Impact of Transition Metal Layer Vacancy on the Structure and Performance of P2 Type Layered Sodium Cathode Material.

This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na0.6[Ni0.3Ru0.3Mn0.4]O2 (NRM) cathode material. The incorporation of Ru, Ni, and vacancy enhances the structural stability during extensive cycling, increases the operation voltage, and induces a capacity increase while also activating oxygen redox, respectively, in Na0.7[Ni0.2VNi0.1Ru0.3Mn0.4]O2 (V-NRM) compound. Various analytical techniques including transmission electron microscopy, X-ray absorption near edge spectroscopy, operando X-ray diffraction, and operando differential electrochemical mass spectrometry are employed to assess changes in the average oxidation states and structural distortions. The results demonstrate that V-NRM exhibits higher capacity than NRM and maintains a moderate capacity retention of 81% after 100 cycles. Furthermore, the formation of additional lone-pair electrons in the O 2p orbital enables V-NRM to utilize more capacity from the oxygen redox validated by density functional calculation, leading to a widened dominance of the OP4 phase without releasing O2 gas. These findings offer valuable insights for the design of advanced high-capacity cathode materials with improved performance and sustainability in sodium-ion batteries.

Relaxation of Stress Propagation in Alloying-Type Sn Anodes for K-Ion Batteries.

Alloying-type metallic tin is perceived as a potential anode material for K-ion batteries owing to its high theoretical capacity and reasonable working potential. However, pure Sn still face intractable issues of inferior K+ storage capability owing to the mechanical degradation of electrode against large volume changes and formation of intermediary insulating phases K4 Sn9 and KSn during alloying reaction. Herein, the TiC/C-carbon nanotubes (CNTs) is prepared as an effective buffer matrix and composited with Sn particles (Sn-TiC/C-CNTs) through the high-energy ball-milling method. Owing to the conductive and rigid properties, the TiC/C-CNTs matrix enhances the electrical conductivity as well as mechanical integrity of Sn in the composite material and thus ultimately contributes to performance supremacy in terms of electrochemical K+ storage properties. During potassiation process, the TiC/C-CNTs matrix not only dissipates the internal stress toward random radial orientations within the Sn particle but also provides electrical pathways for the intermediate insulating phases; this tends to reduce microcracking and prevent considerable electrode degradation.

Gold-Nanolayer-Derived Zincophilicity Suppressing Metallic Zinc Dendrites and Its Efficacy in Improving Electrochemical Stability of Aqueous Zinc-Ion Batteries.

Herein, an Au-coating layer adjusted on the surface of a Zn metal electrode that effectively suppresses the dendrite growth as well as the mechanisms underlying the dendrite suppression as a result of the zincophilic character of Au is introduced. For the Au-coated Zn metal symmetric cell, uniform deposition of Zn-derived compounds was revealed by operando synchrotron tomography. Microscopic studies demonstrate that the Au-coating layer is induced to form a new Zn-Au alloy during the initial Zn deposition, resulting in stabilized long-term stripping/plating of Zn via the 'embracing effect' that intimately accommodates Zn deposition for further cycles. This property supports the successful operation of symmetrical cells up to 50 mA cm-2 . According to Zn electrodeposition simulation, it is verified that the suppression of dendrite growth is responsible for the electro-conducting Au nanolayer that uniformly distributes the electric field and protects the Zn electrode from corrosion, ultimately promoting uniform Zn growth. The compatibility of the Au-coating layer for full cell configuration is verified using NaV3 O8 as a cathode material over 1 000 cycles. This finding provides a new pathway for the enhancement of the electrochemical performance of ZIBs by suppressing the dendritic growth of Zn by means of a zincophilic Au nanolayer.

Anion-Induced Interfacial Liquid Layers on LiCoO2 in Salt-in-Water Lithium-Ion Batteries.

