Regulating cathode surface hydroxyl chemistry enables superior potassium storage.

Potassium vanadium fluorophosphate (KVPO4F) is regarded as a promising cathode candidate for potassium-ion batteries due to its high working voltage and satisfactory theoretical capacity. However, the usage of electrochemically inactive binders and redundant current collectors typically results in inferior electrochemical performance and low energy density, thus implying the important role of rational electrode structure design. Herein, we have reported a scalable and cost-effective synthesis of a cellulose-derived KVPO4F self-supporting electrode, which features a special surface hydroxyl chemistry, three-dimensional porous and conductive framework, as well as super flexible and stable architecture. The cellulose not only serves as a flexible substrate, a pore-forming agent, and a versatile binder for KVPO4F/conductive carbon but also enhances the K-ion migration ability. Benefiting from the special hydroxyl chemistry-induced storage mechanism and electrode structural stability, the flexible freestanding KVPO4F cathode exhibits high-rate performance (53.0% capacity retention with current densities increased 50-fold, from 0.2 C to 10 C) and impressive cycling stability (capacity retention up to 74.9% can be achieved over 1,000 cycles at a rate of 5 C). Such electrode design and surface engineering strategies, along with a deeper understanding of potassium storage mechanisms, provide invaluable guidance for better electrode design to boost the performance of potassium-ion energy storage systems.

Extremely Durable K-Ion Batteries Enabled by Heteroatom Co-Doped Highly-Ordered Porous Carbon Spheres with Nearly 100% Capacity Retention up to 11,000 Cycles.

Currently, one major target for exploring K-ion batteries (KIBs) is enhancing their cycle stability due to the intrinsically sluggish kinetics of large-radius K+ ions. Herein, we report a rationally designed electrode, the S/O co-doped hard carbon spheres with highly ordered porous characteristics (SPC), for extremely durable KIBs. Experimental results and theory calculations confirm that this structure offers exceptional advantages for high-performance KIBs, facilitating rapid K+ diffusion and (de)-intercalation, efficient electrolyte penetration and transport, improved K+ storage sites, and enhanced redox reaction kinetics, thus ensuring the long-term cycle stability. As a result, the as-constructed SPC anode delivers a high reversible capacity of ca. 200 mAh g-1 at a high current density of 2.0 A g-1 and robust stability with ∼100% capacity retention up to 11,000 cycles, outperforming most carbon-based KIB anodes. This work offers insight into developing advanced KIBs with durable stability toward practical applications.

Ether-Based Gel Polymer Electrolyte for High-Voltage Potassium Ion Batteries.

Low-concentration ether electrolytes cannot efficiently achieve oxidation resistance and excellent interface behavior, resulting in severe electrolyte decomposition at a high voltage and ineffective electrode-electrolyte interphase. Herein, we utilize sandwich structure-like gel polymer electrolyte (GPE) to enhance the high voltage stability of potassium-ion batteries (PIBs). The GPE contact layer facilitates stable electrode-electrolyte interphase formation, and the GPE transport layer maintains good ionic transport, which enabled GPE to exhibit a wide electrochemical window and excellent electrochemical performance. In addition, Al corrosion under a high voltage is suppressed through the restriction of solvent molecules. Consequently, when using the designed GPE (based on 1 m), the K||graphite cell exhibits excellent cycling stability of 450 cycles with a capacity retention of 91%, and the K||FeFe-Prussian blue cell (2-4.2 V) delivers a high average Coulombic efficiency of 99.9% over 2200 cycles at 100 mA g-1. This study provides a promising path in the application of ether-based electrolytes in high-voltage and long-lasting PIBs.

Deciphering the Formation and Accumulation of Solid-Electrolyte Interphases in Na and K Carbonate-Based Batteries.

