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.     

Sodium‐Ion Battery Materials and Electrochemical Properties Reviewed

The demand for electrochemical energy storage technologies is rapidly increasing due to the proliferation of renewable energy sources and the emerging markets of grid‐scale battery applications. The properties of batteries are ideal for most electrical energy storage (EES) needs, yet, faced with resource constraints, the ability of current lithium‐ion batteries (LIBs) to match this overwhelming demand is uncertain. Sodium‐ion batteries (SIBs) are a novel class of batteries with similar performance characteristics to LIBs. Since they are composed of earth‐abundant elements, cheaper and utility scale battery modules can be assembled. As a result of the learning curve in the LIB technology, a phenomenal progression in material development has been realized in the SIB technology. In this review, innovative strategies used in SIB material development, and the electrochemical properties of anode, cathode, and electrolyte combinations are elucidated. Attractive performance characteristics are herein evidenced, based on comparative gravimetric and volumetric energy densities to state‐of‐the‐art LIBs. In addition, opportunities and challenges toward commercialization are herein discussed based on patent data trend analysis. With extensive industrial adaptations expected, the commercial prospects of SIBs look promising and this once discarded technology is set to play a major role in EES applications.     

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.     

Boosting Fast Sodium Storage of a Large‐Scalable Carbon Anode with an Ultralong Cycle Life

Sodium‐ion batteries (SIBs) are considered to be a promising alternative for large‐scale electricity storage. However, it is urgent to develop new anode materials with superior ultralong cycle life performance at high current rates. Herein, a low‐cost and large‐scalable sulfur‐doped carbon anode material that exhibits the best high‐rate cycle performance and the longest cycle life ever reported for carbon anodes is developed. The material delivers a reversible capacity of 142 mA h g^?1 at a current rate up to 10 A g^?1. After 10 000 cycles the capacity is remained at 126.5 mA h g^?1; 89.1% of the initial value. Density functional theory computations demonstrate that the sulfur‐doped carbon has a strong binding affinity for sodium which promotes sodium storage. Meanwhile, the kinetics analysis identifies the capacitive charge storage as a large contributor to sodium storage, which favors ultrafast storage of sodium ions. These results demonstrate a new way to design carbon‐based SIBs anodes for next‐generation large‐scale electricity storage.     

Comprehensive New Insights and Perspectives into Ti‐Based Anodes for Next‐Generation Alkaline Metal (Na+, K+) Ion Batteries

Sodium ion batteries (NIBs) and potassium ion batteries (KIBs) are promising candidates for large‐scale energy storage systems, with a similar “rocking chair” working principle to lithium ion batteries due to their earth abundance and lower cost. One of the major challenges in NIB research is the search for suitable anode materials with long lifetimes and high specific capacities. The research on KIBs is still in its infancy. Titanium‐based anodes present low lattice strain, high safety, and overall stability during cycling, which make them promising for large‐scale systems, especially for stationary batteries. In this review, the latest progress on titanium‐based anodes for NIBs and KIBs is summarized, including titanium dioxide and its composite, Na _x TiO₂ systems, NaTi₂(PO₄)₃, titanates, and MXenes. The synthesis methods, modification methods, and sodium or potassium ion storage mechanisms of titanium‐based anodes are detailed; also the current challenges and future opportunities are discussed.     

Theoretical investigation of the use of nanocages with an adsorbed halogen atom as anode materials in metal-ion batteries

The applicability of C₄₄, B₂₂N₂₂, Ge₄₄, and Al₂₂P₂₂ nanocages, as well as variants of those nanocages with an adsorbed halogen atom, as high-performance anode materials in Li-ion, Na-ion, and K-ion batteries was investigated theoretically via density functional theory. The results obtained indicate that, among the nanocages with no adsorbed halogen atom, Al₂₂P₂₂ would be the best candidate for a novel anode material for use in metal-ion batteries. Calculations also suggest that K-ion batteries which utilize these nanocages as anode materials would give better performance and would yield higher cell voltages than the corresponding Li-ion and Na-ion batteries with nanocage-based anodes. Also, the results for the nanocages with an adsorbed halogen atom imply that employing them as anode materials would lead to higher cell voltages and better metal-ion battery performance than if the nanocages with no adsorbed halogen atom were to be used as anode materials instead. Results further implied that nanocages with an adsorbed F atom would give higher cell voltages and better battery performance than nanocages with an adsorbed Cl or Br atom. We were ultimately able to conclude that a K-ion battery that utilized Al₂₁P₂₂ with an adsorbed F atom as its anode material would afford the best metal-ion battery performance; we therefore propose this as a novel highly efficient metal-ion battery.

