Recent Advances in Pristine Iron Triad Metal-Organic Framework Cathodes for Alkali Metal-Ion Batteries.

Pristine iron triad metal-organic frameworks (MOFs), i.e., Fe-MOFs, Co-MOFs, Ni-MOFs, and heterometallic iron triad MOFs, are utilized as versatile and promising cathodes for alkali metal-ion batteries, owing to their distinctive structure characteristics, including modifiable and designable composition, multi-electron redox-active sites, exceptional porosity, and stable construction facilitating rapid ion diffusion. Notably, pristine iron triad MOFs cathodes have recently achieved significant milestones in electrochemical energy storage due to their exceptional electrochemical properties. Here, the recent advances in pristine iron triad MOFs cathodes for alkali metal-ion batteries are summarized. The redox reaction mechanisms and essential strategies to boost the electrochemical behaviors in associated electrochemical energy storage devices are also explored. Furthermore, insights into the future prospects related to pristine iron triad MOFs cathodes for lithium-ion, sodium-ion, and potassium-ion batteries are also delivered.

2D Se-Rich ZnSe/CoSe2@C Heterostructured Composite as Ultrastable Anodes for Alkaline-Ion Batteries.

2D transitional metal selenide heterostructures are promising electrode materials for potassium-ion batteries (PIBs) owing to the large surface area, high mechanical strength, and short diffusion pathways. However, the cycling performance remains a significant challenge, particularly concerning the electrochemical conversion reaction. Herein, 2D Se-rich ZnSe/CoSe2@C heterostructured composite is fabricated via a convenient hydrothermal approach followed by selenization process, and then applied as high-performance anodes for PIBs. For example, the capacity delivered by the heterostructured composite is mainly contributed to the synergistic effect of conversion and alloy/de-alloy processes aroused by K+, where K+ may highly insert or de-insert into Se-rich ZnSe/CoSe2@C. The obtained electrode delivers an outstanding reversible charge capacity of 214 mA h g-1 at 1 A g-1 after 4000 cycles for PIBs, and achieves 262 mAh g-1 when coupled with a PTCDA cathode in the full cell. The electrochemical conversion mechanism of the optimized electrode during cycling is investigated through in situ XRD, Raman, and ex situ HRTEM. In addition, the heterostructured composite as anodes also displays excellent electrochemical performances for sodium-ion batteries (SIBs) and lithium-ion batteries (LIBs). This work opens up a new window for investigating novel electrode materials with excellent capacity and long durability.

Revealing Roles of High-Electronegativity Fluorine Atoms in Boosting Redox Potential of Layered Sodium Cathodes.

The development of high-energy-density cathode materials is regarded as the ultimate goal of alkali metal-ion batteries energy storage. However, the strategy of regulating specific capacity is limited by the theoretical capacity, and meanwhile focusing on improving capacity will lead to structural destructions. Herein, a novel perspective is proposed that tuning the electronic band structure by introducing highly electronegative fluoride atoms in NaxTMO2-yFy (0 < x < 1, 0 < y < 2) model compounds to improve redox potential for developing high-energy-density layered oxides. Highly electronegative fluoride atoms is introduced into P2-type Na0.67Fe0.5Mn0.5O2 (NFM), and the thus fluoride NFM (F-NFM) cathode achieved high redox potential (3.0 V) and high energy density (446 Wh kg-1). Proved by structural characterizations, fluorine atoms are successfully incorporated into oxygen sites in NFM lattice. Ultraviolet photoelectron spectroscopy is applied to quantitatively analyze the improved redox potential of F-NFM, which is achieved by the decreased valence band energy in electronic band structure due to the strongly electrophilic fluoride ions. Moreover, fluoride atoms can stabilize the local environment of NFM and improve its redox potential. The work provides a perspective to improve redox potential by tuning the electronic band structure in layered oxides and developing high-energy-density alkali metal-ion batteries.

Covalent Organic Frameworks as Electrode Materials for Alkali Metal-ion Batteries.