The continuous solid-electrolyte interphase (SEI) accumulation has been blamed for the rapid capacity loss of carbon anodes in Na and K ethylene carbonate (EC)/diethyl carbonate (DEC) electrolytes, but the understanding of the SEI composition and its formation chemistry remains incomplete. Here, we explain this SEI accumulation as the continuous production of organic species in solution-phase reactions. By comparing the NMR spectra of SEIs and model compounds we synthesized, alkali metal ethyl carbonate (MEC, M = Na or K), long-chain alkali metal ethylene carbonate (LCMEC, M = Na or K), and poly(ethylene oxide) (PEO) oligomers with ethyl carbonate ending groups are identified in Na and K SEIs. These components can be continuously generated in a series of solution-phase nucleophilic reactions triggered by ethoxides. Compared with the Li SEI formation chemistry, the enhancement of the nucleophilicity of an intermediate should be the cause of continuous nucleophilic reactions in the Na and K cases.

Unleashing the Power of Sn2S3 Quantum Dots: Advancing Ultrafast and Ultrastable Sodium/Potassium-Ion Batteries with N, S Co-Doped Carbon Fiber Network.

Tin sulfide (Sn2S3) has been recognized as a potential anode material for sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) due to its high theoretical capacities. However, the sluggish ion diffusion kinetics, low conductivity, and severe volume changes during cycling have limited its practical application. In this study, Sn2S3 quantum dots (QDs) (≈1.6 nm) homogeneously embedded in an N, S co-doped carbon fiber network (Sn2S3-CFN) are successfully fabricated by sequential freeze-drying, carbonization, and sulfidation strategies. As anode materials, the Sn2S3-CFN delivers high reversible capacities and excellent rate capability (300.0 mAh g-1 at 10 A g-1 and 250.0 mAh g-1 at 20 A g-1 for SIBs; 165.3 mAh g-1 at 5 A g-1 and 100.0 mAh g-1 at 10 A g-1 for PIBs) and superior long-life cycling capability (279.6 mAh g-1 after 10 000 cycles at 5 A g-1 for SIBs; 166.3 mAh g-1 after 5 000 cycles at 2 A g-1 for PIBs). According to experimental analysis and theoretical calculations, the exceptional performance of the Sn2S3-CFN composite can be attributed to the synergistic effect of the conductive carbon fiber network and the Sn2S3 quantum dots, which contribute to the structural stability, reversible electrochemical reactions, and superior electron transportation and ions diffusion.

KI-Assisted Formation of Spindle-like Prussian White Nanoparticles for High-Performance Potassium-Ion Battery Cathodes.

Prussian white (PW) is considered as a promising cathode material for potassium-ion batteries (KIBs) due to its low cost and high theoretical capacity. However, the high water content and structural defects and the strict synthesis conditions of PW lead to its unsatisfactory cycling performance and low specific capacity, hindering its practical applications. Herein, a template-engaged reduction method is proposed, using MIL-88B(Fe) as a self-template and KI as the reducing agent to prepare K-rich PW with low defects and water content. Furthermore, the hierarchical porous spindle-like morphology can be inherited from the precursor, furnishing sufficient active sites and reducing the ion diffusion path. Consequently, when applied as a KIB cathode material, spindle-like PW (K1.72Fe[Fe(CN)6]0.96·0.342H2O) manifested remarkable potassium storage properties. Notably, a full cell assembled by the spindle-like PW cathode and graphite anode exhibited a large energy density of ∼216.7 Wh kg-1, demonstrating its huge potential for energy storage systems.

Ultrathin Cobalt-Based Prussian Blue Analogue Nanosheet-Assembled Nanoboxes Interpenetrated with Carbon Nanotubes as a Fast Electron/Potassium-Ion Conductor for Superior Potassium Storage.

