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.
The interplay among the guest ions, solvent, and graphite host in various alkali metal intercalated graphite intercalation compounds (GICs) is investigated. It is demonstrated that the particularly repulsive local interaction between Na ions and the graphene layer destabilizes binary Na‐GICs and proposed that the high Na solvation energy and chemical stability of Na‐solvent complexes are critical for the reversible cointercalation.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Lithium metal batteries using solid electrolytes are considered to be the next-generation lithium batteries due to their enhanced energy density and safety. However, interfacial instabilities between ...Li-metal and solid electrolytes limit their implementation in practical batteries. Herein, Li-metal batteries using tailored garnet-type Li
La
Zr
O
(LLZO) solid electrolytes is reported, which shows remarkable stability and energy density, meeting the lifespan requirements of commercial applications. We demonstrate that the compatibility between LLZO and lithium metal is crucial for long-term stability, which is accomplished by bulk dopant regulating and dopant-specific interfacial treatment using protonation/etching. An all-solid-state with 5 mAh cm
cathode delivers a cumulative capacity of over 4000 mAh cm
at 3 mA cm
, which to the best of our knowledge, is the highest cycling parameter reported for Li-metal batteries with LLZOs. These findings are expected to promote the development of solid-state Li-metal batteries by highlighting the efficacy of the coupled bulk and interface doping of solid electrolytes.
Grid‐scale energy storage systems (ESSs) that can connect to sustainable energy resources have received great attention in an effort to satisfy ever‐growing energy demands. Although recent advances ...in Li‐ion battery (LIB) technology have increased the energy density to a level applicable to grid‐scale ESSs, the high cost of Li and transition metals have led to a search for lower‐cost battery system alternatives. Based on the abundance and accessibility of Na and its similar electrochemistry to the well‐established LIB technology, Na‐ion batteries (NIBs) have attracted significant attention as an ideal candidate for grid‐scale ESSs. Since research on NIB chemistry resurged in 2010, various positive and negative electrode materials have been synthesized and evaluated for NIBs. Nonetheless, studies on NIB chemistry are still in their infancy compared with LIB technology, and further improvements are required in terms of energy, power density, and electrochemical stability for commercialization. Most recent progress on electrode materials for NIBs, including the discovery of new electrode materials and their Na storage mechanisms, is briefly reviewed. In addition, efforts to enhance the electrochemical properties of NIB electrode materials as well as the challenges and perspectives involving these materials are discussed.
The development of novel electrode materials for sodium‐ion batteries is reviewed. Insights and information on recent progress in the area of electrode materials for sodium‐ion batteries is provided, including the discovery of new electrode materials and their Na storage mechanism as well as efforts to enhance the electrochemical properties.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Here, we demonstrate that graphite can serve as a versatile electrode for various rechargeable battery types by reversibly accommodating solvated alkali ions (such as K, Na, and Li) through ...co-intercalation in its galleries. The co-intercalation of alkali ions is observed to occur via staging reactions. Notably, their insertion behaviors, including their specific capacity, are remarkably similar regardless of the alkali ion species despite the different solubility limits of K, Na, and Li ions in graphite. Nevertheless, the insertion potentials of the solvated alkali ions differ from each other and are observed to be correlated with the interlayer distance in the intercalated graphite gallery.
Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is ...widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.
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FZAB, GEOZS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Rechargeable calcium batteries have attracted increasing attention as promising multivalent ion battery systems due to the high abundance of calcium. However, the development has been hampered by the ...lack of suitable cathodes to accommodate the large and divalent Ca
ions at a high redox potential with sufficiently fast ionic conduction. Herein, we report a new intercalation host which presents 500 cycles with a capacity retention of 90% and a remarkable power capability at ~3.2 V (vs. Ca/Ca
) in a calcium battery. The cathode material derived from Na
VPO
F
is demonstrated to reversibly accommodate a large amount of Ca
ions, forming a series of Ca
Na
VPO
F
(0 < x < 0.5) phases without any noticeable structural degradation. The robust framework enables one of the smallest volume changes (1.4%) and the lowest diffusion barriers for Ca
among the cathodes reported to date, offering the basis for the outstanding cycle life and power capability.
The insertion of guest species in graphite is the key feature utilized in applications ranging from energy storage and liquid purification to the synthesis of graphene. Recently, it was discovered ...that solvated-Na-ion intercalation can occur in graphite even though the insertion of Na ions alone is thermodynamically impossible; this phenomenon enables graphite to function as a promising anode for Na-ion batteries. In an effort to understand this unusual behavior, we investigate the solvated-Na-ion intercalation mechanism using in operandoX-ray diffraction analysis, electrochemical titration, real-time optical observation, and density functional theory (DFT) calculations. The ultrafast intercalation is demonstrated in real time using millimeter-sized highly ordered pyrolytic graphite, in which instantaneous insertion of solvated-Na-ions occurs (in less than 2 s). The formation of various stagings with solvated-Na-ions in graphite is observed and precisely quantified for the first time. The atomistic configuration of the solvated-Na-ions in graphite is proposed based on the experimental results and DFT calculations. The correlation between the properties of various solvents and the Na ion co-intercalation further suggests a strategy to tune the electrochemical performance of graphite electrodes in Na rechargeable batteries.
Calcium‐ion batteries (CIBs) are considered to be promising next‐generation energy storage systems because of the natural abundance of calcium and the multivalent calcium ions with low redox ...potential close to that of lithium. However, the practical realization of high‐energy and high‐power CIBs is elusive owing to the lack of suitable electrodes and the sluggish diffusion of calcium ions in most intercalation hosts. Herein, it is demonstrated that calcium‐ion intercalation can be remarkably fast and reversible in natural graphite, constituting the first step toward the realization of high‐power calcium electrodes. It is shown that a graphite electrode exhibits an exceptionally high rate capability up to 2 A g−1, delivering ≈75% of the specific capacity at 50 mA g−1 with full calcium intercalation in graphite corresponding to ≈97 mAh g−1. Moreover, the capacity stably maintains over 200 cycles without notable cycle degradation. It is found that the calcium ions are intercalated into graphite galleries with a staging process. The intercalation mechanisms of the “calciated” graphite are elucidated using a suite of techniques including synchrotron in situ X‐ray diffraction, nuclear magnetic resonance, and first‐principles calculations. The versatile intercalation chemistry of graphite observed here is expected to spur the development of high‐power CIBs.
Graphite as a reliable anode material for calcium‐ion batteries is realized. By selecting a proper dimethylacetamide‐based electrolyte, reversible Ca (de)insertion is enabled in graphite at room temperature with large Ca‐storage capacities, remarkable reversibility, and exceptionally high power capability (≈75% capacity retention at 2 A g−1 to that at 50 mA g−1).
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Co-intercalation reactions make graphite as promising anodes for sodium ion batteries, however, the high redox potentials significantly lower the energy density. Herein, we investigate the factors ...that influence the co-intercalation potential of graphite and find that the tuning of the voltage as large as 0.38 V is achievable by adjusting the relative stability of ternary graphite intercalation compounds and the solvent activity in electrolytes. The feasibility of graphite anode in sodium ion batteries is confirmed in conjunction with Na
VPO
F
cathodes by using the optimal electrolyte. The sodium ion battery delivers an improved voltage of 3.1 V, a high power density of 3863 W kg
, negligible temperature dependency of energy/power densities and an extremely low capacity fading rate of 0.007% per cycle over 1000 cycles, which are among the best thus far reported for sodium ion full cells, making it a competitive choice in large-scale energy storage systems.
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