Covalent organic frameworks (COFs) are a class of porous crystalline polymeric materials constructed by linking organic small molecules through covalent bonds. COFs have the advantages of strong covalent bond network, adjustable pore structure, large specific surface area and excellent thermal stability, and have broad application prospects in various fields. Based on these advantages, rational COFs design strategies such as the introduction of active sites, construction of conjugated structures, and carbon material composite, etc. can effectively improve the conductivity and stability of the electrode materials in the field of batteries. This paper introduces the latest research results of high-performance COFs electrode materials in alkali metal-ion batteries (LIBs, SIBs, PIBs and LSBs) and other advanced batteries. The current challenges and future design directions of COFs-based electrode are discussed. It provides useful insights for the design of novel COFs structures and the development of high-performance alkali metal-ion batteries.

First principles theoretical of designing sandwich-like metallic BP4monolayer as anode for alkali metal-ion batteries.

Phosphorene has been widely used as anode material for batteries. However, the huge volume change during charging and discharging process, the semiconductor properties, and the high open circuit voltage limit its application. Based on this, by introducing the electron-deficient boron atoms into blue phosphorene, we proposed a P-rich sandwich-like BP4monolayer by density functional theory calculation and particle swarm optimization. The BP4monolayer shows good thermodynamic and dynamic stability, as well as chemical stability in O2atmosphere, mainly due to the strengthened P-P bond of the outer layer by the middle boron atoms adoptingsp3hybridization. According to the band structure, the BP4monolayer shows metallic property, which is beneficial to electron conductivity. Furthermore, compared with blue phosphorene and black phosphorene, the P-rich BP4monolayer shows higher theoretical capacity for Li, Na, and K of 1193.90, 1119.28, and 397.97 mA h g-1, respectively. The lattice constant of BP4monolayer increases only 3.73% (Li), 2.52% (Na) after Li/Na fully adsorbed on the anode. More importantly, the wettability of BP4monolayer in the electrolyte is comparable to that of graphene. These findings show that the stable sandwich-like BP4monolayer has potential as a lightweight anode material.

Functionalized MBenes as promising anode materials for high-performance alkali-ion batteries: a first-principles study.

The discovery of novel electrode materials based on two-dimensional (2D) structures is critical for alkali metal-ion batteries. Herein, we performed first-principles computations to investigate functionalized MXenes, Mo2BT2(T = O, S), which are also regarded as B-based MXenes, or named as MBenes, as potential anode materials for Li-ion batteries and beyond. The pristine and T-terminated Mo2BT2(T = O, S) monolayers reveal metallic character with higher electronic conductivity and are thermodynamically stable with an intrinsic dipole moment. Both Mo2BO2and Mo2BS2monolayers exhibit high theoretical Li/Na/K storage capacity and low ion diffusion barriers. These findings suggest that functionalized Mo2BT2(T = O, S) monolayers are promising for designing viable anode materials for high-performance alkali-ion batteries.

Antimony Oxides-Based Anode Materials for Alkali Metal-Ion Storage.

With the increasing demand for renewable energy, alkali metal-ion (lithium/sodium/potassium-ion) batteries play more and more important roles in the field of static storage and electrical vehicle industry. Novel anode materials with high reversible capacity, safety and long-term cycling stability are desiderated to meet the ever-growing demand for alkali metal-ion batteries with high electrochemical performance. Antimony oxides (Sbx Oy ) show electrochemical reaction activity with all of lithium, sodium and potassium, and are expected to be promising anode materials for alkali metal-ion storage due to their high theoretical capacities, appropriate operating potential and excellent safety properties. This review is devoted to overview the research progress on reaction mechanism and improvements in electrochemical performance of antimony oxides for alkali metal-ion storage, and look forward to their further prospects.

Vanadium Tetrasulfide for Next-Generation Rechargeable Batteries: Advances and Challenges.

Alkali metal-ion batteries (SIBs and PIBs) and multivalent metal-ion batteries (ZIBs, MIBs, and AIBs), among the next-generation rechargeable batteries, are deemed appealing alternatives to lithium-ion batteries (LIBs) because of their cost competitiveness. Improving the electrochemical properties of electrode materials can greatly accelerate the pace of development in battery systems to cover the increasing demands of realistic applications. Vanadium tetrasulfide (VS4 ) is known as a prospective electrode material due to its unique one-dimensional atomic chain structure with a large chain spacing, weak interactions between adjacent chains, and high sulfur content. This review summarizes the synthetic strategies and recent advances of VS4 as cathodes/anodes for rechargeable batteries. Meanwhile, we describe the structural characteristics and electrochemical properties of VS4 . And we describe in detail its specific applications in batteries such as SIBs, PIBs, ZIBs, MIBs, and AIBs as well as modification strategies. Finally, the opportunities and challenges of VS4 in the domain of energy research are described.

