Critical Factors to Understanding the Electrochemical Performance of All-Solid-State Batteries: Solid Interfaces and Non-Zero Lattice Strain.

All-solid-state lithium batteries have been developed to secure safety by substituting a flammable liquid electrolyte with a non-flammable solid electrolyte. However, owing to the nature of solids, interfacial issues between cathode materials and solid electrolytes, including chemical incompatibility, electrochemo-mechanical behavior, and physical contact, pose significant challenges for commercialization. Herein, critical factors for understanding the performance of all-solid-state batteries in terms of solid interfaces and non-zero lattice strains are identified through a strategic approach. The initial battery capacity can be increased via surface coating and electrode-fabrication methods; however, the increased lattice strain causes significant stress to the solid interface, which degrades the battery cycle life. However, this seesaw effect can be alleviated using a more compacted electrode microstructure between the solid electrolyte and oxide cathode materials. The compact solid interfaces contribute to low charge-transfer resistance and a homogeneous reaction between particles, thereby leading to improved electrochemical performance. These findings demonstrate, for the first time, a correlation between the uniformity of the electrode microstructure and electrochemical performance through the investigation of the reaction homogeneity among particles. Additionally, this study furthers the understanding of the relationship between electrochemical performance, non-zero lattice strain, and solid interfaces.

Exploring Anomalous Charge Storage in Anode Materials for Next-Generation Li Rechargeable Batteries.

To advance current Li rechargeable batteries further, tremendous emphasis has been made on the development of anode materials with higher capacities than the widely commercialized graphite. Some of these anode materials exhibit capacities above the theoretical value predicted based on conventional mechanisms of Li storage, namely insertion, alloying, and conversion. In addition, in contrast to conventional observations of loss upon cycling, the capacity has been found to increase during repeated cycling in a significant number of cases. As the internal environment in the battery is very complicated and continuously changing, these abnormal charge storage behaviors are caused by diverse reactions. In this review, we will introduce our current understanding of reported reactions accounting for the extra capacity. It includes formation/decomposition of electrolyte-derived surface layer, the possibility of additional charge storage at sharp interfaces between electronic and ionic sinks, redox reactions of Li-containing species, unconventional activity of structural defects, and metallic-cluster like Li storage. We will also discuss how the changes in the anode can induce capacity increase upon cycling. With this knowledge, new insights into possible strategies to effectively and sustainably utilize these abnormal charge storage mechanisms to produce vertical leaps in performance of anode materials will be laid out.

Polymorphic Effects on Electrochemical Performance of Conversion-Based MnO2 Anode Materials for Next-Generation Li Batteries.

In this study, four different MnO2 polymorphs are synthesized with a controlled morphology of hollow porous structures to systematically investigate the influences of polymorphs in conversion-based material. As the structure of these materials transforms into nanosized metal and maintains an extremely low-crystalline phase during cell operation, the effects of polymorphs are overlooked as compared to the case of insertion-based materials. Thus, differences in the ion storage behaviors among various MnO2 polymorphs are not well identified. Herein, the structural changes, charge storage reaction, and electrochemical performance of the different MnO2 polymorphs are investigated in detail. The experimental results demonstrate that the charge storage reactions, as part of which spinel-phased MnO2 formation is observed after lithiation and delithiation instead of recovery of the original phases, are similar for all the samples. However, the electrochemical performance varies depending on the initial crystal structure. Among the four polymorphs, the spinel-type λ-MnO2 delivers the highest reversible capacity of ≈1270 mAh g-1 . The structural similarity between the cycled and pristine states of λ-MnO2 induces faster kinetics, resulting in the better electrochemical performance. These findings suggest that polymorphs are another important factor to consider when designing high-performance materials for next-generation rechargeable batteries.

Nanoengineered Organic Electrodes for Highly Durable and Ultrafast Cycling of Organic Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have become increasingly important as next-generation energy storage systems for application in large-scale energy storage. It is very crucial to develop an eco-friendly and green SIB technique with superior performance for sustainable future use. Replacing the conventional inorganic electrode materials with green and safe organic electrodes will be a promising approach. However, the poor electrochemical kinetics, unstable electrode-electrolyte interface, high solubility of the electrodes in the electrolyte, and large amount of conductive carbon present great challenges for organic SIBs. In this study, the issues of organic electrodes are addressed through atomic-level manipulation of these organic molecules using a series of ultrathin (Å-level) metal oxide coatings (Al2 O3 , ZnO, and TiO2 ). Uniform and precise coatings on the perylene-3,4,9,10-tetracarboxylicacid dianhydride by gas-phase atomic layer deposition technique shows a stable interphase, enhanced electrochemical kinetics (71C, 10 A g-1 ), and excellent stability (89%-500 cycles) compared to conventional organic electrode (70%-200 cycles). Further studies reveal that the chemical stability of the metal oxide coating layer plays a critical role in influencing the redox behavior, and improving kinetics of organic electrodes. This study opens a new avenue for developing high-energy organic SIBs with performance equivalent to inorganic counterparts.

