A High-Entropy Intergrowth Layered-Oxide Cathode with Enhanced Stability for Sodium-Ion Batteries.

Layered transition metal oxides are widely considered as ideal cathode materials for SIBs. However, the existing P2 and O3 structures possess specific issues, which limit their practical applications. To address these issues, this work designed a novel intergrowth layered oxide cathode with P2 and O3 phases by implementing Cu and Ti into the structure with the formation of high-entropy cathode materials with superior performance for SIBs. The electrochemical test results show that the optimized high-entropy cathode with the P2/O3 intergrowth structure possesses a high initial discharge capacity of 157.85 mAh g-1 at 0.1 C, an excellent rate performance of 84.41 mAh g-1 at 10 C, and long-term stability with capacity retention of 83.25% after 500 cycles at 5C. Furthermore, the analysis results of ex situ XRD and in situ XRD indicate that the adverse phase transition of P2-O2 under high voltage is effectively suppressed. This work indicates that the integration of high-entropy strategy with the two-phase intergrowth structure can effectively stabilize the layered structure, suppress the slipping of transition metal layers, and improve electrochemical performance, which provides a new approach for designing high-performance and practical layered transition metal oxide cathode materials for advanced SIBs.

Yolk-Shell Construction of Na3 V2 (PO4 )2 F3 with Copper Substitution Microsphere as High-Rate and Long-Cycling Cathode Materials for Sodium-Ion Batteries.

Na3 V2 (PO4 )2 F3 (NVPF) is emerging as a promising cathode material for high-voltage sodium-ion batteries. Whereas, the inferior intrinsic electrical conductivity leading to poor rate performance and cycling stability. To address this issue, a strategy of synthesizing unique yolk-shell structured NVPF with copper substitution via spray drying method is proposed. Besides, the synergistic modulation of both crystalline structure and interfacial properties results in significantly enhanced intrinsic and interfacial conductivity of NVPF. The optimized yolk-shell structured cathode materials can possess a high capacity of 117.4 mAh g-1 at 0.1 C, and remains a high-capacity retention of 91.3% after 5000 cycles. A detailed investigation of kinetic properties combined with in situ XRD technology and DFT calculations, has been implemented, particularly with regard to electron conduction and sodium ion diffusion. Consequently, the yolk-shell structured composition of Na3 V1.94 Cu0.06 (PO4 )2 F3 with nitrogen-modified carbon coating layer shows the lowest polarization potential because of the effectively enhanced electronic conductivity and Na+ diffusion process in the bulk phase. The robust electrochemical performance suggests that developing the unique yolk-shell structure with the collaboration of interface and bulk crystal properties is a favorable strategy to design cathode material with a high performance for sodium-ion batteries.

Progress on Fe-Based Polyanionic Oxide Cathodes Materials toward Grid-Scale Energy Storage for Sodium-Ion Batteries.

The development of large-scale energy storage systems (EESs) is pivotal for applying intermittent renewable energy sources such as solar energy and wind energy. Lithium-ion batteries with LiFePO4 cathode have been explored in the integrated wind and solar power EESs, due to their long cycle life, safety, and low cost of Fe. Considering the penurious reserve and regional distribution of lithium resources, the Fe-based sodium-ion battery cathodes with earth-abundant elements, environmental friendliness, and safety appear to be the better substitutes in impending grid-scale energy storage. Compared to the transition metal oxide and Prussian blue analogs, the Fe-based polyanionic oxide cathodes possess high thermal stability, ultra-long cycle life, and adjustable voltage, which is more commercially viable in the future. This review summarizes the research progress of single Fe-based polyanionic and mixed polyanionic oxide cathodes for the potential sodium-ion batteries EESs candidates. In detail, the synthesized method, crystal structure, electrochemical properties, bottlenecks, and optimization method of Fe-based polyanionic oxide cathodes are discussed systematically. The insights presented in this review may serve as a guideline for designing and optimizing Fe-based polyanionic oxide cathodes for coming commercial sodium-ion batteries EESs.

Importance of Crystallographic Sites on Sodium-Ion Extraction from NASICON-Structured Cathodes for Sodium-Ion Batteries.