Metal-Organic Frameworks and Their Derivatives: Designing Principles and Advances toward Advanced Cathode Materials for Alkali Metal Ion Batteries.

Metal-organic frameworks (MOFs) and their derivatives have attracted enormous attention in the field of energy storage, due to their high specific surface area, tunable structure, highly ordered pores, and uniform metal sites. Compared with the wide research of MOFs and their related materials on anode materials for alkali metal ion batteries, few works are on cathode materials. In this review, design principles for promoting the electrochemical performance of MOF-related materials in terms of component/structure design, composite fabrication, and morphology engineering are presented. By summarizing the advancement of MOFs and their derivatives, Prussian blue and its analogs, and MOF surface coating, challenges and opportunities for future outlooks of MOF-related cathode materials are discussed.

Iron Selenide Microcapsules as Universal Conversion-Typed Anodes for Alkali Metal-Ion Batteries.

Rechargeable alkali metal-ion batteries (AMIBs) are receiving significant attention owing to their high energy density and low weight. The performance of AMIBs is highly dependent on the electrode materials. It is, therefore, quite crucial to explore suitable electrode materials that can fulfil the future requirements of AMIBs. Herein, a hierarchical hybrid yolk-shell structure of carbon-coated iron selenide microcapsules (FeSe2 @C-3 MCs) is prepared via facile hydrothermal reaction, carbon-coating, HCl solution etching, and then selenization treatment. When used as the conversion-typed anode materials (CTAMs) for AMIBs, the yolk-shell FeSe2 @C-3 MCs show advantages. First, the interconnected external carbon shell improves the mechanical strength of electrodes and accelerates ionic migration and electron transmission. Second, the internal electroactive FeSe2 nanoparticles effectively decrease the extent of volume expansion and avoid pulverization when compared with micro-sized solid FeSe2 . Third, the yolk-shell structure provides sufficient inner void to ensure electrolyte infiltration and mobilize the surface and near-surface reactions of electroactive FeSe2 with alkali metal ions. Consequently, the designed yolk-shell FeSe2 @C-3 MCs demonstrate enhanced electrochemical performance in lithium-ion batteries, sodium-ion batteries, and potassium-ion batteries with high specific capacities, long cyclic stability, and outstanding rate capability, presenting potential application as universal anodes for AMIBs.

Urchin-Type Architecture Assembled by Cobalt Phosphide Nanorods Encapsulated in Graphene Framework as an Advanced Anode for Alkali Metal Ion Batteries.

Urchin-type cobalt phosphide microparticles assembled by nanorod were encapsulated in a graphene framework membrane (CoP@GF), and used as a binder-free electrode for alkali metal ion batteries. Electrochemical measurements indicate that this membrane exhibits enhanced reversible lithium, sodium, and potassium storage capabilities. Moreover, the energy storage properties of CoP@GF electrodes in alkali metal ion batteries display an order of Li>Na>K. DFT calculations on adsorption energy of CoP surfaces for Li, Na, and K indicated that CoP surfaces were more favorable to transfer electrons to Li atoms than Na and K, and the surface reactivity can be ordered as Li-CoP>Na-CoP>K-CoP; thus, CoP@GF exhibits better storage capacity for lithium. This work provides experimental and theoretical basis for understanding the electrochemical performance of cobalt phosphide-based membranes for alkali metal ion batteries.

A Black Phosphorus-Graphite Composite Anode for Li-/Na-/K-Ion Batteries.

Black phosphorus (BP) is a desirable anode material for alkali metal ion storage owing to its high electronic/ionic conductivity and theoretical capacity. In-depth understanding of the redox reactions between BP and the alkali metal ions is key to reveal the potential and limitations of BP, and thus to guide the design of BP-based composites for high-performance alkali metal ion batteries. Comparative studies of the electrochemical reactions of Li+ , Na+ , and K+ with BP were performed. Ex situ X-ray absorption near-edge spectroscopy combined with theoretical calculation reveal the lowest utilization of BP for K+ storage than for Na+ and Li+ , which is ascribed to the highest formation energy and the lowest ion diffusion coefficient of the final potassiation product K3 P, compared with Li3 P and Na3 P. As a result, restricting the formation of K3 P by limiting the discharge voltage achieves a gravimetric capacity of 1300 mAh g-1 which retains at 600 mAh g-1 after 50 cycles at 0.25 A g-1 .