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Graphical abstract The results of a theoretical investigation indicated that Al₂₂P₂₂ is a better candidate for a high-performance anode material in metal-ion batteries than Ge₄₄ is. Calculations also showed that K-ion batteries with nanocage-based anodes would produce higher cell voltages and perform better than the equivalent Li-ion and Na-ion batteries with nanocage-based anodes, and that anodes based on nanocages with an adsorbed F atom would perform better than anodes based on nanocages with an adsorbed Cl or Br atom

     

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.     

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.     

Low-Temperature Sodium-Ion Batteries: Challenges and Progress

As an ideal candidate for the next generation of large-scale energy storage devices, sodium-ion batteries (SIBs) have received great attention due to their low cost. However, the practical utility of SIBs faces constraints imposed by geographical and environmental factors, particularly in high-altitude and cold regions. In these areas, the low-temperature (LT) performance of SIBs presents a pressing technological challenge that requires significant breakthroughs. In LT environments, the electrochemical reaction kinetics of SIBs are sluggish, the electrode/electrolyte interface is unstable, and the diffusion of sodium ions in electrode materials is slow, leading to a decrease in battery performance. Therefore, the reasonable design of electrolyte and electrode materials is of great significance for optimizing the LT performance of SIBs. In this review, the research progress of LT SIBs electrolytes, cathode, and anode materials, as well as sodium metal batteries and solid-state electrolytes is systematically summarized in recent years, aiming to understand the design principles of LT SIBs, clarify the basic research and development of high-performance SIBs in practical applications, and promote the development of SIBs technology in the full temperature range.     

3D Amorphous Carbon with Controlled Porous and Disordered Structures as a High‐Rate Anode Material for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have a promising application prospect for energy storage systems due to the abundant resource. Amorphous carbon with high electronic conductivity and high surface area is likely to be the most promising anode material for SIBs. However, the rate capability of amorphous carbon in SIBs is still a big challenge because of the sluggish kinetics of Na⁺ ions. Herein, a three‐dimensional amorphous carbon (3DAC) with controlled porous and disordered structures is synthesized via a facile NaCl template‐assisted method. Combination of open porous structures of 3DAC, the increased disordered structures can not only facilitate the diffusion of Na⁺ ions but also enhance the reversible capacity of Na storage. When applied as anode materials for SIBs, 3DAC exhibits excellent rate capability (66 mA h g^?1 at 9.6 A g^?1) and high reversible capacity (280 mA h g^?1 at a low current density of 0.03 A g^?1). Moreover, the controlled porous structures by the NaCl template method provide an appropriate specific surface area, which contributes to a relatively high initial Coulombic efficiency of 75%. Additionally, the high‐rate 3DAC material is prepared via a green approach originating from low‐cost pitch and NaCl template, demonstrating an appealing development of carbon anode materials for SIBs.     

Air‐Stable and Dendrite‐Free Lithium Metal Anodes Enabled by a Hybrid Interphase of C60 and Mg

Li metal is an ideal anode material for rechargeable high energy density batteries, but its sensitivity to humid air and uncontrolled dendrite growth limit its practical applications. A novel hybrid interphase is fabricated to address these issues. This interphase consists of dense fullerene (C₆₀) and magnesium metal bilayers, which are deposited successively on lithium foil by vacuum evaporation deposition and contribute to moisture resistance and lithium dendrite suppression. Thanks to this dual‐functional feature, the assembled cells with the modified anodes and commercial LiFePO₄ cathodes exhibit long cycle life (>200 cycles) with high capacity retention (>98.5%). Moreover, even the modified anodes that are exposed to humid air (30% relative humidity) for over 12 h; the cells still deliver excellent performance, comparable to those without exposure. Such a unique hybrid interphase provides a new promising method for fabricating air‐stable and dendrite‐free lithium metal batteries.     

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Hard carbon (HC) is the state‐of‐the‐art anode material for sodium‐ion batteries (SIBs). However, its performance has been plagued by the limited initial Coulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium‐pretreated HC (LPHC) as high‐performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)‐based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g^?1 specific capacity, twice of the capacity (≈100 mAh g^?1) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g^?1 current density (4 C rate, 1 C = 250 mA g^?1) with a specific capacity of ≈150 mAh g^?1, ≈15 times of the capacity (10 mAh g^?1) in carbonate. The full cell of Na₃V₂(PO₄)₃‐LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g^?1 based on Na₃V₂(PO₄)₃ cathode, ≈2.5 times of the value (≈40 mAh g^?1) with nontreated HC. This work provides new perception on the anode development for SIBs.     

