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1.
K‐ion batteries (KIBs) are promising for large‐scale energy storage owing to various advantages like the high abundance of potassium resources in the Earth's crust, high operational potentials, and high power due to fast diffusion of K+ ions. However, to realize the practical application of KIBs, electrode materials are needed with high operational voltage, good capacity, long cycle life, and low‐cost. This work reports a layered open framework material, K2[(VOHPO4)2(C2O4)], composited with reduced graphene oxide (rGO) as a 4 V positive electrode material for KIBs. The material is prepared by a simple precipitation reaction at room temperature. The material demonstrates reversible K‐extraction/insertion with conventional carbonate ester KPF6 solutions; however, with low specific capacity and low Coulombic efficiency. A high discharge capacity of >100 mAh g?1 with good cycling stability and higher Coulombic efficiency is achieved in a highly concentrated electrolyte, 7 mol kg?1 of potassium bis(fluorosulfonyl)amide (KFSA) in dimethoxyethane (DME) at 0.1 C rate. Due to the facile migration of K+ ions in the framework, the material exhibits excellent rate capability with a discharge capacity of 80 mAh g?1 at 10 C rate, and a good capacity retention of 67% after 500 cycles at 2 C rate.  相似文献   

2.
Identifying suitable electrode materials for sodium‐ion and potassium‐ion storage holds the key to the development of earth‐abundant energy‐storage technologies. This study reports an anode material based on self‐assembled hierarchical spheroid‐like KTi2(PO4)3@C nanocomposites synthesized via an electrospray method. Such an architecture synergistically combines the advantages of the conductive carbon network and allows sufficient space for the infiltration of the electrolyte from the porous structure, leading to an impressive electrochemical performance, as reflected by the high reversible capacity (283.7 mA h g?1 for Na‐ion batteries; 292.7 mA h g?1 for K‐ion batteries) and superior rate capability (136.1 mA h g?1 at 10 A g?1 for Na‐ion batteries; 133.1 mA h g?1 at 1 A g?1 for K‐ion batteries) of the resulting material. Moreover, the different ion diffusion behaviors in the two systems are revealed to account for the difference in rate performance. These findings suggest that KTi2(PO4)3@C is a promising candidate as an anode material for sodium‐ion and potassium‐ion batteries. In particular, the present synthetic approach could be extended to other functional electrode materials for energy‐storage materials.  相似文献   

3.
Although potassium‐ion batteries (KIBs) have been considered to be promising alternatives to conventional lithium‐ion batteries due to large abundance and low cost of potassium resources, their development still stays at the infancy stage due to the lack of appropriate cathode and anode materials with reversible potassium insertion/extraction as well as good rate and cycling performance. Herein, a novel dual‐carbon battery based on a potassium‐ion electrolyte (named as K‐DCB), utilizing expanded graphite as cathode material and mesocarbon microbead as anode material is developed. The working mechanism of the K‐DCB is investigated, which is further demonstrated to deliver a high reversible capacity of 61 mA h g‐1 at a current density of 1C over a voltage window of 3.0–5.2 V, as well as good cycling performance with negligible capacity decay after 100 cycles. Moreover, the high working voltage with medium discharge voltage of 4.5 V also enables the K‐DCB to meet the requirement of some high‐voltage devices. With the merits of environmental friendliness, low cost and high energy density, the K‐DCB shows attractive potential for future energy storage application.  相似文献   