Anionic Redox Chemistry as a Clue for Understanding the Structural Behavior in Layered Cathode Materials.

The anionic redox chemistries of layered cathode materials have been in focus recently due to an intriguing phenomenon that cannot be described by the number of electrons of transition metal ions. However, even though several studies have investigated the anionic redox chemistry of layered materials in terms of the charge compensation, the relationship between the origin of the structural behavior and anionic redox chemistry in layered materials remains poorly understood. In addition, a simultaneous redox process of transition metal ions could occur through the d bands interaction. Here, it is demonstrated that the anionic redox chemistry is associated with the anisotropic structural behavior of the layered cathode materials albeit without providing additional capacities exceeding the theoretical values. These findings will provide a foundation of a new chapter in the understanding of the properties of materials.

Additional Lithium Storage on Dynamic Electrode Surface by Charge Redistribution in Inactive Ru Metal.

Beyond a traditional view that metal nanoparticles formed upon electrochemical reaction are inactive against lithium, recently their electrochemical participations are manifested and elucidated as catalytic and interfacial effects. Here, ruthenium metal composed of ≈5 nm nanoparticles is prepared and the pure ruthenium as a lithium-ion battery anode for complete understanding on anomalous lithium storage reaction mechanism is designed. In particular, the pure metal electrode is intended for eliminating the electrochemical reaction-derived Li2 O phase accompanied by catalytic Li2 O decomposition and the interfacial lithium storage at Ru/Li2 O phase boundary, and thereby focusing on the ruthenium itself in exploring its electrochemical reactivity. Intriguingly, unusual lithium storage not involving redox reactions with electron transfer but leading to lattice expansion is identified in the ruthenium electrode. Size-dependent charge redistribution at surface enables additional lithium adsorption to occur on the inactive but more environmentally sensitive nanoparticles, providing innovative insight into dynamic electrode environments in rechargeable lithium chemistry.

A multiscale investigation elucidating the structural complexities and electrochemical properties of layered-layered composite cathode materials synthesized at low temperatures.

Layered-layered composite (xLi2MnO3·(1 -x) LiMO2, M = Mn, Ni, Co, and Fe) cathode materials have attracted much attention as cathodes for high energy density lithium ion batteries. However, these materials are structurally unstable resulting from complicated phase transformation mechanisms during cycling. Additionally, the complex structural characteristics and structural stability of these materials largely depend on their preparation methods. Studying the correlation between multiscale structural properties and preparation methods is important in the development of layered-layered composite cathode materials. In this work, 0.5Li2MnO3·0.5LiCoO2 composite materials were prepared with different heating and cooling rates with a maximum temperature of 600 °C. The structural properties of the 0.5Li2MnO3·0.5LiMO2 composite materials were investigated using combined in situ X-ray absorption spectroscopy (XAS), in situ X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and high resolution transmission electron microscopy (HRTEM) techniques. Heating and cooling rates have no significant effect on either the crystal or local atomic structures of the prepared samples. However, the microstructure was critically important for its impact on electrochemical properties.

Advances in the Cathode Materials for Lithium Rechargeable Batteries.

The accelerating development of technologies requires a significant energy consumption, and consequently the demand for advanced energy storage devices is increasing at a high rate. In the last two decades, lithium-ion batteries have been the most robust technology, supplying high energy and power density. Improving cathode materials is one of the ways to satisfy the need for even better batteries. Therefore developing new types of positive electrode materials by increasing cell voltage and capacity with stability is the best way towards the next-generation Li rechargeable batteries. To achieve this goal, understanding the principles of the materials and recognizing the problems confronting the state-of-the-art cathode materials are essential prerequisites. This Review presents various high-energy cathode materials which can be used to build next-generation lithium-ion batteries. It includes nickel and lithium-rich layered oxide materials, high voltage spinel oxides, polyanion, cation disordered rock-salt oxides and conversion materials. Particular emphasis is given to the general reaction and degradation mechanisms during the operation as well as the main challenges and strategies to overcome the drawbacks of these materials.

Nanostructural Uniformity of Ordered Mesoporous Materials: Governing Lithium Storage Behaviors.