Reliable and General Route to Inverse Opal Structured Nanohybrids of Carbon‐Confined Transition Metal Sulfides Quantum Dots for High‐Performance Sodium Storage

Sodium‐ion batteries (SIBs) have recently attracted increasing attention as the promising alternative to lithium‐ion batteries due to their multiple advantages of abundant reserves and low cost. However, the development of highly desirable anode materials suitable for SIBs is still hampered by a rather low capacity, poor rate capability, and cycling stability. Herein, a deliberate design to implement reliable and simple fabrication of an inverse opal structured nanohybrid of carbon‐confined various transition metal sulfides quantum dots (QDs) is presented. Comprehensive characterizations demonstrate that the hybrids hold a 3D architecture with uniform dispersion of QDs in a conductive carbon matrix that in turn encapsulates these quantum dots. With Co₉S₈ as an example, such a unique architecture, when applied as the anode of SIBs, endows the hybrids with multiple advantages including a high reversible specific capacity, extraordinary high rate capability, and excellent durability over 2000 cycles charging–discharging process.     

Graphitic Carbon Nanocage as a Stable and High Power Anode for Potassium‐Ion Batteries

As an emerging electrochemical energy storage device, potassium‐ion batteries (PIBs) have drawn growing interest due to the resource‐abundance and low cost of potassium. Graphite‐based materials, as the most common anodes for commercial Li‐ion batteries, have a very low capacity when used an anode for Na‐ion batteries, but they show reasonable capacities as anodes for PIBs. The practical application of graphitic materials in PIBs suffers from poor cyclability, however, due to the large interlayer expansion/shrinkage caused by the intercalation/deintercalation of potassium ions. Here, a highly graphitic carbon nanocage (CNC) is reported as a PIBs anode, which exhibits excellent cyclability and superior depotassiation capacity of 175 mAh g^?1 at 35 C. The potassium storage mechanism in CNC is revealed by cyclic voltammetry as due to redox reactions (intercalation/deintercalation) and double‐layer capacitance (surface adsorption/desorption). The present results give new insights into structural design for graphitic anode materials in PIBs and understanding the double‐layer capacitance effect in alkali metal ion batteries.     

Strategies Toward Stable Nonaqueous Alkali Metal–O2 Batteries

Alkali metal–O₂ batteries, by coupling high‐capacity alkali metal anodes with gaseous oxygen, possess extremely high gravimetric energy density that is comparable to gasoline and are potential energy storage technologies beyond lithium–ion batteries. The development of alkali metal–O₂ batteries has achieved great progress in recent years, from materials to prototype devices and on fundamental mechanisms. The stability of alkali metal–O₂ batteries is still poor, however, leading to a huge gap between laboratory research and commercial applications. A series of parasitic reactions result in the instability, which occur during electrochemical discharging and charging. The ubiquitous active oxygen species attack both the organic electrolyte and the carbon cathode, triggering various parasitic reactions. Meanwhile, dendrite growth and volume expansion upon repeated plating/stripping and O₂ crossover severely limit the reversibility of alkali metal anodes. Here, an overview of the strategies against these issues is given to improve the stability of nonaqueous alkali metal–O₂ batteries, which is discussed from three aspects: air cathodes, alkali metal anodes, and aprotic electrolytes. Furthermore, perspectives for future research of stable alkali metal–O₂ batteries are outlined.     

Exploration of Advanced Electrode Materials for Rechargeable Sodium‐Ion Batteries

As the rapid growth of the lithium‐ion battery (LIB) market raises concerns about limited lithium resources, rechargeable sodium‐ion batteries (SIBs) are attracting growing attention in the field of electrical energy storage due to the large abundance of sodium. Compared with the well‐developed commercial LIBs, all components of the SIB system, such as the electrode, electrolyte, binder, and separator, need further exploration before reaching a practical industrial application level. Drawing lessons from the LIB research, the SIB electrode materials are being extensively investigated, resulting in tremendous progress in recent years. In this article, the progress of the research on the development of electrode materials for SIBs is summarized. A variety of new electrode materials for SIBs, including transition‐metal oxides with a layered or tunnel structure, polyanionic compounds, and organic molecules, have been proposed and systematically investigated. Several promising materials with moderate energy density and ultra‐long cycling performance are demonstrated. Appropriate doping and/or surface treatment methodologies are developed to effectively promote the electrochemical properties. The challenges of and opportunities for exploiting satisfactory SIB electrode materials for practical applications are outlined.     

