Glass‐Ceramic‐Like Vanadate Cathodes for High‐Rate Lithium‐Ion Batteries

Nanostructured electrode materials are good candidates in batteries especially for high‐rate applications, yet they often suffer from extensive side reactions due to anomalously large surface areas. While micrometer‐size materials provide better stability, the lattice diffusivity is often too slow for lithium ion intercalation over the same length scale in a short time. Herein, a simple method to synthesize glass‐ceramic‐like vanadate cathodes for lithium‐ion batteries with abundant internal boundaries that allow fast lithium ion diffusion while maintaining a small surface area that thus minimize the contact and side reactions with organic electrolyte, is reported. Such samples heat‐treated under optimized conditions can deliver an impressive high‐rate capacity of 103 mAh g^?1 at 4000 mA g^?1 over 500 cycles, which has better kinetics and cycling stability than similar vanadate‐based materials. A striking grain‐size refinement effect accompanied by a low‐temperature growth‐controlled phase transition, can be achieved by fine tuning the heat‐treatment process. It is believed that the findings are general for other transition metal oxides for energy applications.     

Highly Reversible Oxygen‐Redox Chemistry at 4.1 V in Na4/7−x[□1/7Mn6/7]O2 (□: Mn Vacancy)

Increasing the energy density of rechargeable batteries is of paramount importance toward achieving a sustainable society. The present limitation of the energy density is owing to the small capacity of cathode materials, in which the (de)intercalation of ions is charge‐compensated by transition‐metal redox reactions. Although additional oxygen‐redox reactions of oxide cathodes have been recognized as an effective way to overcome this capacity limit, irreversible structural changes that occur during charge/discharge cause voltage drops and cycle degradation. Here, a highly reversible oxygen‐redox capacity of Na₂Mn₃O₇ that possesses inherent Mn vacancies in a layered structure is found. The cross validation of theoretical predictions and experimental observations demonstrates that the nonbonding 2p orbitals of oxygens neighboring the Mn vacancies contribute to the oxygen‐redox capacity without making the Mn?O bond labile, highlighting the critical role of transition‐metal vacancies for the design of reversible oxygen‐redox cathodes.     

Fundamental Understanding and Material Challenges in Rechargeable Nonaqueous Li–O2 Batteries: Recent Progress and Perspective

Energy storage challenges have triggered growing interest in various battery technologies and electrocatalysis. As a particularly promising variety, the Li–O₂ battery with an extremely high energy density is of great significance, offering tremendous opportunities to improve cell performance via understanding catalytic mechanisms and the exploration of new materials. Furthermore, focus on nonaqueous electrolyte‐based Li–O₂ batteries has markedly intensified since there could be a higher probability of commercialization, compared to that of solid‐state or aqueous electrolytes. The recent advancements of the nonaqueous Li–O₂ battery in terms of fundamental understanding and material challenges, including electrolyte stability, water effect, and noncarbon cathode materials are summarized in this review. Further, the current status of water impact on discharge products, possible mechanisms, and parasitic reactions in nonaqueous electrolytes are reviewed for the first time. The key challenges of noncarbon oxygen electrode materials, such as noble metals and metal oxides‐based cathodes, transition metals, transition metal compounds (carbides, oxides) based cathodes as well as noncarbon supported catalysts are discussed. This review concludes with a perspective on future research directions for nonaqueous Li–O₂ batteries.     

Fluorination of Lithium‐Excess Transition Metal Oxide Cathode Materials

Fluorination of Li‐ion cathode materials is of significant interest as it is claimed to lead to significant improvements in long‐term reversible capacity. However, the mechanism by which LiF incorporates and improves performance remains uncertain. Indeed, recent evidence suggests that fluorine is often present as a coating layer rather than incorporated into the bulk of the material. In this work, first‐principles calculations are used to investigate the thermodynamics of fluorination in transition metal oxide cathodes to determine the conditions under which bulk fluorination is possible. It is found that unlike classic well‐ordered cathodes, which cannot incorporate fluorine, disordered rock salt‐structured materials achieve significant fluorination levels due to the presence of locally metal‐poor, lithium‐rich environments that are highly preferred for fluorine. As well as explaining the fluorination process in known materials, this finding is encouraging for the development of new disordered rock salt lithium‐excess transition metal oxides, a promising new class of Li‐ion battery cathode materials that offer superior practical capacity to traditional layered oxides. In particular, it is found that bulk fluorination may serve as an alternative source of Li‐excess in these compounds that can replace the conventional substitution of a heavy redox‐inactive element on the transition metal sublattice.     