4.
Reversible intercalation of potassium‐ion (K+) into graphite makes it a promising anode material for rechargeable potassium‐ion batteries (PIBs). However, the current graphite anodes in PIBs often suffer from poor cyclic stability with low coulombic efficiency. A stable solid electrolyte interphase (SEI) is necessary for stabilizing the large interlayer expansion during K+ insertion. Herein, a localized high‐concentration electrolyte (LHCE) is designed by adding a highly fluorinated ether into the concentrated potassium bis(fluorosulfonyl)imide/dimethoxyethane, which forms a durable SEI on the graphite surface and enables highly reversible K+ intercalation/deintercalation without solvent cointercalation. Furthermore, this LHCE shows a high ionic conductivity (13.6 mS cm?1) and excellent oxidation stability up to 5.3 V (vs K+/K), which enables compatibility with high‐voltage cathodes. The kinetics study reveals that K+ intercalation/deintercalation does not follow the same pathway. The potassiated graphite exhibits excellent depotassiation rate capability, while the formation of a low stage intercalation compound is the rate‐limiting step during potassiation.  相似文献   

5.
Potassium‐ion batteries (KIBs) have attracted increasing attention for grid‐scale energy storage due to the abundance of potassium resources, low cost, and competitive energy density. The key challenge for KIBs is to develop high‐performance electrode materials. However, the exploration of high‐capacity and ultrastable electrodes for KIBs remains challenging because of the sluggish diffusion kinetics of K+ ions during the charging/discharging processes. This study reports for the first time a facile ion‐intercalation‐mediated exfoliation method with Mg2+ cations and NO3 anions as ion assistants for the fabrication of expanded few‐layered ternary Ta2NiSe5 (EF‐TNS) flakes with interlayer spacing up to 1.1 nm and abundant Se sites (NiSe4 tetrahedra/TaSe6 octahedra clusters) for superior potassium‐ion storage. The EF‐TNS deliver a high capacity of 315 mAh g–1, excellent rate capability (121 mAh g–1 at a current density of 1000 mA g–1), and ultrastable cycling performance (81.4% capacity retention after 1100 cycles). Detailed theoretical analysis via first‐principles calculations and experimental results elucidate that K+ ions intercalate through the expanded interlayers effectively and prefer to transport along zigzag pathways in layered Ta2NiSe5. This work provides a new avenue for designing novel ternary intercalation/pseudocapacitance‐type KIBs with high capacity, excellent rate capability, and superior long‐term cycling performance.  相似文献   

6.
Thanks to low costs and the abundance of the resources, sodium‐ion (SIBs) and potassium‐ion batteries (PIBs) have emerged as leading candidates for next‐generation energy storage devices. So far, only few materials can serve as the host for both Na+ and K+ ions. Herein, a cubic phase CuSe with crystal‐pillar‐like morphology (CPL‐CuSe) assembled by the nanosheets are synthesized and its dual functionality in SIBs and PIBs is comprehensively studied. The electrochemical measurements demonstrate that CPL‐CuSe enables fast Na+ and K+ storage as well as the sufficiently long duration. Specifically, the anode delivers a specific capacity of 295 mA h g?1 at current density of 10 A g?1 in SIBs, while 280 mA h g?1 at 5 A g?1 in PIBs, as well as the high capacity retention of nearly 100% over 1200 cycles and 340 cycles, respectively. Remarkably, CPL‐CuSe exhibits a high initial coulombic efficiency of 91.0% (SIBs) and 92.4% (PIBs), superior to most existing selenide anodes. A combination of in situ X‐ray diffraction and ex situ transmission electron microscopy tests fundamentally reveal the structural transition and phase evolution of CuSe, which shows a reversible conversion reaction for both cells, while the intermediate products are different due to the sluggish K+ insertion reaction.  相似文献   

7.
Given the merits of low cost, fast ionic transport in electrolyte, and high operating voltage, potassium ion batteries (PIBs) are promising alternatives to lithium‐ion batteries. However, developing suitable electrode materials that can reversibly accommodate large potassium ions is a great challenge. Here, guided by density functional theory (DFT) calculations, it is demonstrated that the strategy of interfacial engineering via surface amorphization of VO2 (B) nanorods (SA‐VO2), which results in the formation of a crystalline core/amorphous shell heterostructure, enables superior K+ storage performance in terms of large capacity, outstanding rate capability, and long cycle stability working as an anode for PIBs. DFT calculations reveal that the created crystalline/amorphous heterointerface in SA‐VO2 can substantially lower the surface energy, narrow the band gap, and reduce the K+ diffusion barrier of VO2 (B). These conditions enable enhanced K+ storage capacity and rapid K+/electron transfer, which result in large capacity and outstanding rate capability. Using in situ X‐ray diffraction and in situ transmission electron microscopy complemented by ex situ microscopic and spectroscopic techniques, it is unveiled that the superior cycling stability originates from the excellent phase reversibility with negligible strain response and robust mechanical behavior of SA‐VO2 upon (de)potassiation.  相似文献   

