Although sodium-ion batteries (SIBs) offer promising low-cost alternatives to lithium-ion batteries (LIBs), several challenges need to be overcome for their widespread adoption. A primary concern is the optimization of carbon anodes. Graphite, vital to the commercial viability of LIBs, has a limited capacity for sodium ions. Numerous alternatives to graphite are explored, particularly focusing on disordered carbons, including hard carbon. However, compared with graphite, most of these materials underperform in LIBs. Furthermore, the reaction mechanism between carbon and sodium ions remains ambiguous owing to the structural diversity of disordered carbon. A straightforward mechanical approach is introduced to enhance the sodium ion storage capacity of graphite, supported by comprehensive analytical techniques. Mechanically activated graphite delivers a notable reversible capacity of 290.5 mAh·g-1 at a current density of 10 mA·g-1. Moreover, it maintains a capacity of 157.7 mAh·g-1 even at a current density of 1 A·g-1, benefiting from the defect-rich structure achieved by mechanical activation. Soft X-ray analysis revealed that this defect-rich carbon employs a sodium-ion storage mechanism distinct from that of hard carbon. This leads to an unexpected reversible reaction on the solid electrolyte surface. These insights pave the way for innovative design approaches for carbon electrodes in SIB anodes.
Application of Si anodes is hindered by severe capacity fading due to pulverization of Si particles during the large volume changes of Si during charge/discharge and repeated formation of the solid-electrolyte interphase. To address these issues, considerable efforts have been devoted to the development of Si composites with conductive carbons (Si/C composites). However, Si/C composites with high C content inevitably show low volumetric capacity because of low electrode density. For practical applications, the volumetric capacity of a Si/C composite electrode is more important than gravimetric capacity, but volumetric capacity in pressed electrodes is rarely reported. Herein, a novel synthesis strategy is demonstrate for a compact Si nanoparticle/graphene microspherical assembly with interfacial stability and mechanical strength achieved by consecutively formed chemical bonds using 3-aminopropyltriethoxysilane and sucrose. The unpressed electrode (density: 0.71 g cm-3 ) shows a reversible specific capacity of 1470 mAh g-1 with a high initial coulombic efficiency of 83.7% at a current density of 1 C-rate. The corresponding pressed electrode (density: 1.32 g cm-3 ) exhibits high reversible volumetric capacity of 1405 mAh cm-3 and gravimetric capacity of 1520 mAh g-1 with a high initial coulombic efficiency of 80.4% and excellent cycling stability of 83% over 100 cycles at 1 C-rate.
Oxygen evolution reaction (OER) under acidic conditions becomes of significant importance for the practical use of a proton exchange membrane (PEM) water electrolyzer. In particular, maximizing the mass activity of iridium (Ir) is one of the maiden issues. Herein, the authors discover that the Ir-doped calcium copper titanate (CaCu3Ti4O12, CCTO) perovskite exhibits ultrahigh mass activity up to 1000 A gIr -1 for the acidic OER, which is 66 times higher than that of the benchmark catalyst, IrO2 . By substituting Ti with Ir in CCTO, metal-oxygen (M-O) covalency can be significantly increased leading to the reduced energy barrier for charge transfer. Further, highly polarizable CCTO perovskite referred to as "colossal dielectric", possesses low defect formation energy for oxygen vacancy inducing a high number of oxygen vacancies in Ir-doped CCTO (Ir-CCTO). Electron transfer occurs from the oxygen vacancies and Ti to the substituted Ir consequentially resulting in the electron-rich Ir and -deficient Ti sites. Thus, favorable adsorptions of oxygen intermediates can take place at Ti sites while the Ir ensures efficient charge supplies during OER, taking a top position of the volcano plot. Simultaneously, the introduced Ir dopants form nanoclusters at the surface of Ir-CCTO, which can boost catalytic activity for the acidic OER.
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.
It is challenging to develop alloying anodes with ultrafast charging and large energy storage using bulk anode materials because of the difficulty of carrier-ion diffusion and fragmentation of the active electrode material. Herein, a rational strategy is reported to design bulk Bi anodes for Na-ion batteries that feature ultrafast charging, long cyclability, and large energy storage without using expensive nanomaterials and surface modifications. It is found that bulk Bi particles gradually transform into a porous nanostructure during cycling in a glyme-based electrolyte, whereas the resultant structure stores Na ions by forming phases with high Na diffusivity. These features allow the anodes to exhibit unprecedented electrochemical properties; the developed Na-Bi half-cell delivers 379 mA h g-1 (97% of that measured at 1C) at 7.7 A g-1 (20C) during 3500 cycles. It also retained 94% and 93% of the capacity measured at 1C even at extremely fast-charging rates of 80C and 100C, respectively. The structural origins of the measured properties are verified by experiments and first-principles calculations. The findings of this study not only broaden understanding of the underlying mechanisms of fast-charging anodes, but also provide basic guidelines for searching battery anodes that simultaneously exhibit high capacities, fast kinetics, and long cycling stabilities.