The V4+/V3+ (3.4 V) redox couple has been well-documented in cathode material Na3V2(PO4)3 for sodium-ion batteries. Recently, partial cation substitution at the vanadium site of Na3V2(PO4)3 has been actively explored to access the V5+/V4+ redox couple to achieve high energy density. However, the V5+/V4+ redox couple in partially substituted Na3V2(PO4)3 has a voltage far below its theoretical voltage in Na3V2(PO4)3, and the access of the V5+/V4+ redox reaction is very limited. In this work, we compare the extraction/insertion behavior of sodium ions from/into two isostructural compounds of Na3VGa(PO4)3 and Na3VAl(PO4)3, found that, by DFT calculations, the lower potential of the V5+/V4+ redox couple in Na3VM(PO4)3 (M = Ga or Al) than that in Na3V2(PO4)3 is because of the extraction/insertion of sodium ions through the V5+/V4+ redox reaction at different crystallographic sites, that is, sodium ions extracting from the Na(2) site in Na3VM(PO4)3 while from the Na(1) site in Na3V2(PO4)3, and further evidenced that the full access of the V5+/V4+ redox reaction is restrained by the excessive diffusion activation energy in Na3VM(PO4)3.

Elevating Energy Density for Sodium-Ion Batteries through Multielectron Reactions.

It remains a great challenge to explore desirable cathodes for sodium-ion batteries to satisfy the ever-increasing demand for large-scale energy storage systems. In this Letter, we report a NASICON-structured Na4MnCr(PO4)3 cathode with high specific capacity and operation potential. The reversible access of the Mn2+/Mn3+ (3.75/3.4 V), Mn3+/Mn4+ (4.25/4.1 V), and Cr3+/Cr4+ (4.4/4.3 V vs Na/Na+) redox couples in a Na4MnCr(PO4)3 cathode endows a distinct three-electron redox reaction during the insertion/extraction process. The highly stable NASICON structure with a small volume variation upon cycling ensures long-time cycling stability (73.3% capacity retention after 500 cycles within the potential region of 2.5-4.6 V). The impedance analysis and interface characterization indicate that the evolution of a cathode electrolyte interphase at high potential is correlated with the capacity fading, while the robustness of the NASICON framework is redemonstrated.

A Ternary Hybrid-Cation Room-Temperature Liquid Metal Battery and Interfacial Selection Mechanism Study.

The dendrite-free sodium-potassium (Na-K) liquid alloy composed of two alkali metals is one of the ideal alternatives for Li metal as an anode material while maintaining large capacity, low potential, and high abundance. However, Na- or K-ion batteries have limited cathode materials that can deliver stably large capacity. Combining advantages of both, a hybrid-cation liquid metal battery is designed for a Li-ion-insertion-based cathode to deliver stable high capacity using a Na-K liquid anode to avoid dendrites. The mechanical property of the Na-K alloy is confirmed by simulation and experimental characterization, which leads to stable cycling performance. The charge carrier selection principle in this ternary hybrid-cation system is investigated, showing consistency with the proposed interfacial layer formation and ion distribution mechanism for the electrochemical process as well as the good stability. With Li ions contributing stable cycling as the cathode charge carrier, the K ion working as charge carrier on the anode, and Na as the medium to liquefy K metal, such a ternary hybrid battery system not only inherits the rich battery chemistry of Li-insertion cathodes but also broadens the understanding of alkali metal alloys and hybrid-ion battery chemistry.

In Situ Formation of Liquid Metals via Galvanic Replacement Reaction to Build Dendrite-Free Alkali-Metal-Ion Batteries.

Galvanic replacement reactions have been studied as a versatile route to synthesize nanostructured alloys. However, the galvanic replacement chemistry of alkali metals has rarely been explored. A protective interphase layer will be formed outside templates when the redox potential exceeds the potential windows of nonaqueous solutions, and the complex interfacial chemistry remains elusive. Here, we demonstrate the formation of room-temperature liquid metal alloys of Na and K via galvanic replacement reaction. The fundamentals of the reaction at such low potentials are investigated via a combined experimental and computational method, which uncovers the critical role of solid-electrolyte interphase in regulating the migration of Na ions and thus the alloying reaction kinetics. With in situ formed NaK liquid alloys as an anode, the dendritic growth of alkali metals can be eliminated thanks to the deformable and self-healing features of liquid metals. The proof-of-concept battery delivers reasonable electrochemical performance, confirming the generality of this in situ approach and design principle for next-generation dendrite-free batteries.