The incompatibility of lithium intercalation electrodes with water has impeded the development of aqueous Li-ion batteries. The key challenge is protons which are generated by water dissociation and deform the electrode structures through intercalation. Distinct from previous approaches utilizing large amounts of electrolyte salts or artificial solid-protective films, we developed liquid-phase protective layers on LiCoO2 (LCO) using a moderate concentration of 0.5∼3 mol kg-1 lithium sulfate. Sulfate ion strengthened the hydrogen-bond network and easily formed ion pairs with Li+, showing strong kosmotropic and hard base characteristics. Our quantum mechanics/molecular mechanics (QM/MM) simulations revealed that sulfate ion paired with Li+ helped stabilize the LCO surface and reduced the density of free water in the interface region below the point of zero charge (PZC) potential. In addition, in situ electrochemical surface-enhanced infrared absorption spectroscopy (SEIRAS) proved the appearance of inner-sphere sulfate complexes above the PZC potential, serving as the protective layers of LCO. The role of anions in stabilizing LCO was correlated with kosmotropic strength (sulfate > nitrate > perchlorate > bistriflimide (TFSI-)) and explained better galvanostatic cyclability in LCO cells.

In Situ Mesopore Formation in SiOx Nanoparticles by Chemically Reinforced Heterointerface and Use of Chemical Prelithiation for Highly Reversible Lithium-Ion Battery Anode.

SiOx is a promising next-generation anode material for lithium-ion batteries. However, its commercial adoption faces challenges such as low electrical conductivity, large volume expansion during cycling, and low initial Coulombic efficiency. Herein, to overcome these limitations, an eco-friendly in situ methodology for synthesizing carbon-containing mesoporous SiOx nanoparticles wrapped in another carbon layers is developed. The chemical reactions of vinyl-terminated silanes are designed to be confined inside the cationic surfactant-derived emulsion droplets. The polyvinylpyrrolidone-based chemical functionalization of organically modified SiO2 nanoparticles leads to excellent dispersion stability and allows for intact hybridization with graphene oxide sheets. The formation of a chemically reinforced heterointerface enables the spontaneous generation of mesopores inside the thermally reduced SiOx nanoparticles. The resulting mesoporous SiOx -based nanocomposite anodes exhibit superior cycling stability (≈100% after 500 cycles at 0.5 A g-1 ) and rate capability (554 mAh g-1 at 2 A g-1 ), elucidating characteristic synergetic effects in mesoporous SiOx -based nanocomposite anodes. The practical commercialization potential with a significant enhancement in initial Coulombic efficiency through a chemical prelithiation reaction is also presented. The full cell employing the prelithiated anode demonstrated more than 2 times higher Coulombic efficiency and discharge capacity compared to the full cell with a pristine anode.

Resolving the Incomplete Charging Behavior of Redox-Mediated Li-O2 Batteries via Sustainable Protection of Li Metal Anode.

Lithium-oxygen batteries (LOBs) have attracted worldwide attention due to their high specific energy. However, the poor rechargeability and cycling stability of LOBs hinders their practical use in applications. Here, we explore the incomplete charging behavior of redox-mediated LOBs operated at a feasible capacity for a practical level (3.25 mAh cm-2) and resolve it using a sustainable lithium protection strategy. The incomplete charging behavior, promoted by self-discharge of redox mediators (RMs), hampers the reversible cycling of LOBs, which was investigated through multiangle in situ and ex situ analyses. Meanwhile, the proposed lithium protection strategy, introducing an inorganic/organic hybrid artificial composite layer with a preformed stable interface between the lithium metal and the composite layer, enhances the stability of the lithium metal anode during the prolonged cycling by preventing the chemical/electrochemical interactions of RMs on the lithium metal surface, thus improving the overall rechargeability of LOBs. This work provides guidelines for the effective use of RMs with an adequate lithium protection strategy to achieve sustainable cycling of LOBs, creating a feasible approach for the practical use of LOBs with high areal capacity.

Facile Method for the Formation of Intimate Interfaces in Sulfide-Based All-Solid-State Batteries.