Transition Metal Oxide Anodes for Electrochemical Energy Storage in Lithium‐ and Sodium‐Ion Batteries

Lithium‐ion batteries (LIBs) with outstanding energy and power density have been extensively investigated in recent years, rendering them the most suitable energy storage technology for application in emerging markets such as electric vehicles and stationary storage. More recently, sodium, one of the most abundant elements on earth, exhibiting similar physicochemical properties as lithium, has been gaining increasing attention for the development of sodium‐ion batteries (SIBs) in order to address the concern about Li availability and cost—especially with regard to stationary applications for which size and volume of the battery are of less importance. Compared with traditional intercalation reactions, conversion reaction‐based transition metal oxides (TMOs) are prospective anode materials for rechargeable batteries thanks to their low cost and high gravimetric specific capacities. In this review, the recent progress and remaining challenges of conversion reactions for LIBs and SIBs are discussed, covering an overview about the different synthesis methods, morphological characteristics, as well as their electrochemical performance. Potential future research directions and a perspective toward the practical application of TMOs for electrochemical energy storage are also provided.     

Going beyond Intercalation Capacity of Aqueous Batteries by Exploiting Conversion Reactions of Mn and Zn electrodes for Energy‐Dense Applications

The recent trend in zinc (Zn) anode aqueous batteries has been to explore layered structures like manganese dioxides and vanadium oxides as Zn‐ion intercalation hosts. These structures, although novel, face limitations like their layered counterparts in lithium (Li)‐ion batteries, where the capacity is limited to the host's intercalation capacity. In this paper, a new strategy is proposed in enabling new generation of energy dense aqueous‐based batteries, where the conversion reactions of rock salt/spinel manganese oxides and carbon nanotube‐nested nanosized Zn electrodes are exploited to extract significantly higher capacity compared to intercalation systems. Accessing the conversion reactions allows to achieve high capacities of 750 mAh g^?1 (≈30 mAh cm^?2) from manganese oxide (MnO) and 810 mAh g^?1 (≈30 mAh cm^?2) from nanoscale Zn anodes, respectively. The high areal capacities help to attain unprecedented energy densities of 210 Wh per L‐cell and 320 Wh per kg‐total (398 Wh per kg‐active) from aqueous MnO|CNT‐Zn batteries, which allows an assessment of its viable use in a small‐scale automobile.     

Localized High‐Concentration Electrolytes Boost Potassium Storage in High‐Loading Graphite

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.     

Routes to High Energy Cathodes of Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) are now being actively developed as low cost and sustainable alternatives to lithium‐ion batteries (LIBs) for large‐scale electric energy storage applications. In recent years, various inorganic and organic Na compounds, mostly mimicked from their Li counterparts, have been synthesized and tested for SIBs, and some of them indeed demonstrate comparable specific capacity to the presently developed LIB electrodes. However, the lack of suitable cathode materials is still a major obstacle to the commercial development of SIBs. Here, we present a brief review on the recent developments of SIB cathodes, with a focus on low cost and high energy density materials (> 450 Wh kg^?1 vs Na) together with discussion of their Na‐storage mechanisms. The considerable differences in the structural requirements for Li‐ and Na‐storage reactions mean that it is not sufficient to design SIB cathode materials by simply mimicking LIB materials, and therefore great efforts are needed to discover new materials and reaction mechanisms to further develop variable cathodes for advanced SIB technology. Some directions for future research and possible strategies for building advanced cathode materials are also proposed here.     

Lithium Polyacrylate (LiPAA) as an Advanced Binder and a Passivating Agent for High‐Voltage Li‐Ion Batteries