Nanostructured materials make a considerable impact on the performance of lithium-storage characteristics in terms of the energy density, power density, and cycle life. Direct experimental observation, by a comparison of controlled nanostructural uniformity of electrode materials, reveals that the lithium-storage behaviors of mesoporous MoO2 and CuO electrodes are linearly correlated with their nanostructural uniformity. Reversible capacities of mesoporous MoO2 and CuO electrodes with well-developed nanostructures (1569 mA h g-1 for MoO2 and 1029 mA h g-1 for CuO) exceed their theoretical capacity based on the conversion reaction (838 mA h g-1 for MoO2 and 674 mA h g-1 for CuO). Given that exact understanding of the origin of the additional capacity is essential in maximizing the energy density of electrode material, this work may help to gain some insights into the development of high energy-density lithium-storage materials for next-generation lithium rechargeable batteries.

In situ analyses for ion storage materials.

Development of high performance electrode materials for energy storage is one of the most important issues for our future society. However, a lack of clear analytical views limits critical understanding of electrode materials. This review covers useful analytical work using X-ray diffraction, X-ray absorption spectroscopy, microscopy and neutron diffraction for ion storage systems. The in situ observation facilitates comprehending real-time ion storage behaviour while the ion storage system is operating, which help us to understand detailed physical and chemical properties. We will discuss how the tools have been used to reveal detailed reaction mechanisms and underlying properties of electrode materials.

The First Complete Chloroplast Genome of Campanula carpatica: Genome Characterization and Phylogenetic Diversity.

Campanula carpatica is an ornamental flowering plant belonging to the family Campanulaceae. The complete chloroplast genome of C. carpatica was obtained using Illumina HiSeq X and Oxford Nanopore (Nanopore GridION) platforms. The chloroplast genome exhibited a typical circular structure with a total length of 169,341 bp, comprising a large single-copy region of 102,323 bp, a small single-copy region of 7744 bp, and a pair of inverted repeats (IRa/IRb) of 29,637 bp each. Out of a total 120 genes, 76 were protein-coding genes, 36 were transfer RNA genes, and eight were ribosomal RNA genes. The genomic characteristics of C. carpatica are similar to those of other Campanula species in terms of repetitive sequences, sequence divergence, and contraction/expansion events in the inverted repeat regions. A phylogenetic analysis of 63 shared genes in 16 plant species revealed that Campanula zangezura is the closest relative of C. carpatica. Phylogenetic analysis indicated that C. carpatica was within the Campanula clade, and C. pallida occupied the outermost position of that clade.

Achieving structural stability and enhanced electrochemical performance through Nb-doping into Li- and Mn-rich layered cathode for lithium-ion batteries.

Although Li- and Mn-rich layered oxides are attractive cathode materials possessing high energy densities, they have not been commercialized owing to voltage decay, low rate capability, poor capacity retention, and high irreversible capacity in the first cycle. To circumvent these issues, we propose a Li1.2Ni0.13Co0.13Mn0.53Nb0.01O2 (Nb-LNCM) cathode material, wherein Nb doping strengthens the transition metal oxide (TM-O) bond and alleviates the anisotropic lattice distortion while stabilizing the layered structure. During long-term cycling, maintaining a wider LiO6 interslab thickness in Nb-LNCM creates a favorable Li+ diffusion path, which improves the rate capability. Moreover, Nb doping can decrease oxygen loss, suppress the phase transition from layered to spinel and rock-salt structures, and relieve structural degradation. Nb doping results in less capacity contributions of Mn and Co and more reversible Ni and O redox reactions compared to pristine Li1.2Ni0.133Co0.133Mn0.533O2 (LNCM), which significantly mitigates the voltage decay (Δ0.289 and Δ0.516 V for Nb-LNCM and LNCM, respectively) and ensures stable capacity retention (82.7 and 70.3% for Nb-LNCM and LNCM, respectively) during the initial 100 cycles. Our study demonstrates that Nb doping is an effective and practical strategy to enhance the structural and electrochemical integrity of Li- and Mn-rich layered oxides. This promotes the development of stable cathode materials for high-energy-density lithium-ion batteries.

Colloidal Synthesis of Ultrathin and Se-Rich V2Se9 Nanobelts as High-Performance Anode Materials for Li-Ion Batteries.