Rechargeable potassium-ion batteries (PIBs) are regarded as potential substitutes for industrial lithium-ion batteries in large scale energy storage systems due to the world's abundant potassium supplies. Althogh cobalt hexacyanocobaltate (CoHCC) exhibits broad potential as a PIB anode material, its performance is currently unsatisfactory. Herein, novel 5 nm scale ultrathin CoHCC nanosheet-assembled nanoboxes with interspersed carbon nanotubes (CNTs/CoHCC nanoboxes) are fabricated to realize a highly reactive PIB anode. The ultrathin CoHCC layers substantially accelerate electron conduction and provide numerous active sites, while the connected CNTs provide fast axial electron transport. Consequently, the optimized anode exhibits a remarkable discharge capacity of 580.9 mAh g-1 at 0.1 A g-1 and long-term stability with 71.3% retention over 1000 cycles. In situ and ex situ characterizations and density functional theory calculations are further employed to elucidate the K+ storage process and the reason for the enhanced performance of the CNTs/CoHCC nanoboxes.

Uniform P2-K0.6CoO2 Microcubes as a High-Energy Cathode Material for Potassium-Ion Batteries.

Layered transition-metal (TM) oxides have drawn ever-growing interest as positive electrode materials in potassium-ion batteries (PIBs). Nevertheless, the practical implementation of these positive electrode materials is seriously hampered by their inferior cyclic property and rate performance. Reported here is a self-templating strategy to prepare homogeneous P2-K0.6CoO2 (KCO) microcubes. Benefiting from the unusual microcube architecture, the interface between the electrolyte and the active material is considerably diminished. As a result, the KCO microcubes manifest boosted electrochemical properties for potassium storage including large reversible capacity (87.2 mAh g-1 under 20 mA g-1), superior rate performance, and ultralong cyclic steady (an improved capacity retention of 86.9% under 40 mA g-1 after 1000 cycles). More importantly, the fabrication approach can be effectively extended to prepare other layered TM oxide (P3-K0.5MnO2, P3-K0.5Mn0.8Fe0.2O2, P2-K0.6Co0.67Mn0.33O2, and P2-K0.6Co0.66Mn0.17Ni0.17O2) microcubes and nonlayered TM oxide (KFeO2) microcubes.

Scaly MoS2/rGO Composite as an Anode Material for High-Performance Potassium-Ion Battery.

Potassium-ion batteries (PIBs) have been widely studied owing to the abundant reserves, widespread distribution, and easy extraction of potassium (K) resources. Molybdenum disulfide (MoS2) has received a great deal of attention as a key anode material for PIBs owing to its two-dimensional diffusion channels for K+ ions. However, due to its poor electronic conductivity and the huge influence of embedded K+ ions (with a large ionic radius of 3.6 Å) on MoS2 layer, MoS2 anodes exhibit a poor rate performance and easily collapsed structure. To address these issues, the common strategies are enlarging the interlayer spacing to reduce the mechanical strain and increasing the electronic conductivity by adding conductive agents. However, simultaneous implementation of the above strategies by simple methods is currently still a challenge. Herein, MoS2 anodes on reduced graphene oxide (MoS2/rGO) composite were prepared using one-step hydrothermal methods. Owing to the presence of rGO in the synthesis process, MoS2 possesses a unique scaled structure with large layer spacing, and the intrinsic conductivity of MoS2 is proved. As a result, MoS2/rGO composite anodes exhibit a larger rate performance and better cycle stability than that of anodes based on pure MoS2, and the direct mixtures of MoS2 and graphene oxide (MoS2-GO). This work suggests that the composite material of MoS2/rGO has infinite possibilities as a high-quality anode material for PIBs.

A P2/P3 Biphasic Layered Oxide Composite as a High-Energy and Long-Cycle-Life Cathode for Potassium-Ion Batteries.

Layered transition metal oxides are extensively considered as appealing cathode candidates for potassium-ion batteries (PIBs) due to their abundant raw materials and low cost, but their further implementations are limited by slow dynamics and impoverished structural stability. Herein, a layered composite having a P2 and P3 symbiotic structure is designed and synthesized to realize PIBs with large energy density and long-term cycling stability. The unique intergrowth of P2 and P3 phases in the obtained layered oxide is plainly characterized by X-ray diffraction refinement, high-angle annular dark field and annular bright field-scanning transmission electron microscopy at atomic resolution, and Fourier transformation images. The synergistic effect of the two phases of this layered P2/P3 composite is well demonstrated in K+ intercalation/extraction process. The as-prepared layered composite can present a large discharge capacity with the remarkable energy density of 321 Wh kg-1 and also manifest excellent capacity preservation after 600 cycles of K+ uptake/removal.

