycles at 1C rate. In operando XRD indicates a reversible structural evolution through an O3‐P3‐P3‐O3 sequence of Na_0.9Ca_0.05NFM cathode during cycling. Compared to NaNMF, the Na_0.9Ca_0.05NFM cathode shows a wider voltage range in pure P3 phase state during the charge/discharge process and exhibits better structure recoverability after cycling. The superior cycling stability of Na_0.9Ca_0.05NFM makes it a promising material for practical applications in sodium‐ion batteries.     

High‐Performance Aqueous Zinc–Ion Battery Based on Layered H2V3O8 Nanowire Cathode

Rechargeable aqueous zinc–ion batteries have offered an alternative for large‐scale energy storage owing to their low cost and material abundance. However, developing suitable cathode materials with excellent performance remains great challenges, resulting from the high polarization of zinc ion. In this work, an aqueous zinc–ion battery is designed and constructed based on H₂V₃O₈ nanowire cathode, Zn(CF₃SO₃)₂ aqueous electrolyte, and zinc anode, which exhibits the capacity of 423.8 mA h g⁻¹ at 0.1 A g⁻¹, and excellent cycling stability with a capacity retention of 94.3% over 1000 cycles. The remarkable electrochemical performance is attributed to the layered structure of H₂V₃O₈ with large interlayer spacing, which enables the intercalation/de‐intercalation of zinc ions with a slight change of the structure. The results demonstrate that exploration of the materials with large interlayer spacing is an effective strategy for improving electrochemical stability of electrodes for aqueous Zn ion batteries.     

K2Ti2O5@C Microspheres with Enhanced K+ Intercalation Pseudocapacitance Ensuring Fast Potassium Storage and Long‐Term Cycling Stability

Benefiting from the natural abundance and low standard redox potential of potassium, potassium‐ion batteries (PIBs) are regarded as one of the most promising alternatives to lithium‐ion batteries for low‐cost energy storage. However, most PIB electrode materials suffer from sluggish thermodynamic kinetics and dramatic volume expansion during K⁺ (de)intercalation. Herein, it is reported on carbon‐coated K₂Ti₂O₅ microspheres (S‐KTO@C) synthesized through a facile spray drying method. Taking advantage of both the porous microstructure and carbon coating, S‐KTO@C shows excellent rate capability and cycling stability as an anode material for PIBs. Furthermore, the intimate integration of carbon coating through chemical vapor deposition technology significantly enhances the K⁺ intercalation pseudocapacitive behavior. As a proof of concept, a potassium‐ion hybrid capacitor is constructed with the S‐KTO@C (battery‐type anode material) and the activated carbon (capacitor‐type cathode material). The assembled device shows a high energy density, high power density, and excellent capacity retention. This work can pave the way for the development of high‐performance potassium‐based energy storage devices.     

ZIF‐8@ZIF‐67‐Derived Nitrogen‐Doped Porous Carbon Confined CoP Polyhedron Targeting Superior Potassium‐Ion Storage

Potassium ion batteries (KIB) have become a compelling energy‐storage system owing to their cost effectiveness and the high abundance of potassium in comparison with lithium. However, its practical applications have been thwarted by a series of challenges, including marked volume expansion and sluggish reaction kinetics caused by the large radius of potassium ions. In line with this, the exploration of reliable anode materials affording high electrical conductivity, sufficient active sites, and structural robustness is the key. The synthesis of ZIF‐8@ZIF‐67 derived nitrogen‐doped porous carbon confined CoP polyhedron architectures (NC@CoP/NC) to function as innovative KIB anode materials is reported. Such composites enable an outstanding rate performance to harvest a capacity of ≈200 mAh g^?1 at 2000 mA g^?1. Additionally, a high cycling stability can be gained by maintaining a high capacity retention of 93% after 100 cycles at 100 mA g^?1. Furthermore, the potassium ion storage mechanism of the NC@CoP/NC anode is systematically probed through theoretical simulations and experimental characterization. This contribution may offer an innovative and feasible route of emerging anode design toward high performance KIBs.     

Sand-Fixation Model for Interface Engineering of Layered Titania and N/O-Doped Carbon Composites to Enhance Potassium/Sodium Storage

Layered titania (L-TiO₂) holds great potential for potassium-ion batteries (PIBs) and sodium-ion batteries (SIBs) due to their high specific capacity. Synthesizing L-TiO₂ functional materials for high-capacity and long cyclability battery remains challenging due to the unstable and poor conductivity of bare L-TiO₂. In nature, plant growth can stabilize land by preventing sands from dispersing following desertification. Inspired by nature's “sand-fixation model,” Al³⁺ “seeds” are in situ grown on layered Ti₃C₂T_x “land.” Subsequently, NH₂-MIL-101(Al) “plants” with Al as metal nodes are grown on the Ti₃C₂T_x “land” by self-assembly. After annealing and etching processes (similar to desertification), NH₂-MIL-101(Al) is transformed into interconnected N/O-doped carbon (MOF-NOC), which not only acts as a plant-like function to prevent the pulverization of L-TiO₂ transformed from Ti₃C₂T_x but also improves the conductivity and stability of MOF-NOC@L-TiO₂. Al species are selected as seeds to improve interfacial compatibility and form intimate interface heterojunction. Systematic ex situ analysis discloses that the ions storage mechanism can be endowed by mixed contribution of non-Faradaic and Faradaic capacitance. Consequently, the MOF-NOC@L-TiO₂ electrodes exhibit high interfacial capacitive charge storage and outstanding cycling performance. The interface engineering strategy inspired by “sand-fixation model” provides a reference for designing stable layered composites.     