Size-, Water-, and Defect-Regulated Potassium Manganese Hexacyanoferrate with Superior Cycling Stability and Rate Capability for Low-Cost Sodium-Ion Batteries.

Potassium manganese hexacyanoferrate (KMHCF) is a low-cost Prussian blue analogue (PBA) having a rigid and open framework that can accommodate large alkali ions. Herein, the synthesis of KMHCF and its application as a high-performance cathode in sodium-ion batteries (NIBs) is reported. High-quality KMHCF with low amounts of crystal water and defects and with homogeneous microstructure is obtained by controlling the nucleation and grain growth by using a high-concentration citrate solution as a precipitation medium. The obtained KMHCF exhibits superior cycling and rate performance as a NIB cathode, showing 80% capacity retention after 1000 cycles at 1 C and a high capacity of 95 mA h g-1 at 20 C. Unlike conventional single-cation batteries, the hybrid NIB with KMHCF as cathode and Na as anode in Na-ion electrolyte displays three reversible plateaus that involve stepwise insertion/extraction of both K+ and Na+ in the PBA framework. In later cycling, the K+ -Na+ cointercalated phase is partially converted into a cubic sodium manganese hexacyanoferrate (NaMHCF) phase due to the increasing replacement of Na+ for K+ .

Na3MnZr(PO4)3: A High-Voltage Cathode for Sodium Batteries.

Sodium batteries have been regarded as promising candidates for large-scale energy storage application, provided cathode hosts with high energy density and long cycle life can be found. Herein, we report NASICON-structured Na3MnZr(PO4)3 as a cathode for sodium batteries that exhibits an electrochemical performance superior to those of other manganese phosphate cathodes reported in the literature. Both the Mn4+/Mn3+ and Mn3+/Mn2+ redox couples are reversibly accessed in Na3MnZr(PO4)3, providing high discharge voltage plateaus at 4.0 and 3.5 V, respectively. A high discharge capacity of 105 mAh g-1 was obtained from Na3MnZr(PO4)3 with a small variation of lattice parameters and a small volume change on extraction of two Na+ ions per formula unit. Moreover, Na3MnZr(PO4)3 exhibits an excellent cycling stability, retaining 91% of the initial capacity after 500 charge/discharge cycles at 0.5 C rate. On the basis of structural analysis and density functional theory calculations, we have proposed a detailed desodiation pathway from Na3MnZr(PO4)3 where Mn and Zr are disordered within the structure. We further show that the cooperative Jahn-Teller distortion of Mn3+ is suppressed in the cathode and that Na2MnZr(PO4)3 is a stable phase.

Polyanthraquinone-Triazine-A Promising Anode Material for High-Energy Lithium-Ion Batteries.

A novel covalent organic framework polymer material that bears conjugated anthraquinone and triazine units in its skeleton has been prepared via a facile one-pot condensation reaction and employed as an anode material for Li-ion batteries. The conjugated units consist of C═N groups, C═O groups, and benzene groups, which enable a 17-electron redox reaction with Li per repeating unit and bring a theoretical specific capacity of 1450 mA h g-1. The polymer also shows a large specific surface area and a hierarchically porous structure to trigger interfacial Li storage and contribute to an additional capacity. The highly conductive conjugated polymer skeleton enables fast electron transport to facilitate the Li storage. In this way, the polymer electrode shows a large specific capacity and favorable cycling and rate performance, making it an appealing anode choice for the next-generation high-energy batteries.

Selective CO Evolution from Photoreduction of CO2 on a Metal-Carbide-Based Composite Catalyst.