Sulfide-based inorganic solid electrolytes have been considered promising candidates for all-solid-state batteries owing to their high ionic conductivity. Compared with oxide-based inorganic solid electrolytes which require high-temperature sintering, the intrinsic deformability of sulfide electrolytes enables the fabrication of all-solid-state batteries by a simple cold pressing method. Nevertheless, the performance of sulfide-based all-solid-state batteries is still unsatisfactory, owing to the insufficient interfacial properties within the composite electrodes. Using cold pressing alone, it is challenging to form intimate contacts with rigid oxide-based cathode materials. Here, we demonstrate a mild-temperature pressing (MP) method for the fabrication of all-solid-state batteries. The mild temperature (85 °C) increases the deformability of the sulfide and therefore helps to form more enhanced interfacial contacts in the composite cathode without side reactions. Compared with the conventional cold pressing cell, the MP cell possesses more favorable contacts, resulting in higher capacity, cyclability, and rate capability. In addition, we demonstrate that the charge-transfer resistance in composite cathodes dominates the electrochemical performance of all-solid-state batteries.

Self-Constructed Intimate Interface on a Silicon Anode Enabled by a Phase-Convertible Electrolyte for Lithium-Ion Batteries.

Promising high-capacity anodes of Si-based materials suffer from large volume expansions, thereby limiting their practical applications, especially in combination with safe inorganic solid electrolytes. Here, to achieve a high level of safety by applying Si anodes, we introduced a quasi-solid-state succinonitrile-based electrolyte (QS-SCN) that enables the practical application of the anode with long-term cycling performance. By exploiting the unique phase-convertible property of QS-SCN, the Si electrode was successfully impregnated with the liquid-state electrolyte above its melting temperature, and a simple cooling process was then used to form a quasi-solid-state Li-Si cell. Additionally, through a precycling process, the formation of a stable and rigid solid-electrolyte interphase (SEI) was induced, and the intimate contacts between the QS-SCN and Si particles were preserved. The soft QS-SCN played an important role as a buffer in the large volume expansions while maintaining favorable interface contacts, and the formation of the SEI layers contributed to the reversible lithiation and delithiation in the Si particles. As a result, the quasi-solid-state Li-Si cell fabricated with QS-SCN exhibited significantly improved capacity retention compared with an all-solid-state cell.

Multiscale Understanding of Covalently Fixed Sulfur-Polyacrylonitrile Composite as Advanced Cathode for Metal-Sulfur Batteries.

Metal-sulfur batteries (MSBs) provide high specific capacity due to the reversible redox mechanism based on conversion reaction that makes this battery a more promising candidate for next-generation energy storage systems. Recently, along with elemental sulfur (S8 ), sulfurized polyacrylonitrile (SPAN), in which active sulfur moieties are covalently bounded to carbon backbone, has received significant attention as an electrode material. Importantly, SPAN can serve as a universal cathode with minimized metal-polysulfide dissolution because sulfur is immobilized through covalent bonding at the carbon backbone. Considering these unique structural features, SPAN represents a new approach beyond elemental S8 for MSBs. However, the development of SPAN electrodes is in its infancy stage compared to conventional S8 cathodes because several issues such as chemical structure, attached sulfur chain lengths, and over-capacity in the first cycle remain unresolved. In addition, physical, chemical, or specific treatments are required for tuning intrinsic properties such as sulfur loading, porosity, and conductivity, which have a pivotal role in improving battery performance. This review discusses the fundamental and technological discussions on SPAN synthesis, physicochemical properties, and electrochemical performance in MSBs. Further, the essential guidance will provide research directions on SPAN electrodes for potential and industrial applications of MSBs.

State-of-the-art anodes of potassium-ion batteries: synthesis, chemistry, and applications.

The growing demand for green energy has fueled the exploration of sustainable and eco-friendly energy storage systems. To date, the primary focus has been solely on the enhancement of lithium-ion battery (LIB) technologies. Recently, the increasing demand and uneven distribution of lithium resources have prompted extensive attention toward the development of other advanced battery systems. As a promising alternative to LIBs, potassium-ion batteries (KIBs) have attracted considerable interest over the past years owing to their resource abundance, low cost, and high working voltage. Capitalizing on the significant research and technological advancements of LIBs, KIBs have undergone rapid development, especially the anode component, and diverse synthesis techniques, potassiation chemistry, and energy storage applications have been systematically investigated and proposed. In this review, the necessity of exploring superior anode materials is highlighted, and representative KIB anodes as well as various structural construction approaches are summarized. Furthermore, critical issues, challenges, and perspectives of KIB anodes are meticulously organized and presented. With a strengthened understanding of the associated potassiation chemistry, the composition and microstructural modification of KIB anodes could be significantly improved.