In this study, the one-dimensional (1D) material V2Se9 was successfully synthesized using a colloidal method with VO(acac)2 and Se powder as precursors in a 1-octadecene solvent. The obtained colloidally synthesized V2Se9 (C-V2Se9) has an ultrathin nanobelt shape and a 4.5 times higher surface area compared with the bulk V2Se9, which is synthesized in a solid-state reaction as previously reported. In addition, all surfaces of C-V2Se9 are exposed to Se atoms, which is advantageous for storing Li through the conversion reaction into the Li2Se phase. Herein, the electrochemical performance of the C-V2Se9 anode material is evaluated; thus, the novelty of C-V2Se9 as a Se-rich 1D anode material is verified. The C-V2Se9 electrode exhibits a reversible capacity of 893.21 mA h g-1 and a Coulombic efficiency of 97.82% at the 100th cycle and excellent structural stability. Compared with the bulk V2Se9 electrode, the outstanding electrochemical performance of C-V2Se9 is attributed to its ultrathin nanobelt shape, high surface area, shorter Li diffusion length, and more electrochemically active sites. This work indicates the great potential of the Se-rich 1D material, C-V2Se9, as a post-transition metal dichalcogenide material for high-performance LIBs.

Unveiling the Genesis and Effectiveness of Negative Fading in Nanostructured Iron Oxide Anode Materials for Lithium-Ion Batteries.

Iron oxide anode materials for rechargeable lithium-ion batteries have garnered extensive attention because of their inexpensiveness, safety, and high theoretical capacity. Nanostructured iron oxide anodes often undergo negative fading, that is, unconventional capacity increase, which results in a capacity increasing upon cycling. However, the detailed mechanism of negative fading still remains unclear, and there is no consensus on the provenance. Herein, we comprehensively investigate the negative fading of iron oxide anodes with a highly ordered mesoporous structure by utilizing advanced synchrotron-based analysis. Electrochemical and structural analyses identified that the negative fading originates from an optimization of the electrolyte-derived surface layer, and the thus formed layer significantly contributes to the structural stability of the nanostructured electrode materials, as well as their cycle stability. This work provides an insight into understanding the origin of negative fading and its influence on nanostructured anode materials.

Understanding the effect of nonmetallic impurities in regenerated cathode materials for lithium-ion battery recycling by tracking down impurity elements.

The regeneration of cathode materials would be the highest value-added direction in lithium-ion battery (LIB) recycling research. Li[NixMnyCoz]O2 (NMC) is regenerated from actual industrial scale LIB leachate and purified leachate to investigate the precipitation behavior of impurities, which include potentially toxic elements, such as F, Cl, and S. Regenerated precursors from the actual leachate, purified precursors, and a control sample are synthesized using the hydroxide co-precipitation method. Additionally, simulated precursors from simulated leachate are prepared in order to separate the effects of nonmetallic elements from the effects of metallic elements. The structure and electrochemical properties of the regenerated precursors and the corresponding cathode materials are examined. We first detect the presence of a significant amount of nonmetal elements, such as F as well as well-known metal elements, which include Al, Cu, and Fe, in the regenerated NMC. The concept of yield of precipitation (YOP) is introduced to assess the precipitation behavior of each element during the co-precipitation of the precursors. According to the concentration and YOP in the leachate and the precursors, six metal and three nonmetal elements are categorized. This categorization of impurity elements will certainly provide the LIB recycling industry with a valuable quality control guide.

Tracking the Influence of Thermal Expansion and Oxygen Vacancies on the Thermal Stability of Ni-Rich Layered Cathode Materials.

The ever-growing demand for high-energy lithium-ion batteries in portable electronics and electric vehicles has triggered intensive research efforts over the past decade. An efficient strategy to boost the energy and power density of lithium-ion batteries is to increase the Ni content in the cathode materials. However, a higher Ni content in the cathode materials gives rise to safety issues. Herein, thermal expansion and oxygen vacancies are proposed as new critical factors that affect the thermal stability of charged Ni-rich cathode materials based on a systematic synchrotron-based X-ray study of Li0.33Ni0.5+ x Co0.2Mn0.3- x O2 (x = 0, 0.1, 0.2) cathode materials during a heating process. Charged cathode materials with higher Ni contents show larger thermal expansion, which accelerates transition metal migration to the Li layers. Oxygen vacancies are formed and accumulate mainly around Ni ions until the layered-to-spinel phase transition begins. The oxygen vacancies also facilitate transition metal migration to the Li layers. Thermal expansion and the presence of oxygen vacancies decrease the energy barrier for cation migration and facilitate the phase transitions in charged cathode materials during the heating process. These results provide valuable guidance for developing new cathode materials with improved safety characteristics.

Fully Exploited Oxygen Redox Reaction by the Inter-Diffused Cations in Co-Free Li-Rich Materials for High Performance Li-Ion Batteries.