Chloro-Functionalized Ether-Based Electrolyte for High-Voltage and Stable Potassium-Ion Batteries.

Ether-based electrolyte is beneficial to obtaining good low-temperature performance and high ionic conductivity in potassium ion batteries. However, the dilute ether-based electrolytes usually result in ion-solvent co-intercalation of graphite, poor cycling stability, and hard to withstand high voltage cathodes above 4.0 V. To address the aforementioned issues, an electron-withdrawing group (chloro-substitution) was introduced to regulate the solid-electrolyte interphase (SEI) and enhance the oxidative stability of ether-based electrolytes. The dilute (~0.91 M) chloro-functionalized ether-based electrolyte not only facilitates the formation of homogeneous dual halides-based SEI, but also effectively suppress aluminum corrosion at high voltage. Using this functionalized electrolyte, the K||graphite cell exhibits a stability of 700 cycles, the K||Prussian blue (PB) cell (4.3 V) delivers a stability of 500 cycles, and the PB||graphite full-cell reveals a long stability of 6000 cycles with a high average Coulombic efficiency of 99.98 %. Additionally, the PB||graphite full-cell can operate under a wide temperature range from -5 °C to 45 °C. This work highlights the positive impact of electrolyte functionalization on the electrochemical performance, providing a bright future of ether-based electrolytes application for long-lasting, wide-temperature, and high Coulombic efficiency PIBs and beyond.

Nonflammable Phosphate-Based Electrolyte for Safe and Stable Potassium Batteries Enabled by Optimized Solvation Effect.

Current potassium-ion batteries (PIBs) are limited in safety and lifetime owing to the lack of suitable electrolyte solutions. To address these issues, herein, we report an innovative non-flammable electrolyte design strategy that leverages an optimal moderate solvation phosphate-based solvent which strikes a balance between solvation capability and salt dissociation ability, leading to superior electrochemical performance. The formulated electrolyte simultaneously exhibits the advantages of low salt concentration (only 0.6 M), low viscosity, high ionic conductivity, high oxidative stability, and safety. Our electrolyte also promotes the formation of self-limiting inorganic-rich interphases at the anode surface, alongside robust cathode-electrolyte interphase on iron-based Prussian blue analogues, mitigating electrode/electrolyte side reactions and preventing Fe dissolution. Notably, the PIBs employing our electrolyte exhibit exceptional durability, with 80 % capacity retention after 2,000 cycles at high-voltage of 4.2 V in a coin cell. Impressively, in a larger scale pouch cell, it maintains over 81 % of its initial capacity after 1,400 cycles at 1 C-rate with high average Coulombic efficiency of 99.6 %. This work represents a significant advancement toward the realization of safe, sustainable, and high-performance PIBs.

Tunable Interfacial Electric Field-Mediated Cobalt-Doped FeSe/Fe3Se4 Heterostructure for High-Efficiency Potassium Storage.

The interfacial electric field (IEF) in the heterostructure can accelerate electron transport and ion migration, thereby enhancing the electrochemical performance of potassium-ion batteries (PIBs). Nevertheless, the quantification and modulation of the IEF for high-efficiency PIB anodes currently remains a blank slate. Herein, we achieve for the first time the quantification and tuning of IEF via amorphous carbon-coated undifferentiated cobalt-doped FeSe/Fe3Se4 heterostructure (denoted UN-CoFe4Se5/C) for efficient potassium storage. Co doping can increase the IEF in FeSe/Fe3Se4, thereby improving the electron transport, promoting the potassium adsorption capacity, and lowering the diffusion barrier. As expected, the IEF magnitude in UN-CoFe4Se5/C is experimentally quantified as 62.84 mV, which is 3.65 times larger than that of amorphous carbon-coated FeSe/Fe3Se4 heterostructure (Fe4Se5/C). Benefiting from the strong IEF, UN-CoFe4Se5/C as a PIB anode exhibits superior rate capability (145.8 mAh g-1 at 10.0 A g-1) and long cycle lifespan (capacity retention of 95.1 % over 3000 cycles at 1.0 A g-1). Furthermore, this undifferentiated doping strategy can universally regulate the IEF magnitude in CoSe2/Co9Se8 and FeS2/Fe7S8 heterostructures. This work can provide fundamental insights into the design of advanced PIB electrodes.