Functionalized Sulfide Solid Electrolyte with Air-Stable and Chemical-Resistant Oxysulfide Nanolayer for All-Solid-State Batteries.

Sulfide solid electrolytes (SEs) with high Li-ion conductivities (σion) and soft mechanical properties have limited applications in wet casting processes for commercial all-solid-state batteries (ASSBs) because of their inherent atmospheric and chemical instabilities. In this study, we fabricated sulfide SEs with a novel core-shell structure via environmental mechanical alloying, while providing sufficient control of the partial pressure of oxygen. This powder possesses notable atmospheric stability and chemical resistance because it is covered with a stable oxysulfide nanolayer that prevents deterioration of the bulk region. The core-shell SEs showed a σion of more than 2.50 mS cm-1 after air exposure (for 30 min) and reaction with slurry chemicals (mixing and drying for 31 min), which was approximately 82.8% of the initial σion. The ASSB cell fabricated through wet casting provided an initial discharge capacity of 125.6 mAh g-1. The core-shell SEs thus exhibited improved powder stability and reliability in the presence of chemicals used in various wet casting processes for commercial ASSBs.

Theoretical Design of Lithium Chloride Superionic Conductors for All-Solid-State High-Voltage Lithium-Ion Batteries.

The development of solid electrolytes (SEs) is a promising pathway to improve the energy density and safety of conventional Li-ion batteries. Several lithium chloride SEs, Li3MCl6 (M = Y, Er, In, and Sc), have gained popularity due to their high ionic conductivity, wide electrochemical window, and good chemical stability. This study systematically investigated 17 Li3MCl6 SEs to identify novel and promising lithium chloride SEs. Calculation results revealed that 12 Li3MCl6 (M = Bi, Dy, Er, Ho, In, Lu, Sc, Sm, Tb, Tl, Tm, and Y) were stable phase with a wide electrochemical stability window and excellent chemical stability against cathode materials and moisture. Li-ion transport properties were examined using bond valence site energy (BVSE) and ab initio molecular dynamics (AIMD) calculation. Li3MCl6 showed the lower migration energy barrier in monoclinic structures, while orthorhombic and trigonal structures exhibited higher energy barriers due to the sluggish diffusion along the two-dimensional path based on the BVSE model. AIMD results confirmed the slower ion migration along the 2D path, exhibiting lower ionic diffusivity and higher activation energy in orthorhombic and trigonal structures. For the further increase of ionic conductivity in monoclinic structures, Li-ion vacancy was formed by the substitution of M3+ with Zr4+. Zr-substituted phase (Li2.5M0.5Zr0.5Cl6, M = In, Sc) exhibited up to a fourfold increase in ionic conductivity. This finding suggested that the optimization of Li vacancy in the Li3MCl6 SEs could lead to superionic Li3MCl6 SEs.

Superionic Halogen-Rich Li-Argyrodites Using In Situ Nanocrystal Nucleation and Rapid Crystal Growth.

Although several crystalline materials have been developed as Li-ion conductors for use as solid electrolytes in all-solid-state batteries (ASSBs), producing materials with high Li-ion conductivities is time-consuming and cost-intensive. Herein, we introduce a superionic halogen-rich Li-argyrodite (HRLA) and demonstrate its innovative synthesis using ultimate-energy mechanical alloying (UMA) and rapid thermal annealing (RTA). UMA with a 49 G-force milling energy provides a one-pot process that includes mixing, glassification, and crystallization, to produce as-milled HRLA powder that is ∼70% crystallized; subsequent RTA using an infrared lamp increases this crystallinity to ∼82% within 25 min. Surprisingly, this HRLA exhibits the highest Li-ion conductivity among Li-argyrodites (10.2 mS cm-1 at 25 °C, cold-pressed powder compact) reported so far. Furthermore, we confirm that this superionic HRLA works well as a promising solid electrolyte without a decreased intrinsic electrochemical window in various electrode configurations and delivers impressive cell performance (114.2 mAh g-1 at 0.5 C).