8.
Potassium‐ion batteries are attracting great interest for emerging large‐scale energy storage owing to their advantages such as low cost and high operational voltage. However, they are still suffering from poor cycling stability and sluggish thermodynamic kinetics, which inhibits their practical applications. Herein, the synthesis of hierarchical K1.39Mn3O6 microspheres as cathode materials for potassium‐ion batteries is reported. Additionally, an effective AlF3 surface coating strategy is applied to further improve the electrochemical performance of K1.39Mn3O6 microspheres. The as‐synthesized AlF3 coated K1.39Mn3O6 microspheres show a high reversible capacity (about 110 mA h g?1 at 10 mA g?1), excellent rate capability, and cycling stability. Galvanostatic intermittent titration technique results demonstrate that the increased diffusion kinetics of potassium‐ion insertion and extraction during discharge and charge processes benefit from both the hierarchical sphere structure and surface modification. Furthermore, ex situ X‐ray diffraction measurements reveal that the irreversible structure evolution can be significantly mitigated via surface modification. This work sheds light on rational design of high‐performance cathode materials for potassium‐ion batteries.  相似文献   

9.
Finding suitable electrode materials for alkali‐metal‐ion storage is vital to the next‐generation energy‐storage technologies. Polyantimonic acid (PAA, H2Sb2O6 · nH2O), having pentavalent antimony species and an interconnected tunnel‐like pyrochlore crystal framework, is a promising high‐capacity energy‐storage material. Fabricating electrochemically reversible PAA electrode materials for alkali‐metal‐ion storage is a challenge and has never been reported due to the extremely poor intrinsic electronic conductivity of PAA associated with the highest oxidation state Sb(V). Combining nanostructure engineering with a conductive‐network construction strategy, here is reported a facile one‐pot synthesis protocol for crafting uniform internal‐void‐containing PAA nano‐octahedra in a composite with nitrogen‐doped reduced graphene oxide nanosheets (PAA?N‐RGO), and for the first time, realizing the reversible storage of both Li+ and K+ ions in PAA?N‐RGO. Such an architecture, as validated by theoretical calculations and ex/in situ experiments, not only fully takes advantage of the large‐sized tunnel transport pathways (0.37 nm2) of PAA for fast solid‐phase ionic diffusion but also leads to exponentially increased electrical conductivity (3.3 S cm?1 in PAA?N‐RGO vs 4.8 × 10?10 S cm?1 in bare‐PAA) and yields an inside‐out buffer function for accommodating volume expansion. Compared to electrochemically irreversible bare‐PAA, PAA?N‐RGO manifests reversible conversion‐alloying of Sb(V) toward fast and durable Li+‐ and K+‐ion storage.  相似文献   

10.
The exploration of high‐energy‐density cathode materials is vital to the practical use of K‐ion batteries. Layered K‐metal oxides have too high a voltage slope due to their large K+–K+ interaction, resulting in low specific capacity and average voltage. In contrast, the 3D arrangement of K+, with polyanions separating them, reduces the strength of the effective K+‐K+ repulsion, which in turn increases specific capacity and voltage. Here, stoichiometric KVPO4F for use as a high‐energy‐density K‐ion cathode is developed. The KVPO4F cathode delivers a reversible capacity of ≈105 mAh g?1 with an average voltage of ≈4.3 V (vs K/K+), resulting in a gravimetric energy density of ≈450 Wh kg?1. During electrochemical cycling, the KxVPO4F cathode goes through various intermediate phases at x = 0.75, 0.625, and 0.5 upon K extraction and reinsertion, as determined by ex situ X‐ray diffraction characterization and ab initio calculations. This work further explains the role of oxygen substitution in KVPO4+xF1?x: the oxygenation of KVPO4F leads to an anion‐disordered structure which prevents the formation of K+/vacancy orderings without electrochemical plateaus and hence to a smoother voltage profile.  相似文献   