New Binder‐Free Metal Phosphide–Carbon Felt Composite Anodes for Sodium‐Ion Battery

Metal phosphides are promising anode candidates for sodium‐ion batteries (SIBs) due to their high specific capacity and low operating potential but suffer from poor cycling stability caused by huge volume expansion and poor solid‐state ion transfer rate. Herein, a new strategy to grow a new class of mesoporous metal phosphide nanoarrays on carbon felt (CF) as binder‐free anodes for SIBs is reported. The resultant integrated electrodes demonstrate excellent cycling life up to 1000 times (>90% retention rate) and high rate capability of 535 mAh g^?1 at a current density of 4 A g^?1. Detailed characterization reveals that the synergistic effect of unique mesoporous structure for accommodating huge volume expansion during sodiation/desodiation process, ultrasmall primary particle size (≈10 nm) for providing larger electrode/electrolyte contact area and shorter ion diffusion distance, and 3D conductive networks for facilitating the electrochemical reaction, leads to the extraordinary battery performance. Remarkably, a full SIB using the new CoP₄/CF anode and a Na₃V₂(PO₄)₂F₃ cathode delivers an average operating voltage of ≈3.0 V, a reversible capacity of 553 mAh g^?1, and very high energy density of ≈280 Wh kg^?1 for SIBs. A flexible SIB with outstanding mechanical strength based on this binder‐free new anode is also demonstrated.     

3D Flexible Carbon Felt Host for Highly Stable Sodium Metal Anodes

Sodium (Na) metal, which possesses a high theoretical capacity and the lowest electrochemical potential, is regarded as a promising anode material for Na–metal batteries. However, both Na dendrite growth and large volume change in cycling have severely impeded its practical applications. This study demonstrates that a 3D flexible carbon (C) felt which is already commercialized in large‐scale can be employed as a host for prestoring Na via a melt infusion strategy, through which a Na/C composite anode is obtained. The resulting anode exhibits a stable voltage profile and a small hysteresis over 120 cycles in carbonate‐based electrolytes in symmetrical cells owing to the fact that the metallic Na is confined in a conductive carbon felt host, which increases the Na⁺ deposition sites to lower the effective current density and render a uniform Na nucleation, restricting the dimension change in electrochemical cycling. More importantly, effective inhibition of Na dendrite growth and large volume change is achieved. When coupled with a Na_0.67Ni_0.33Mn_0.67O₂ cathode, the Na/C composite demonstrates a good suitability in full cells. This work provides an alternative option for the fabrication of stable Na metal anodes, which is of great significance for the practical applications of Na metal anodes in high‐energy‐density batteries.     

Challenges in Developing Electrodes,Electrolytes, and Diagnostics Tools to Understand and Advance Sodium‐Ion Batteries

Considering the natural abundance and low cost of sodium resources, sodium‐ion batteries (SIBs) have received much attention for large‐scale electrochemical energy storage. However, smart structure design strategies and good mechanistic understanding are required to enable advanced SIBs with high energy density. In recent years, the exploration of advanced cathode, anode, and electrolyte materials, as well as advanced diagnostics have been extensively carried out. This review mainly focuses on the challenging problems for the attractive battery materials (i.e., cathode, anode, and electrolytes) and summarizes the latest strategies to improve their electrochemical performance as well as presenting recent progress in operando diagnostics to disclose the physics behind the electrochemical performance and to provide guidance and approaches to design and synthesize advanced battery materials. Outlook and perspectives on the future research to build better SIBs are also provided.     

A Material Perspective of Rechargeable Metallic Lithium Anodes

Rechargeable lithium‐based batteries are long considered as the most promising candidates for application in various electronic devices, electric vehicles, and even electrical grids owing to their ultrahigh energy densities. However, to date, metallic lithium‐based batteries are still far from practical applications due to the low Coulombic efficiency and fast capacity decay of lithium anodes. The poor electrochemical performances of metallic lithium anodes are inherently related to random growth of lithium dendrites and infinite volume charge of lithium anodes. In this review, the failure mechanisms of metallic lithium anodes are summarized and ascribed to the unstable and inhomogeneous solid electrolyte interphase, uneven distributions of electric field, and lithium‐ion flux during the lithium plating processes. Correspondingly, efficient strategies for mitigating these problems, including surficial engineering, electric field, and lithium‐ion flux regulation are discussed from the perspective of anode materials. Finally, an outlook is proposed for the design and fabrication of next‐generation rechargeable metallic lithium anodes that aims to address the intrinsic problems of metallic lithium anodes.