Nano/Microstructured Silicon-Carbon Hybrid Composite Particles Fabricated with Corn Starch Biowaste as Anode Materials for Li-Ion Batteries.

Silicon has a great potential as an alternative to graphite which is currently used commercially as an anode material in lithium-ion batteries (LIBs) because of its exceptional capacity and reasonable working potential. Herein, a low-cost and scalable approach is proposed for the production of high-performance silicon-carbon (Si-C) hybrid composite anodes for high-energy LIBs. The Si-C composite material is synthesized using a scalable microemulsion method by selecting silicon nanoparticles, using low-cost corn starch as a biomass precursor and finally conducting heat treatment under C3H6 gas. This produces a unique nano/microstructured Si-C hybrid composite comprised of silicon nanoparticles embedded in micron-sized amorphous carbon balls derived from corn starch that is capsuled by thin graphitic carbon layer. Such a dual carbon matrix tightly surrounds the silicon nanoparticles that provides high electronic conductivity and significantly decreases the absolute stress/strain of the material during multiple lithiation-delithiation processes. The Si-C hybrid composite anode demonstrates a high capacity of 1800 mAh g-1, outstanding cycling stability with capacity retention of 80% over 500 cycles, and fast charge-discharge capability of 12 min. Moreover, the Si-C composite anode exhibits good acceptability in practical LIBs assembled with commercial Li[Ni0.6Co0.2Mn0.2]O2 and Li[Ni0.80Co0.15Al0.05]O2 cathodes.

Presodiation Strategies and Their Effect on Electrode-Electrolyte Interphases for High-Performance Electrodes for Sodium-Ion Batteries.

Most active materials for sodium-ion batteries suffer from the problem of low-energy efficiency in the first cycle because of the loss of active sodium ions consumed for the formation of a solid electrolyte interface. To make up for the lost sodium ion, presodiation treatments have been applied, which are effective ways to mitigate the low initial efficiency. Here, we developed a direct-contact method to achieve the presodiation for cathode and anode electrodes and demonstrated the enhanced Coulombic efficiency of the first cycle with improved cyclability and reversible capacity. Moreover, we proved the formation of a thick passivation layer at the cathode-electrolyte interface during the presodiation process; this contributes to the improved cycle stability by preventing the dissolution of the active material and its deposition on the anode surface. The direct-contact method is a simple and cost-effective way to complete presodiation, and this simple process will be widely applicable for practical battery manufacturing.

Deactivation of redox mediators in lithium-oxygen batteries by singlet oxygen.

Non-aqueous lithium-oxygen batteries cycle by forming lithium peroxide during discharge and oxidizing it during recharge. The significant problem of oxidizing the solid insulating lithium peroxide can greatly be facilitated by incorporating redox mediators that shuttle electron-holes between the porous substrate and lithium peroxide. Redox mediator stability is thus key for energy efficiency, reversibility, and cycle life. However, the gradual deactivation of redox mediators during repeated cycling has not conclusively been explained. Here, we show that organic redox mediators are predominantly decomposed by singlet oxygen that forms during cycling. Their reaction with superoxide, previously assumed to mainly trigger their degradation, peroxide, and dioxygen, is orders of magnitude slower in comparison. The reduced form of the mediator is markedly more reactive towards singlet oxygen than the oxidized form, from which we derive reaction mechanisms supported by density functional theory calculations. Redox mediators must thus be designed for stability against singlet oxygen.

Unveiling the mechanism of sodium ion storage for needle-shaped ZnxCo3-xO4 nanosticks as anode materials.