Intensive studies of an advanced energy material are reported and lithium polyacrylate (LiPAA) is proven to be a surprisingly unique, multifunctional binder for high‐voltage Li‐ion batteries. The absence of effective passivation at the interface of high‐voltage cathodes in Li‐ion batteries may negatively affect their electrochemical performance, due to detrimental phenomena such as electrolyte solution oxidation and dissolution of transition metal cations. A strategy is introduced to build a stable cathode–electrolyte solution interphase for LiNi_0.5Mn_1.5O₄ (LNMO) spinel high‐voltage cathodes during the electrode fabrication process by simply using LiPAA as the cathode binder. LiPAA is a superb binder due to unique adhesion, cohesion, and wetting properties. It forms a uniform thin passivating film on LNMO and conducting carbon particles in composite cathodes and also compensates Li‐ion loss in full Li‐ion batteries by acting as an extra Li source. It is shown that these positive roles of LiPAA lead to a significant improvement in the electrochemical performance (e.g., cycle life, cell impedance, and rate capability) of LNMO/graphite battery prototypes, compared with that obtained using traditional polyvinylidene fluoride (PVdF) binder for LNMO cathodes. In addition, replacing PVdF with LiPAA binder for LNMO cathodes offers better adhesion, lower cost, and clear environmental advantages.     

Layered Oxide Cathodes for Sodium‐Ion Batteries: Phase Transition,Air Stability,and Performance

The increasing demand for replacing conventional fossil fuels with clean energy or economical and sustainable energy storage drives better battery research today. Sodium‐ion batteries (SIBs) are considered as a promising alternative for grid‐scale storage applications due to their similar “rocking‐chair” sodium storage mechanism to lithium‐ion batteries, the natural abundance, and the low cost of Na resources. Searching for appropriate electrode materials with acceptable electrochemical performance is the key point for development of SIBs. Layered transition metal oxides represent one of the most fascinating electrode materials owing to their superior specific capacity, environmental benignity, and facile synthesis. However, three major challenges (irreversible phase transition, storage instability, and insufficient battery performance) are known for cathodes in SIBs. Herein, a comprehensive review on the latest advances and progresses in the exploration of layered oxides for SIBs is presented, and a detailed and deep understanding of the relationship of phase transition, air stability, and electrochemical performance in layered oxide cathodes is provided in terms of refining the structure–function–property relationship to design improved battery materials. Layered oxides will be a competitive and attractive choice as cathodes for SIBs in next‐generation energy storage devices.     

Carbon Anodes for Nonaqueous Alkali Metal‐Ion Batteries and Their Thermal Safety Aspects

Since their commercialization by Sony in 1991, graphite anodes in combination with various cathodes have enabled the widespread success of lithium‐ion batteries (LIBs), providing over 10 billion rechargeable batteries to the global population. Next‐generation nonaqueous alkali metal‐ion batteries, namely sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs), are projected to utilize intercalation‐based carbon anodes as well, due to their favorable electrochemical properties. While traditionally graphite anodes have dominated the market share of LIBs, other carbon materials have been investigated, including graphene, carbon nanotubes, and disordered carbons. The relationship between carbon material properties, electrochemical performance, and charge storage mechanisms is clarified for these alkali metal‐ion batteries, elucidating possible strategies for obtaining enhanced cycling stability, specific capacity, rate capability, and safety aspects. As a key component in determining cell performance, the solid electrolyte interphase layer is described in detail, particularly for its dependence on the carbon anode. Finally, battery safety at extreme temperatures is discussed, where carbon anodes are susceptible to dendrite formation, accelerated aging, and eventual thermal runaway. As society pushes toward higher energy density LIBs, this review aims to provide guidance toward the development of sustainable next‐generation SIBs and PIBs.     

Stabilizing Reversible Oxygen Redox Chemistry in Layered Oxides for Sodium‐Ion Batteries

Triggering oxygen‐related activity is demonstrated as a promising strategy to effectively boost energy density of layered cathodes for sodium‐ion batteries. However, irreversible lattice oxygen loss will induce detrimental structure distortion, resulting in voltage decay and cycle degradation. Herein, a layered structure P2‐type Na_0.66Li_0.22Ru_0.78O₂ cathode is designed, delivering reversible oxygen‐related and Ru‐based redox chemistry simultaneously. Benefiting from the combination of strong Ru 4d‐O 2p covalency and stable Li location within the transition metal layer, reversible anionic/cationic redox chemistry is achieved successfully, which is proved by systematic bulk/surface analysis by in/ex situ spectroscopy (operando Raman and hard X‐ray absorption spectroscopy, etc.). Moreover, the robust structure and reversible phase transition evolution revealed by operando X‐ray diffraction further establish a high degree reversible (de)intercalation processes (≈150 mAh g^?1, reversible capacity) and long‐term cycling (average capacity drop of 0.018%, 500 cycles).     