Heat-Resistant Carbon-Coated Potassium Magnesium Hexacyanoferrate Nanoplates for High-Performance Potassium-Ion Batteries.

Metal hexacyanoferrates (HCFs) are regarded as promising cathode materials for potassium-ion batteries (PIBs) on account of their low cost and high energy density. However, the difficult-to-remove [Fe(CN)6] vacancies and crystal water lead to structural instability and capacity deterioration as well as the stereotype of poor thermostability of conventional HCFs. Herein, we report (100) face-oriented potassium magnesium hexacyanoferrate (KMgHCF) nanoplates with low [Fe(CN)6] vacancies and high crystallinity, enabling thermostability up to 550 °C, high-temperature carbon coating and crystal water elimination. The as-obtained KMgHCF/C nanoplates exhibit superior potassium storage properties, including a large reversible capacity of 84.6 mAh g-1, a high voltage plateau of 3.87 V, excellent long-term cycling performance over 15000 cycles and high rate capability at 5 A g-1. The unprecedented cycling stability of KMgHCF/C is attributed to the synergistic effect of a highly reversible two-phase reaction, low [Fe(CN)6] vacancies and no crystal water, a specially exposed steady (100) surface, and a protective carbon coating. This work provides a new material selection and modification strategy for the practical application of HCFs in PIBs.

Highly Crystalline Prussian Blue for Kinetics Enhanced Potassium Storage.

Prussian blue analogs (PBAs) are promising cathode materials for potassium-ion batteries (KIBs) owing to their large open framework structure. As the K+ migration rate and storage sites rely highly on the periodic lattice arrangement, it is rather important to guarantee the high crystallinity of PBAs. Herein, highly crystalline K2 Fe[Fe(CN)6 ] (KFeHCF-E) is synthesized by coprecipitation, adopting the ethylenediaminetetraacetic acid dipotassium salt as a chelating agent. As a result, an excellent rate capability and ultra-long lifespan (5000 cycles at 100 mA g-1 with 61.3% capacity maintenance) are achieved when tested in KIBs. The highest K+ migration rate of 10-9 cm2 s-1 in the bulk phase is determined by the galvanostatic intermittent titration technique. Remarkably, the robust lattice structure and reversible solid-phase K+ storage mechanism of KFeHCF-E are proved by in situ XRD. This work offers a simple crystallinity optimization method for developing high-performance PBAs cathode materials in advanced KIBs.

In situ healing of dendrites in a potassium metal battery.

The use of potassium (K) metal anodes could result in high-performance K-ion batteries that offer a sustainable and low-cost alternative to lithium (Li)-ion technology. However, formation of dendrites on such K-metal surfaces is inevitable, which prevents their utilization. Here, we report that K dendrites can be healed in situ in a K-metal battery. The healing is triggered by current-controlled, self-heating at the electrolyte/dendrite interface, which causes migration of surface atoms away from the dendrite tips, thereby smoothening the dendritic surface. We discover that this process is strikingly more efficient for K as compared to Li metal. We show that the reason for this is the far greater mobility of surface atoms in K relative to Li metal, which enables dendrite healing to take place at an order-of-magnitude lower current density. We demonstrate that the K-metal anode can be coupled with a potassium cobalt oxide cathode to achieve dendrite healing in a practical full-cell device.