The interest in the development of micro-nanostructured metal oxides has been increasing recently because of their advantages as electrode materials in energy storage applications. In this study, dandelion-like ZnxCo3-xO4 microspheres assembled with porous needle-shaped nanosticks were synthesized by co-precipitation followed by a post-annealing treatment. The open space between neighboring nanosticks enables easy infiltration of the electrolyte; therefore, each nanostick is surrounded by the electrolyte solution, which ensures proper utilization of the active material during the electrochemical reaction. The dandelion-like ZnxCo3-xO4 hierarchical microspheres exhibit a greatly improved electrochemical performance with a high capacity and good cyclability as anodes for sodium-ion batteries (SIBs). A high initial reversible capacity of 612 mA h g-1 (at 35 mA g-1, ∼0.04C) is obtained and a capacity of 349 mA h g-1 is retained after 200 cycles. Meanwhile, the electrode shows a high rate performance with a capacity of 246 mA h g-1 at 2.0C-rate. The conversion of ZnxCo3-xO4 with Na is followed by ex situ X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) in different sodiation/de-sodiation states during electrochemical cycling. These analyses reveal that Na insertion/extraction is followed by complete reduction/oxidation of both metallic cobalt and zinc. The development of metallic Co and Zn after complete discharge and the formation of Co3O4 and ZnO when the electrode was fully recharged were identified by ex situ TEM analysis. In addition, the ZnxCo3-xO4 anode demonstrates feasible operation in a full cell by pairing with a NaNi2/3Bi1/3O2 cathode, affording a sodium-ion battery with an average working voltage of 2.6 V.

Atomistic Assessments of Lithium-Ion Conduction Behavior in Glass-Ceramic Lithium Thiophosphates.

We determined the interatomic potentials of the Li-[PS43-] building block in (Li2S)0.75(P2S5)0.25 (LPS) and predicted the Li-ion conductivity (σLi) of glass-ceramic LPS from molecular dynamics. The Li-ion conduction characteristics in the crystalline/interfacial/glassy structure were decomposed by considering the structural ordering differences. The superior σLi of the glassy LPS could be attributed to the fact that ∼40% of its structure consists of the short-ranged cubic S-sublattice instead of the hexagonally close-packed γ-phase. This glassy LPS has a σLi of 4.08 × 10-1 mS cm-1, an improvement of ∼100 times relative to that of the γ-phase, which is in agreement with the experiments.

Kinetic and Electrochemical Reaction Mechanism Investigations of Rodlike CoMoO4 Anode Material for Sodium-Ion Batteries.

Sodium-ion batteries are considered the most promising power source for electrical energy storage systems because of the abundance of sodium and their significant cost advantages. However, high-performance electrode materials are required for their successful application. Herein, we report a monoclinic-type CoMoO4 material which is synthesized by a simple solution method. An optimized calcination temperature with a high crystallinity and a rodlike morphology of the material are selected after analyzing the as-synthesized powder by temperature-dependent time-resolved X-ray diffraction. The CoMoO4 rods exhibit initial discharge and charge capacities of 537 and 410 mA h g-1, respectively, when used as an anode for sodium-ion batteries. The sodium diffusion coefficient in the bimetallic CoMoO4 anode is measured using the galvanostatic intermittent titration technique and calculated in the range of 1.565 × 10-15 to 4.447 × 10-18 cm2 s-1 during the initial cycle. Further, the reaction mechanism is investigated using ex situ X-ray diffraction and X-ray absorption spectroscopy, and the obtained results suggest an amorphous-like structure and reduction/oxidation of Co and Mo during the sodium insertion/extraction process. Ex situ transmission electron microscopy and energy-dispersive spectroscopy images of the CoMoO4 anode in fully discharged and recharged state reveal the rodlike morphology with homogenous element distribution.

Quantitative Analysis of Microstructures and Reaction Interfaces on Composite Cathodes in All-Solid-State Batteries Using a Three-Dimensional Reconstruction Technique.

The composite cathode of an all-solid-state battery composed of various solid-state components requires a dense microstructure and a highly percolated solid-state interface different from that of a conventional liquid-electrolyte-based Li-ion battery. Indeed, the preparation of such a system is particularly challenging. In this study, quantitative analyses of composite cathodes by three-dimensional reconstruction analysis were performed beyond the existing qualitative analysis, and their microstructures and reaction interfaces were successfully analyzed. Interestingly, various quantitative values of structure properties (such as the volume ratio, connectivity, tortuosity, and pore formation) associated with material optimization and process development were predicted, and they were found to result in limited electrochemical charge/discharge performances. We also verified that the effective two-phase boundaries were significantly suppressed to ∼23% of the total volume because of component dispersion and packing issues.