11.
K‐ion batteries are a potentially exciting and new energy storage technology that can combine high specific energy, cycle life, and good power capability, all while using abundant potassium resources. The discovery of novel cathodes is a critical step toward realizing K‐ion batteries (KIBs). In this work, a layered P2‐type K0.6CoO2 cathode is developed and highly reversible K ion intercalation is demonstrated. In situ X‐ray diffraction combined with electrochemical titration reveals that P2‐type K0.6CoO2 can store and release a considerable amount of K ions via a topotactic reaction. Despite the large amount of phase transitions as function of K content, the cathode operates highly reversibly and with good rate capability. The practical feasibility of KIBs is further demonstrated by constructing full cells with a graphite anode. This work highlights the potential of KIBs as viable alternatives for Li‐ion and Na‐ion batteries and provides new insights and directions for the development of next‐generation energy storage systems.  相似文献   

12.
The inherent short‐term transience of solar and wind sources cause significant challenges for the electricity grid. Energy storage systems that can simultaneously provide high power, long cycle life, and high energy efficiency are required to accommodate the fast‐changing output fluctuations. Here, an ultrafast aqueous K‐ion battery based on the potassium‐rich mesoporous nickel ferrocyanide (II) (K2NiFe(CN)6·1.2H2O) is developed. This battery achieves an unprecedented rate capability up to 500 C (8214 W kg?1), which only takes 4.1 s for one charge or discharge. The open‐framework structure of K2NiFe(CN)6·1.2H2O with small volume variation supports the capacity retention of 98.6% after 5000 cycles, and a superior round‐trip energy efficiency of 95.6% at a 5 C rate. Beyond monovalent ion storage, K2NiFe(CN)6·1.2H2O can also function as a versatile high‐rate cathode for divalent‐ion batteries (Mg2+), trivalent‐ion batteries (Al3+), and hybrid full‐cells applications. These properties represent a significant step forward in the exploitation of ultrafast metal ions storage, and accelerate the development of intermittent grid‐scale energy storage technologies.  相似文献   

13.
The current Na+ storage performance of carbon‐based materials is still hindered by the sluggish Na+ ion transfer kinetics and low capacity. Graphene and its derivatives have been widely investigated as electrode materials in energy storage and conversion systems. However, as anode materials for sodium‐ion batteries (SIBs), the severe π–π restacking of graphene sheets usually results in compact structure with a small interlayer distance and a long ion transfer distance, thus leading to low capacity and poor rate capability. Herein, partially reduced holey graphene oxide is prepared by simple H2O2 treatment and subsequent low temperature reduction of graphene oxide, leading to large interlayer distance (0.434 nm), fast ion transport, and larger Na+ storage space. The partially remaining oxygenous groups can also contribute to the capacity by redox reaction. As anode material for SIBs, the optimized electrode delivers high reversible capacity, high rate capability (365 and 131 mAh g?1 at 0.1 and 10 A g?1, respectively), and good cycling performance (163 mAh g?1 after 3000 cycles at a current density of 2 A g?1), which is among the best reported performances for carbon‐based SIB anodes.  相似文献   