A selective CO evolution from photoreduction of CO2 in water was achieved on a noble-metal-free, carbide-based composite catalyst, as demonstrated by a CO selectivity of 98.3% among all carbon-containing products and a CO evolution rate of 29.2 µmol h-1, showing superiority to noble-metal-based catalyst. A rapid separation of the photogenerated electron-hole pairs and improved CO2 adsorption on the surface of the carbide component are responsible for the excellent performance of the catalyst. The high CO selectivity is accompanied by a predominant H2 evolution, which is believed to provide a proton-deficient environment around the catalyst to favor the formation of hydrogen-deficient carbon products. The present work provides general insights into the design of a catalyst with a high product selectivity and also the carbon evolution chemistry during a photocatalytic reaction.

Room-Temperature Liquid Na-K Anode Membranes.

The Na-K alloy is a liquid at 25 °C over a large compositional range. The liquid alloy is also immiscible in the organic-liquid electrolytes of an alkali-ion rechargeable battery, providing dendrite-free liquid alkali-metal batteries with a liquid-liquid anode-electrolyte interface at room temperature. The two liquids are each immobilized in a porous matrix. In previous work, the porous matrix used to immobilize the alloy was a carbon paper that is wet by the alloy at 420 °C; the alloy remains in the paper at room temperature. Here we report a room-temperature vacuum infiltration of the alloy into a porous Cu or Al membrane and a reversible stripping/plating of the liquid alloy with the immobilized organic-liquid electrolyte; no self-diacharge is observed since the liquid Na-K does not dissolve into the liquid carbonate electrolytes. The preparation and stripping/plating of the liquid alkali-metal anode can both now be done safely at room temperature.

A High-Energy-Density Potassium Battery with a Polymer-Gel Electrolyte and a Polyaniline Cathode.

A safe, rechargeable potassium battery of high energy density and excellent cycling stability has been developed. The anion component of the electrolyte salt is inserted into a polyaniline cathode upon charging and extracted from it during discharging while the K+ ion of the KPF6 salt is plated/stripped on the potassium-metal anode. The use of a p-type polymer cathode increases the cell voltage. By replacing the organic-liquid electrolyte in a glass-fiber separator with a polymer-gel electrolyte of cross-linked poly(methyl methacrylate), a dendrite-free potassium anode can be plated/stripped, and the electrode/electrolyte interface is stabilized. The potassium anode wets the polymer, and the cross-linked architecture provides small pores of adjustable sizes to stabilize a solid-electrolyte interphase formed at the anode/electrolyte interface. This alternative electrolyte/cathode strategy offers a promising new approach to low-cost potassium batteries for the stationary storage of electric power.

Cathode Dependence of Liquid-Alloy Na-K Anodes.

Alkali ions can be plated dendrite-free into a liquid alkali-metal anode. Commercialized Na-S battery technology operates above 300 °C. A low-cost Na-K alloy is liquid at 25 °C from 9.2 to 58.2 wt% of sodium; sodium and/or potassium can be plated dendrite-free in the liquid range at room temperature. The co-existence of two alkali metals in an anode raises a question: whether the liquid Na-K alloy acts as a Na or a K anode. Here we show the alkali-metal that is stripped from the liquid Na-K anode is dependent on the preference of the cathode host. It acts as the anode of a sodium rechargeable cell if the cathode host structure selectively accepts only Na+ ions; as the anode of a potassium rechargeable cell if the cathode accepts K+ ions in preference to Na+ ions. This dual-anode behavior means the liquid Na-K alkali-alloy can be applied as a dendrite-free anode in Na-metal batteries as well as K-metal batteries.

Nitrogen-Doped Perovskite as a Bifunctional Cathode Catalyst for Rechargeable Lithium-Oxygen Batteries.

In this work, nitrogen-doped LaNiO3 perovskite was prepared and studied, for the first time, as a bifunctional electrocatalyst for oxygen cathode in a rechargeable lithium-oxygen battery. N doping was found to significantly increase the Ni3+ contents and oxygen vacancies on the bulk surface of the perovskite, which helped to promote the oxygen reduction reaction and oxygen evolution reaction of the cathode and, therefore, enabled reversible Li2O2 formation and decomposition on the cathode surface. As a result, the oxygen cathodes loaded with N-doped LaNiO3 catalyst showed an improved electrochemical performance in terms of discharge capacity and cycling stability to promise practical Li-O2 batteries.