Rubik's cube PBA frameworks for optimizing the electrochemical performance in alkali metal-ion batteries.

PBA frameworks have stood out among metal-organic frameworks because of their easy preparation, excellent stability, porous structures, and rich redox properties. Unfortunately, their non-ideal conductivity and significant volume expansion during cycling prevent more widespread application in alkali-metal-ion (Li+, Na+, and K+) batteries. By changing the type and molar ratio of metal ions, Rubik's PBA frameworks with infinite structural variations were obtained in this study, just like the Rubik's cube undergoes infinite changes during the rotation. X-ray adsorption fine structure measurements have documented the existence and determined the coordination environment of the metal ions in the Rubik's PBA framework. Benefiting from the more stable Rubik's cube structures with diverse composition, enhanced conductivity, and greater adsorption capacity, the obtained Rubik's cubes CoM-PBA anodes, especially CoZn-PBA deliver the enhanced cycling and rate performance in all the alkali-metal-ion batteries. The findings are supported by density functional theory calculations. Ex-situ X-ray photoelectron spectroscopy, and in-situ X-ray diffraction measurements were undertaken to explore the storage mechanism of CoZn-PBA anodes. Our results further demonstrate that the Rubik's cube PBA framework-based materials could be widely applied in the field of alkali-metal-ion batteries.

Versatile Nitrogen-Centered Organic Redox-Active Materials for Alkali Metal-Ion Batteries.

Versatile nitrogen-centered organic redox-active molecules have gained significant attention in alkali metal-ion batteries (AMIBs) due to their low cost, low toxicity, and ease of preparation. Specially, their multiple reaction categories (anion/cation insertion types of reaction) and higher operating voltage, when compared to traditional conjugated carbonyl materials, underscore their promising prospects. However, the high solubility of nitrogen-centered redox active materials in organic electrolyte and their low electronic conductivity contribute to inferior cycling performance, sluggish reaction kinetics, and limited rate capability. This review provides a detailed overview of nitrogen-centered redox-active materials, encompassing their redox chemistry, solutions to overcome shortcomings, characterization of charge storage mechanisms, and recent progress. Additionally, prospects and directions are proposed for future investigations. It is anticipated that this review will stimulate further exploration of underlying mechanisms and interface chemistry through in situ characterization techniques, thereby promoting the practical application of nitrogen-centered redox-active materials in AMIBs.

Advanced Insights on MXenes: Categories, Properties, Synthesis, and Applications in Alkali Metal Ion Batteries.

The development and optimization of promising anode material for next-generation alkali metal ion batteries are significant for clean energy evolution. 2D MXenes have drawn extensive attention in electrochemical energy storage applications, due to their multiple advantages including excellent conductivity, robust mechanical properties, hydrophilicity of its functional terminations, and outstanding electrochemical storage capability. In this review, the categories, properties, and synthesis methods of MXenes are first outlined. Furthermore, the latest research and progress of MXenes and their composites in alkali metal ion storage are also summarized comprehensively. A special emphasis is placed on MXenes and their hybrids, ranging from material design and fabrication to fundamental understanding of the alkali ion storage mechanisms to battery performance optimization strategies. Lastly, the challenges and personal perspectives of the future research of MXenes and their composites for energy storage are presented.

Low-Dimensional Vanadium-Based High-Voltage Cathode Materials for Promising Rechargeable Alkali-Ion Batteries.

Owing to their rich structural chemistry and unique electrochemical properties, vanadium-based materials, especially the low-dimensional ones, are showing promising applications in energy storage and conversion. In this invited review, low-dimensional vanadium-based materials (including 0D, 1D, and 2D nanostructures of vanadium-containing oxides, polyanions, and mixed-polyanions) and their emerging applications in advanced alkali-metal-ion batteries (e.g., Li-ion, Na-ion, and K-ion batteries) are systematically summarized. Future development trends, challenges, solutions, and perspectives are discussed and proposed. Mechanisms and new insights are also given for the development of advanced vanadium-based materials in high-performance energy storage and conversion.

In-situ-grown multidimensional Cu-doped Co1-xS2@MoS2 on N-doped carbon nanofibers as anode materials for high-performance alkali metal ion batteries.