Polypyrenes as High‐Performance Cathode Materials for Aluminum Batteries

The pressing need for low‐cost and large‐scale stationary storage of electricity has led to a new wave of research on novel batteries made entirely of components that have high natural abundances and are easy to manufacture. One example of such an anode–electrolyte–cathode architecture comprises metallic aluminum, AlCl₃:[EMIm]Cl (1‐ethyl‐3‐methylimidazolium chloride) ionic liquid and graphite. Various forms of synthetic and natural graphite cathodes have been tested in recent years in this context. Here, a new type of compelling cathode based on inexpensive pyrene polymers is demonstrated. During charging, the condensed aromatic rings of these polymers are oxidized, which is accompanied by the uptake of aluminum tetrachloride anions (AlCl₄^?) from the chloroaluminate ionic liquid. Discharge is the fast inverse process of reduction and the release of AlCl₄^?. The electrochemical properties of the polypyrenes can be fine‐tuned by the appropriate chemical derivatization. This process is showcased here by poly(nitropyrene‐co‐pyrene), which has a storage capacity of 100 mAh g^?1, higher than the neat polypyrene (70 mAh g^?1) or crystalline pyrene (20 mAh g^?1), at a high discharge voltage (≈1.7 V), energy efficiency (≈86%), and cyclic stability (at least 1000 cycles).     

O3‐Type Layered Ni‐Rich Oxide: A High‐Capacity and Superior‐Rate Cathode for Sodium‐Ion Batteries

Inspired by its high‐active and open layered framework for fast Li⁺ extraction/insertion reactions, layered Ni‐rich oxide is proposed as an outstanding Na‐intercalated cathode for high‐performance sodium‐ion batteries. An O3‐type Na_0.75Ni_0.82Co_0.12Mn_0.06O₂ is achieved through a facile electrochemical ion‐exchange strategy in which Li⁺ ions are first extracted from the LiNi_0.82Co_0.12Mn_0.06O₂ cathode and Na⁺ ions are then inserted into a layered oxide framework. Furthermore, the reaction mechanism of layered Ni‐rich oxide during Na⁺ extraction/insertion is investigated in detail by combining ex situ X‐ray diffraction, X‐ray photoelectron spectroscopy, and electron energy loss spectroscopy. As an excellent cathode for Na‐ion batteries, O3‐type Na_0.75Ni_0.82Co_0.12Mn_0.06O₂ delivers a high reversible capacity of 171 mAh g^?1 and a remarkably stable discharge voltage of 2.8 V during long‐term cycling. In addition, the fast Na⁺ transport in the cathode enables high rate capability with 89 mAh g^?1 at 9 C. The as‐prepared Ni‐rich oxide cathode is expected to significantly break through the limited performance of current sodium‐ion batteries.     

Graphene Scroll‐Coated α‐MnO2 Nanowires as High‐Performance Cathode Materials for Aqueous Zn‐Ion Battery

The development of manganese dioxide as the cathode for aqueous Zn‐ion battery (ZIB) is limited by the rapid capacity fading and material dissolution. Here, a highly reversible aqueous ZIB using graphene scroll‐coated α‐MnO₂ as the cathode is proposed. The graphene scroll is uniformly coated on the MnO₂ nanowire with an average width of 5 nm, which increases the electrical conductivity of the MnO₂ nanowire and relieves the dissolution of the cathode material during cycling. An energy density of 406.6 Wh kg^?1 (382.2 mA h g^?1) at 0.3 A g^?1 can be reached, which is the highest specific energy value among all the cathode materials for aqueous Zn‐ion battery so far, and good long‐term cycling stability with 94% capacity retention after 3000 cycles at 3 A g^?1 are achieved. Meanwhile, a two‐step intercalation mechanism that Zn ions first insert into the layers and then the tunnels of MnO₂ framework is proved by in situ X‐ray diffraction, galvanostatic intermittent titration technique, and X‐ray photoelectron spectroscopy characterizations. The graphene scroll‐coated metallic oxide strategy can also bring intensive interests for other energy storage systems.     

Ti‐Substituted NaNi0.5Mn0.5‐xTixO2 Cathodes with Reversible O3−P3 Phase Transition for High‐Performance Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have been considered as potential candidates for stationary energy storage because of the low cost and wide availability of Na sources. O3‐type layered oxides have been considered as one of the most promising cathodes for SIBs. However, they commonly show inevitable complicated phase transitions and sluggish kinetics, incurring rapid capacity decline and poor rate capability. Here, a series of sodium‐sufficient O3‐type NaNi_0.5Mn_{0.5‐ x} Ti _x O₂ (0 ≤ x ≤ 0.5) cathodes for SIBs is reported and the mechanisms behind their excellent electrochemical performance are studied in comparison to those of their respective end‐members. The combined analysis of in situ X‐ray diffraction, ex situ X‐ray absorption spectroscopy, and scanning transmission electron microscopy for NaNi_0.5Mn_0.2Ti_0.3O₂ reveals that the O3‐type phase transforms reversibly into a P3‐type phase upon Na+ deintercalation/intercalation. The substitution of Ti for Mn enlarges interslab distance and could restrain the unfavorable and irreversible multiphase transformation in the high voltage regions that is usually observed in O3‐type NaNi_0.5Mn_0.5O₂, resulting in improved Na cell performance. This integration of macroscale and atomicscale engineering strategy might open up the modulation of the chemical and physical properties in layered oxides and grasp new insight into the optimal design of high‐performance cathode materials for SIBs.