Multipod Bi(Cu2-xS)n Nanocrystals formed by Dynamic Cation-Ligand Complexation and Their Use as Anodes for Potassium-Ion Batteries.

We report the formation of an intermediate lamellar Cu-thiolate complex, and tuning its relative stability using alkylphosphonic acids are crucial to enabling controlled heteronucleation to form Bi(Cu2-xS)n heterostructures with a tunable number of Cu2-xS stems on a Bi core. The denticity of the phosphonic acid group, concentration, and chain length of alkylphosphonic acids are critical factors determining the stability of the Cu-thiolate complex. Increasing the stability of the Cu-thiolate results in single Cu2-xS stem formation, and decreased stability of the Cu-thiolate complex increases the degree of heteronucleation to form multiple Cu2-xS stems on the Bi core. Spatially separated multiple Cu2-xS stems transform into a support network to hold a fragmented Bi core when used as an anode in a K-ion battery, leading to a more stable cycling performance showing a specific capacity of ∼170 mAh·g-1 after 200 cycles compared to ∼111 mAh·g-1 for Bi-Cu2-xS single-stem heterostructures.

Application of New COF Materials in Secondary Battery Anode Materials.

Covalent organic framework materials (COFs), as a new type of organic porous material, not only have the characteristics of flexible structure, abundant resources, environmental friendliness, etc., but also have the characteristics of a regular structure and uniform pore channels, so they have broad application prospects in secondary batteries. Their functional group structure, type, and number of active sites play a crucial role in the performance of different kinds of batteries. Therefore, this article starts from these aspects, summarizes the application and research progress of the COF anode materials used in lithium-ion batteries, sodium-ion batteries, and potassium-ion batteries in recent years, discusses the energy storage mechanism of COF materials, and expounds the application prospects of COF electrodes in the field of energy storage.

Anthraquinone-Quinizarin Copolymer as a Promising Electrode Material for High-Performance Lithium and Potassium Batteries.

The growing demand for cheap, safe, recyclable, and environmentally friendly batteries highlights the importance of the development of organic electrode materials. Here, we present a novel redox-active polymer comprising a polyaniline-type conjugated backbone and quinizarin and anthraquinone units. The synthesized polymer was explored as a cathode material for batteries, and it delivered promising performance characteristics in both lithium and potassium cells. Excellent lithiation efficiency enabled high discharge capacity values of >400 mA g-1 in combination with good stability upon charge-discharge cycling. Similarly, the potassium cells with the polymer-based cathodes demonstrated a high discharge capacity of >200 mAh g-1 at 50 mA g-1 and impressive stability: no capacity deterioration was observed for over 3000 cycles at 11 A g-1, which was among the best results reported for K ion battery cathodes to date. The synthetic availability and low projected cost of the designed material paves a way to its practical implementation in scalable and inexpensive organic batteries, which are emerging as a sustainable energy storage technology.

Green Ether Electrolytes for Sustainable High-voltage Potassium Ion Batteries.

Ether-based electrolytes are promising for secondary batteries due to their good compatibility with alkali metal anodes and high ionic conductivity. However, they suffer from poor oxidative stability and high toxicity, leading to severe electrolyte decomposition at high voltage and biosafety/environmental concerns when electrolyte leakage occurs. Here, we report a green ether solvent through a rational design of carbon-chain regulation to elicit steric hindrance, such a structure significantly reducing the solvent's biotoxicity and tuning the solvation structure of electrolytes. Notably, our solvent design is versatile, and an anion-dominated solvation structure is favored, facilitating a stable interphase formation on both the anode and cathode in potassium-ion batteries. Remarkably, the green ether-based electrolyte demonstrates excellent compatibility with K metal and graphite anode and a 4.2 V high-voltage cathode (200 cycles with average Coulombic efficiency of 99.64 %). This work points to a promising path toward the molecular design of green ether-based electrolytes for practical high-voltage potassium-ion batteries and other rechargeable batteries.