Transition metal sulfides with the high theoretical capacity and low cost have been considered as advanced anode candidate for alkali metal ion batteries, but suffered from unsatisfactory electrical conductivity and huge volume expansion. Herein, a multidimensional structure Cu-doped Co1-xS2@MoS2 in-situ-grown on N-doped carbon nanofibers (denoted as Cu-Co1-xS2@MoS2 NCNFs) have been elaborately constructed for the first time. The bimetallic zeolitic imidazolate framework CuCo-ZIFs were encapsulated in the one-dimensional (1D) NCNFs through an electrospinning route and then on which the two-dimensional (2D) MoS2 nanosheets were in-situ grown via a hydrothermal process. The architecture of 1D NCNFs can effectively shorten ion diffusion path and enhance electrical conductivity. Besides, the formed heterointerface between MOF-derived binary metal sulfides and MoS2 can provide extra active centers and accelerate reaction kinetics, which guarantee a superior reversibility. As expected, the resulting Cu-Co1-xS2@MoS2 NCNFs electrode delivers excellent specific capacity of Na-ion batteries (845.6 mAh/g at 0.1 A/g), Li-ion batteries (1145.7 mAh/g at 0.1 A/g), and K-ion batteries (474.3 mAh/g at 0.1 A/g). Therefore, this innovative design strategy will bring a meaningful prospect for developing high-performance multi-component metal sulfides electrode for alkali metal ion batteries.

Phosphorus/Phosphide-Based Materials for Alkali Metal-Ion Batteries.

Phosphorus- and phosphide-based materials with remarkable physicochemical properties and low costs have attracted significant attention as the anodes of alkali metal (e.g., Li, Na, K, Mg, Ca)-ion batteries (AIBs). However, the low electrical conductivity and large volume expansion of these materials during electrochemical reactions inhibit their practical applications. To solve these problems, various promising solutions have been explored and utilized. In this review, the recent progress in AIBs using phosphorus- and phosphide-based materials is summarized. Thereafter, the in-depth working principles of diverse AIBs are discussed and predicted. Representative works with design concepts, construction approaches, engineering strategies, special functions, and electrochemical results are listed and discussed in detail. Finally, the existing challenges and issues are concluded and analyzed, and future perspectives and research directions are given. This review can provide new guidance for the future design and practical applications of phosphorus- and phosphide-based materials used in AIBs.

Fly Ash Carbon Anodes for Alkali Metal-Ion Batteries.

Graphite has become a critical material because of its essential role in the lithium-ion battery (LIB) industry. However, the synthesis of graphite requires an energy-intensive thermal treatment. Also, when used in sodium-ion and potassium-ion batteries (SIBs and PIBs), the graphite anode shows poor capacities and cycling stability, which hinders the development of next-generation battery technologies. Finding suitable anode materials for commercial alkali metal-ion batteries is not only urgent for the energy storage industry, but is also important for economic and sustainable development. In this work, we use fly ash carbon (FAC), a residue of crude oil combustion, as an anode material for alkali metal-ion batteries. The FAC anodes show relatively high capacities and excellent cycling stability. The charge storage mechanism of FAC anode is shown to be intercalation coupled with redox reactions of oxygen functional groups. This work shows that FAC is a promising scalable anode material for alkali metal-ion batteries.

Metallothermic Reduction of Molten Adduct [PCl4+][AlCl4-] at 50 °C to Amorphous Phosphorus or Crystallized Phosphides.

A molten salt metallothermic reduction strategy is developed for preparing phosphorus (P) or phosphides controllably at low temperature, which is simple, energy-saving, and easy to scale up. Typically, synthesis of spongelike porous amorphous P (a-P) is realized through reduction of PCl5 with Zn (or Al) at 50 °C assisted by AlCl3. It is demonstrated that an adduct salt PCl5·AlCl3 composed of PCl4+ and AlCl4- ions with a low melting point below 50 °C is formed from covalent salts PCl5 and AlCl3. This system is also suitable for producing nanostructured phosphides by adding corresponding transition-metal (Co, Fe, and Cu) chlorides even at 50 °C. As a Li storage anode, the as-prepared a-P exhibits a capacity of 1605 mA h g-1 at 0.2 C, a good rate capability of 1283 mA h g-1 at 10 C, and a long-term cycling stability of 1082 mA h g-1 after 200 cycles. Additionally, the Na-/K-ion storage performance is investigated systematically.