Atomic‐Scale Visualization of Electrochemical Lithiation Processes in Monolayer MoS2 by Cryogenic Electron Microscopy

While lithium ion batteries with electrodes based on intercalation compounds have dominated the portable energy storage market for decades, the energy density of these materials is fundamentally limited. Today, rapidly growing demand for this type of energy storage is driving research into materials that utilize alternative reaction mechanisms to enable higher energy densities. Transition metal compounds are one such class of materials, with storage enabled by “conversion” reactions, where the material is converted to new compound upon lithiation. MoS₂ is one example of this type of material that has generated a large amount of interest recently due to its high theoretical lithium storage capacity compared to graphite. Here, cryogenic scanning transmission electron microscopy techniques are used to reveal the atomic‐scale processes that occur during reaction of a model monolayer MoS₂ system by enabling the unaltered atomic structure to be determined at various levels of lithiation. It is revealed that monolayer MoS₂ can undergo a conversion reaction even with no substrate, and that the resulting particles are smaller than those that form in bulk MoS₂, likely due to the more limited 2D diffusion. Additionally, while bilayer MoS₂ undergoes intercalation with a corresponding phase transition before conversion, monolayer MoS₂ does not.     

Metal‐Ion Coupled Electron Transfer Kinetics in Intercalation‐Based Transition Metal Oxides

Electrochemical metal‐ion intercalation systems are acknowledged to be a critical energy storage technology. The kinetics of the intercalation processes in transition‐metal based oxides determine the practical characteristics of metal‐ion batteries, such as the energy density, power, and cyclability. With the emergence of post lithium‐ion batteries, such as sodium‐ion and potassium‐ion batteries, which function predominately in nonaqueous electrolytes of special formulation and exhibit quite varied material stability with regard to their surface chemistries and reactivity with electrolytes, the practical routes for the optimization of metal‐ion battery performance become essential. Electrochemical methods offer a variety of means to quantitatively study the diffusional, charge transfer, and phase transformation rates in complex systems, which are, however, rather rarely fully adopted by the metal‐ion battery community, which slows down the progress in rationalizing the rate‐controlling factors in complex intercalation systems. Herein, several practical approaches for diagnosing the origin of the rate limitations in intercalation materials based on phenomenological models are summarized, focusing on the specifics of charge transfer, diffusion, and nucleation phenomena in redox‐active solid electrodes. It is demonstrated that information regarding rate‐determining factors can be deduced from relatively simple analysis of experimental methods including cyclic voltammetry, chronoamperometry, and impedance spectroscopy.     

K‐Ion Batteries Based on a P2‐Type K0.6CoO2 Cathode

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 K_0.6CoO₂ cathode is developed and highly reversible K ion intercalation is demonstrated. In situ X‐ray diffraction combined with electrochemical titration reveals that P2‐type K_0.6CoO₂ 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.     

Aqueous Electrochemical Energy Storage with a Mediator‐Ion Solid Electrolyte

This study presents a battery concept with a “mediator‐ion” solid electrolyte for the development of next‐generation electrochemical energy storage technologies. The active anode and cathode materials in a single cell can be in the solid, liquid, or gaseous form, which are separated by a sodium‐ion solid‐electrolyte separator. The uniqueness of this mediator‐ion strategy is that the redox reactions at the anode and the cathode are sustained by a shuttling of a mediator sodium ion between the anolyte and the catholyte through the solid‐state electrolyte. Use of the solid‐electrolyte separator circumvents the chemical‐crossover problem between the anode and the cathode, overcomes the dendrite‐problem when employing metal‐anodes, and offers the possibility of using different liquid electrolytes at the anode and the cathode in a single cell. The battery concept is demonstrated with two low‐cost metal anodes (zinc and iron), two liquid cathodes (bromine and potassium ferricyanide), and one gaseous cathode (air/O₂) with a sodium‐ion solid electrolyte. This novel battery strategy with a mediator‐ion solid electrolyte is applicable to a wide range of electrochemical energy storage systems with a variety of cathodes, anodes, and mediator‐ion solid electrolytes.     