14.
Potassium‐ion batteries (KIBs) are important alternatives to lithium‐ and sodium‐ion batteries. Herein, microsized a Bi electrode delivers exceptional potassium storage capacity, stability, and rate capability by the formation of an elastic and adhesive oligomer‐containing solid electrolyte interface with the assistance of diglyme electrolytes. The kinetics‐controlled K–Bi phase transitions are unraveled combining electrochemical profiles, in situ X‐ray diffraction and density functional theory calculations. Reversible, stepwise Bi–KBi2–K3Bi2–K3Bi transitions govern the electrochemical processes after the initial continuous surface potassiation. The Bi electrode outperforms the other anode counterparts considering both capacity and potential. This work provides critical insights into the rational design of high‐performance anode materials for KIBs.  相似文献   

15.
Potassium‐ion batteries (KIBs) are very promising alternatives to lithium‐ion batteries (LIBs) for large‐scale energy storage. However, traditional carbon anode materials usually show poor performance in KIBs due to the large size of K ions. Herein, a carbonization‐etching strategy is reported for making a class of sulfur (S) and oxygen (O) codoped porous hard carbon microspheres (PCMs) material as a novel anode for KIBs through pyrolysis of the polymer microspheres (PMs) composed of a liquid crystal/epoxy monomer/thiol hardener system. The as‐made PCMs possess a porous architecture with a large Brunauer–Emmett–Teller surface area (983.2 m2 g?1), an enlarged interlayer distance (0.393 nm), structural defects induced by the S/O codoping and also amorphous carbon nature. These new features are important for boosting potassium ion storage, allowing the PCMs to deliver a high potassiation capacity of 226.6 mA h g?1 at 50 mA g?1 over 100 cycles and be displaying high stability by showing a potassiation capacity of 108.4 mA h g?1 over 2000 cycles at 1000 mA g?1. The density functional theory calculations demonstrate that S/O codoping not only favors the adsorption of K to the PCMs electrode but also reduces its structural deformation during the potassiation/depotassiation. The present work highlights the important role of hierarchical porosity and S/O codoping in potassium storage.  相似文献   

16.
Among the negative electrode materials for potassium ion batteries, carbon is very promising because of its low cost and environmental benignity. However, the relatively low storage capacity and sluggish kinetics still hinder its practical application. Herein, a large scalable sulfur/nitrogen dual‐doped hard carbon is prepared via a facile pyrolysis process with low‐cost sulfur and polyacrylonitrile as precursors. The dual‐doped hard carbon exhibits hierarchical structure, abundant defects, and functional groups. The material delivers a high reversible potassium storage capacity and excellent rate performance. In particular, a high reversible capacity of 213.7 and 144.9 mA h g?1 can be retained over 500 cycles at 0.1 A g?1 and 1200 cycles at 3 A g?1, respectively, demonstrating remarkable cycle stability at both low and high rates, superior to the other carbon materials reported for potassium storage, to the best of the authors' knowledge. Structure and kinetics studies suggest that the dual‐doping enhances the potassium diffusion and storage, profiting from the formation of a hierarchical structure, introduction of defects, and generation of increased graphitic and pyridinic N sites. This study demonstrates that a facile and scalable pyrolysis strategy is effective to realize hierarchical structure design and heteroatom doping of carbon, to achieve excellent potassium storage performance.  相似文献   

17.
Potassium‐ion batteries (PIBs) are promising energy storage systems because of the abundance and low cost of potassium. The formidable challenge is to develop suitable electrode materials and electrolytes for accommodating the relatively large size and high activity of potassium. Herein, Bi‐based materials are reported as novel anodes for PIBs. Nanostructural design and proper selection of the electrolyte salt have been used to achieve excellent cycling performance. It is found that the potassiation of Bi undergoes a solid‐solution reaction, followed by two typical two‐phase reactions, corresponding to Bi ? Bi(K) and Bi(K) ? K5Bi4 ? K3Bi, respectively. By choosing potassium bis(fluorosulfonyl)imide (KFSI) to replace potassium hexafluorophosphate (KPF6) in carbonate electrolyte, a more stable solid electrolyte interphase layer is achieved and results in notably enhanced electrochemical performance. More importantly, the KFSI salt is very versatile and can significantly promote the electrochemical performance of other alloy‐based anode materials, such as Sn and Sb.  相似文献   