A Plastic-Crystal Electrolyte Interphase for All-Solid-State Sodium Batteries.

The development of all-solid-state rechargeable batteries is plagued by a large interfacial resistance between a solid cathode and a solid electrolyte that increases with each charge-discharge cycle. The introduction of a plastic-crystal electrolyte interphase between a solid electrolyte and solid cathode particles reduces the interfacial resistance, increases the cycle life, and allows a high rate performance. Comparison of solid-state sodium cells with 1) solid electrolyte Na3 Zr2 (Si2 PO4 ) particles versus 2) plastic-crystal electrolyte in the cathode composites shows that the former suffers from a huge irreversible capacity loss on cycling whereas the latter exhibits a dramatically improved electrochemical performance with retention of capacity for over 100 cycles and cycling at 5 C rate. The application of a plastic-crystal electrolyte interphase between a solid electrolyte and a solid cathode may be extended to other all-solid-state battery cells.

Low-Cost High-Energy Potassium Cathode.

Potassium has as rich an abundance as sodium in the earth, but the development of a K-ion battery is lagging behind because of the higher mass and larger ionic size of K+ than that of Li+ and Na+, which makes it difficult to identify a high-voltage and high-capacity intercalation cathode host. Here we propose a cyanoperovskite KxMnFe(CN)6 (0 ≤ x ≤ 2) as a potassium cathode: high-spin MnIII/MnII and low-spin FeIII/FeII couples have similar energies and exhibit two close plateaus centered at 3.6 V; two active K+ per formula unit enable a theoretical specific capacity of 156 mAh g-1; Mn and Fe are the two most-desired transition metals for electrodes because they are cheap and environmental friendly. As a powder prepared by an inexpensive precipitation method, the cathode delivers a specific capacity of 142 mAh g-1. The observed voltage, capacity, and its low cost make it competitive in large-scale electricity storage applications.

NaxMV(PO4)3 (M = Mn, Fe, Ni) Structure and Properties for Sodium Extraction.

NASICON (Na+ super ionic conductor) structures of NaxMV(PO4)3 (M = Mn, Fe, Ni) were prepared, characterized by aberration-corrected STEM and synchrotron radiation, and demonstrated to be durable cathode materials for rechargeable sodium-ion batteries. In Na4MnV(PO4)3, two redox couples of Mn3+/Mn2+ and V4+/V3+ are accessed with two voltage plateaus located at 3.6 and 3.3 V and a capacity of 101 mAh g-1 at 1 C. Furthermore, the Na4MnV(PO4)3 cathode delivers a high initial efficiency of 97%, long durability over 1000 cycles, and good rate performance to 10 C. The robust framework structure and stable electrochemical performance makes it a reliable cathode materials for sodium-ion batteries.

An Aqueous Symmetric Sodium-Ion Battery with NASICON-Structured Na3 MnTi(PO4 )3.

A symmetric sodium-ion battery with an aqueous electrolyte is demonstrated; it utilizes the NASICON-structured Na3 MnTi(PO4 )3 as both the anode and the cathode. The NASICON-structured Na3 MnTi(PO4 )3 possesses two electrochemically active transition metals with the redox couples of Ti(4+) /Ti(3+) and Mn(3+) /Mn(2+) working on the anode and cathode sides, respectively. The symmetric cell based on this bipolar electrode material exhibits a well-defined voltage plateau centered at about 1.4 V in an aqueous electrolyte with a stable cycle performance and superior rate capability. The advent of aqueous symmetric sodium-ion battery with high safety and low cost may provide a solution for large-scale stationary energy storage.

Liquid K-Na Alloy Anode Enables Dendrite-Free Potassium Batteries.

A K-Na liquid alloy allows a dendrite-free high-capacity anode; its immiscibility with an organic liquid electrolyte offers a liquid-liquid anode-electrolyte interface. Working with a sodiated Na2 MnFe(CN)6 cathode, the working cation becomes K+ to give a potassium battery of long cycle life with an acceptable capacity at high charge/discharge rates.