Ethers Illume Sodium‐Based Battery Chemistry: Uniqueness,Surprise, and Challenges

Sodium‐ion batteries (SIBs) have the potential to be practically applied in large‐scale energy storage markets. The rapid progress of SIBs research is primarily focused on electrodes, while electrolytes attract less attention. Indeed, the improvement of electrode performance is arguably correlated with the electrolyte optimization. In conventional lithium‐ion batteries (LIBs), ether‐based electrolytes are historically less practical owing to the insufficient passivation of both anodes and cathodes. As an important class of aprotic electrolytes, ethers have revived with the emerging lithium‐sulfur and lithium‐oxygen batteries in recent years, and are even booming in the wave of SIBs. Ether‐based electrolytes are unique to enabling these new battery chemistries in terms of producing stable ternary graphite intercalation compounds, modifying anode solid electrolyte interphases, reducing the solubility of intermediates, and decreasing polarization. Better still, ether‐based electrolytes are compatible with specific inorganic cathodes and could catalyze the assembly of full SIBs prototypes. This Research News article aims to summarize the recent critical reports on ether‐based electrolytes in sodium‐based batteries, to unveil the uniqueness of ether‐based electrolytes to advancing diverse electrode materials, and to shed light on the viability and challenges of ether‐based electrolytes in future sodium‐based battery chemistries.     

Insights into the Effects of Electrolyte Composition on the Performance and Stability of FeF2 Conversion‐Type Cathodes

As an alternative to commercial Ni‐ and Co‐based intercalation‐type cathode materials, conversion‐type metal fluoride (MF_x) cathodes are attracting more interest due to their promises to increase cell‐level energy density when coupled with lithium (Li) or silicon (Si)‐based anodes. Among metal fluorides, iron fluorides (FeF₂ and FeF₃) are regarded as some of the most promising candidates due to their high capacity, moderately high potential and the very low cost of Fe. In this study, the impacts of electrolyte composition on the performance and stability of nanostructured FeF₂ cathodes are systematically investigated. Dramatic impacts of Li salt composition, Li salt concentration, solvent composition, and cycling potential range on the cathode's most critical performance parameters—stability, capacity, rate, and voltage hysteresis are discovered. In contrast to previous beliefs, it is observed that even if the Fe²⁺ cation dissolution could be avoided, the dissolution of F^? anions may still negatively affect cathode performance. Formation of the more favorable cathode solid electrolyte interface (CEI) is found to minimize both processes.     

Conditions for Reversible Na Intercalation in Graphite: Theoretical Studies on the Interplay Among Guest Ions,Solvent, and Graphite Host

Graphite is the most widely used anode material for Li‐ion batteries and is also considered a promising anode for K‐ion batteries. However, Na⁺, a similar alkali ion to Li⁺ or K⁺, is incapable of being intercalated into graphite and thus, graphite is not considered a potential electrode for Na‐ion batteries. This atypical behavior of Na has drawn considerable attention; however, a clear explanation of its origin has not yet been provided. Herein, through a systematic investigation of alkali metal graphite intercalation compounds (AM‐GICs, AM = Li, Na, K, Rb, Cs) in various solvent environments, it is demonstrated that the unfavorable local Na‐graphene interaction primarily leads to the instability of Na‐GIC formation but can be effectively modulated by screening Na ions with solvent molecules. Moreover, it is shown that the reversible Na intercalation into graphite is possible only for specific conditions of electrolytes with respect to the Na‐solvent solvation energy and the lowest unoccupied molecular orbital level of the complexes. It is believed that these conditions are applicable to other electrochemical systems involving guest ions and an intercalation host and hint at a general strategy to tailor the electrochemical intercalation between pure guest ion intercalation and cointercalation.     

Lithium Intercalation Behavior in Multilayer Silicon Electrodes

Next generation lithium battery materials will require a fundamental shift from those based on intercalation to elements or compounds that alloy directly with lithium. Intermetallics, for instance, can electrochemically alloy to Li_4.4M (M = Si, Ge, Sn, etc.), providing order‐of‐magnitude increases in energy density. Unlike the stable crystal structure of intercalation materials, intermetallic‐based electrodes undergo dramatic volume changes that rapidly degrade the performance of the battery. Here, the energy density of silicon is combined with the structural reversibility of an intercalation material using a silicon/metal‐silicide multilayer. In operando X‐ray reflectivity confirms the multilayer's structural reversibility during lithium insertion and extraction, despite an overall 3.3‐fold vertical expansion. The multilayer electrodes also show enhanced long‐term cyclability and rate capabilities relative to a comparable silicon thin film electrode. This intercalation behavior found by dimensionally constraining silicon's lithiation promises applicability to a wide range of conversion reactions.