To meet the growing demand for global electrical energy storage, high-energy-density electrode materials are required for Li-ion batteries. To overcome the limit of the theoretical energy density in conventional electrode materials based solely on the transition metal redox reaction, the oxygen redox reaction in electrode materials has become an essential component because it can further increase the energy density by providing additional available electrons. However, the increase in the contribution of the oxygen redox reaction in a material is still limited due to the lack of understanding its controlled parameters. Here, it is first proposed that Li-transition metals (TMs) inter-diffusion between the phases in Li-rich materials can be a key parameter for controlling the oxygen redox reaction in Li-rich materials. The resulting Li-rich materials can achieve fully exploited oxygen redox reaction and thereby can deliver the highest reversible capacity leading to the highest energy density, ≈1100 Wh kg-1 among Co-free Li-rich materials. The strategy of controlling Li/transition metals (TMs) inter-diffusion between the phases in Li-rich materials will provide feasible way for further achieving high-energy-density electrode materials via enhancing the oxygen redox reaction for high-performance Li-ion batteries.

Cinnamon-Derived Hierarchically Porous Carbon as an Effective Lithium Polysulfide Reservoir in Lithium-Sulfur Batteries.

Lithium-sulfur batteries are attractive candidates for next generation high energy applications, but more research works are needed to overcome their current challenges, namely: (a) the poor electronic conductivity of sulfur, and (b) the dissolution and migration of long-chain polysulfides. Inspired by eco-friendly and bio-derived materials, we synthesized highly porous carbon from cinnamon sticks. The bio-carbon had an ultra-high surface area and large pore volume, which serves the dual functions of making sulfur particles highly conductive and acting as a polysulfide reservoir. Sulfur was predominantly impregnated into pores of the carbon, and the inter-connected hierarchical pore structure facilitated a faster ionic transport. The strong carbon framework maintained structural integrity upon volume expansion, and the unoccupied pores served as polysulfide trapping sites, thereby retaining the polysulfide within the cathode and preventing sulfur loss. These mechanisms contributed to the superior performance of the lithium-sulfur cell, which delivered a discharge capacity of 1020 mAh g-1 at a 0.2C rate. Furthermore, the cell exhibited improved kinetics, with an excellent cycling stability for 150 cycles with a very low capacity decay of 0.10% per cycle. This strategy of combining all types of pores (micro, meso and macro) with a high pore volume and ultra-high surface area had a synergistic effect on improving the performance of the sulfur cathode.

Phase Dynamics on Conversion-Reaction-Based Tin-Doped Ferrite Anode for Next-Generation Lithium Batteries.

The conventional view of conversion reaction is based on the reversibility, returning to an initial material structure through reverse reaction at each cycle in cycle life, which impedes the complete understanding on a working mechanism upon a progression of cycles in conversion-reaction-based battery electrodes. Herein, a series of tin-doped ferrites (Fe3- xSn xO4, x = 0-0.36) are prepared and applied to a lithium-ion battery anode. By achieving the ideal reoxidation into SnO2, the Fe2.76Sn0.24O4 composite anchored on reduced graphene oxide shows a high reversible capacity of 1428 mAh g-1 at 200 mA g-1 after 100 cycles, which is the best performance of Sn-based anode materials so far. Significantly, a newly formed γ-FeOOH phase after 100 cycles is identified from topological features through synchrotron X-ray absorption spectroscopy with electronic and atomic structural information, suggesting the phase transformation from magnetite to lepidocrocite upon cycling. Contrary to the conventional view, our work suggests a variable working mechanism in an iron-based composite with the dynamic phases from iron oxide to iron oxyhydroxide in the battery cycle life, based on the reactivity of metal nanoparticles formed during reaction toward the solid electrolyte interface layer.

Indirect-To-Direct Band Gap Transition of One-Dimensional V2Se9: Theoretical Study with Dispersion Energy Correction.

Recently, we synthesized a one-dimensional (1D) structure of V2Se9. The 1D V2Se9 resembles another 1D material, Nb2Se9, which is expected to have a direct band gap. To determine the potential applications of this material, we calculated the band structures of 1D and bulk V2Se9 using density functional theory by varying the number of chains and comparing their band structures and electronic properties with those of Nb2Se9. The results showed that a small number of V2Se9 chains have a direct band gap, whereas bulk V2Se9 possesses an indirect band gap, like Nb2Se9. We expect that V2Se9 nanowires with diameters less than ∼20 Šwould have direct band gaps. This indirect-to-direct band gap transition could lead to potential optoelectronic applications for this 1D material because materials with direct band gaps can absorb photons without being disturbed by phonons.