18.
Potassium‐ion batteries (PIBs) are an emerging, affordable, and environmentally friendly alternative to lithium‐ion batteries, with their further development driven by the need for suitably performing electrode materials capable of reversibly accommodating the relatively large K+. Layer‐structured manganese oxides are attractive as electrodes for PIBs, but suffer from structural instability and sluggish kinetics of K+ insertion/extraction, leading to poor rate capability. Herein, cobalt is successfully introduced at the manganese site in the KxMnO2 layered oxide electrode material and it is shown that with only 5% Co, the reversible capacity increases by 30% at 22 mA g‐1 and by 92% at 440 mA g‐1. In operando synchrotron X‐ray diffraction reveals that Co suppresses Jahn–Teller distortion, leading to more isotropic migration pathways for K+ in the interlayer, thus enhancing the ionic diffusion and consequently, rate capability. The detailed analysis reveals that additional phase transitions and larger volume change occur in the Co‐doped material as a result of layer gliding, with these associated with faster capacity decay, despite the overall capacity remaining higher than the pristine material, even after 500 cycles. These results assert the importance of understanding the detailed structural evolution that underpins performance that will inform the strategic design of electrode materials for high‐performance PIBs.  相似文献   

19.
Rationally designed P2‐K0.75[Ni1/3Mn2/3]O2 is introduced as a novel cathode material for potassium‐ion batteries (KIBs). P2‐K0.75[Ni1/3Mn2/3]O2 cathode material designed through electrochemical ion‐exchange from P2‐Na2/3[Ni1/3Mn2/3]O2 exhibits satisfactory electrode performances; 110 mAh g?1 (20 mA g?1) retaining 86% of capacity for 300 cycles and unexpectedly high reversible capacity of about 91 mAh g?1 (1400 mA g?1) with excellent capacity retention of 83% over 500 cycles. According to theoretical and experimental investigations, the overall potassium storage mechanism of P2‐K0.75[Ni1/3Mn2/3]O2 is revealed to be a single‐phase reaction with small lattice change upon charge and discharge, presenting the Ni4+/2+ redox couple reaction. Such high power capability is possible through the facile K+ migration in the K0.75[Ni1/3Mn2/3]O2 structure with a low activation barrier energy of ≈210 meV. These findings indicate that P2‐K0.75[Ni1/3Mn2/3]O2 is a promising candidate cathode material for high‐rate and long‐life KIBs.  相似文献   

20.
Soft carbon has attracted tremendous attention as an anode in rocking‐chair batteries owing to its exceptional properties including low‐cost, tunable interlayer distance, and favorable electronic conductivity. However, it fails to exhibit decent performance for sodium‐ion storage owing to difficulties in the formation of sodium intercalation compounds. Here, microporous soft carbon nanosheets are developed via a microwave induced exfoliation strategy from a conventional soft carbon compound obtained by pyrolysis of 3,4,9,10‐perylene tetracarboxylic dianhydride. The micropores and defects at the edges synergistically leads to enhanced kinetics and extra sodium‐ion storage sites, which contribute to the capacity increase from 134 to 232 mAh g?1 and a superior rate capability of 103 mAh g?1 at 1000 mA g?1 for sodium‐ion storage. In addition, the capacitance‐dominated sodium‐ion storage mechanism is identified through the kinetics analysis. The in situ X‐ray diffraction analyses are used to reveal that sodium ions intercalate into graphitic layers for the first time. Furthermore, the as‐prepared nanosheets can also function as an outstanding anode for potassium‐ion storage (reversible capacity of 291 mAh g?1) and dual‐ion full cell (cell‐level capacity of 61 mAh g?1 and average working voltage of 4.2 V). These properties represent the potential of soft carbon for achieving high‐energy, high‐rate, and low‐cost energy storage systems.  相似文献   

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