Metastable phases-kinetically favoured structures-are ubiquitous in nature1,2. Rather than forming thermodynamically stable ground-state structures, crystals grown from high-energy precursors often initially adopt metastable structures depending on the initial conditions, such as temperature, pressure or crystal size1,3,4. As the crystals grow further, they typically undergo a series of transformations from metastable phases to lower-energy and ultimately energetically stable phases1,3,4. Metastable phases sometimes exhibit superior physicochemical properties and, hence, the discovery and synthesis of new metastable phases are promising avenues for innovations in materials science1,5. However, the search for metastable materials has mainly been heuristic, performed on the basis of experiences, intuition or even speculative predictions, namely 'rules of thumb'. This limitation necessitates the advent of a new paradigm to discover new metastable phases based on rational design. Such a design rule is embodied in the discovery of a metastable hexagonal close-packed (hcp) palladium hydride (PdHx) synthesized in a liquid cell transmission electron microscope. The metastable hcp structure is stabilized through a unique interplay between the precursor concentrations in the solution: a sufficient supply of hydrogen (H) favours the hcp structure on the subnanometre scale, and an insufficient supply of Pd inhibits further growth and subsequent transition towards the thermodynamically stable face-centred cubic structure. These findings provide thermodynamic insights into metastability engineering strategies that can be deployed to discover new metastable phases.
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.
We propose a promising electrochemical analysis tool based on the distribution of relaxation times (DRT) to quantify interfacial resistances towards a comprehensive understanding of complex solid-state interfacial phenomena in sulfide-based all-solid-state batteries (ASSBs). Using DRT-assisted impedance analysis, we identify a new resistance component in the range of 102-103 Hz of 3.5 and 0.9 Ω in the absence and presence of a LiNbO3 layer, respectively, at 1C-rate. Experimental and computational studies confirm that this interfacial resistance results from lithium depletion in sulfide solid electrolytes. Furthermore, we expect our approach to provide new insights into complex interfacial phenomena in ASSBs.
The design of atomically dispersed single atom catalysts (SACs) must consider high metal-atom loading amount, effective confinement, and strong interactions with matrix, which can maximize their catalytic performance. Here reported is a promising method to synthesize SACs on highly conductive multiwall carbon nanotube (MWCNT) supports using pulsed laser confinement (PLC) process in liquid. Atomic cobalt (Co) and phosphorus (P) with a high loading density are homogeneously incorporated on the outer wall of the MWCNT (Co-P SAC MWCNT). Density functional theory (DFT) calculations in combination with systematic control experiments found that the incorporated Co and P adatoms act as an adsorption energy optimizer and a charge transfer promoter, respectively. Hence, favorable kinetics and thermodynamics in Co-P SAC MWCNT can be simultaneously achieved for water oxidation resulting in a superior catalytic performance than the benchmark RuO2 catalyst. Crucially, total processing time for assembling Co-P SAC MWCNT via PLC process is less than 60 min, shedding light on the promising practical applications of our SAC design strategy.
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.
Stretchable energy storage devices are of great interest because of their potential applications in body-friendly, skin-like, wearable devices. However, stretchable batteries are very challenging to fabricate. The electrodes must have a degree of stretchability because the active materials occupy most of the volume, and the separator and packaging should also be stretchable. Here, an all-component stretchable lithium-ion battery was realized by leveraging the structural stretchability of re-entrant micro-honeycomb graphene-carbon nanotube (CNT)/active material composite electrodes and a physically cross-linked gel electrolyte, without using an inactive elastomeric substrate or matrix. Active materials interconnected via the entangled CNT and graphene sheets provided a mechanically stable porous network framework, and the inwardly protruding framework in the re-entrant honeycomb structure allowed for structural stretching during deformation. The composite network consisting solely of binder-free, highly conductive materials provided superior electron transfer, and vertically aligned microchannels enabled facile ion transport. Additionally, the physically cross-linked gel electrolyte increased the mechanical stability upon deformation of the electrodes and was effective as a stretchable separator. The resulting stretchable battery showed a high areal capacity of 5.05 mAh·cm-2, superior electrochemical performance up to 50% strain under repeated (up to 500) stretch-release cycles, and long-term stability of 95.7% after 100 cycles in air conditions.
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 â¼70% crystallized; subsequent RTA using an infrared lamp increases this crystallinity to â¼82% 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).
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.
The structural stability of cathode materials during electrochemical reactions, in particular, under high-rate discharge, is pertinent to the design and development of new electrode materials. This study investigates the structural inhomogeneity that develops within a single LiNi0.835 Co0.15 Al0.015 O2 (NCA83) particle during a fast discharging process under different cutoff voltages. Some of the NCA83 particles discharged from a high cutoff voltage (4.8â V) developed surface areas in which the layered structure was recovered, although the interiors retained the degraded spinel structure. These micro- and nano-scale structural inversions from high cutoff voltage seem highly correlated with structural evolutions in the initial charged state, and may ultimately degrade the cycling stability. This study advances understanding of the structural inhomogeneity within primary particles during various electrochemical processes and may facilitate the development of new Ni-rich cathode materials.
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.
In this study, we synthesize two layered and amorphous structures of germanium phosphide (GeP5) and compare their electrochemical performances to better understand the role of layered, crystalline structures and their ability to control large volume expansions. We compare the results obtained with those of previous, conventional viewpoints addressing the effectiveness of amorphous phases in traditional anodes (Si, Ge, and Sn) to hinder electrode pulverization. By means of both comprehensive experimental characterizations and density functional theory calculations, we demonstrate that layered, crystalline GeP5 in a hybrid structure with multiwalled carbon nanotubes exhibits exceptionally good transport of electrons and electrolyte ions and tolerance to extensive volume changes and provides abundant reaction sites relative to an amorphous structure, resulting in a superior solid-electrolyte interphase layer and unprecedented initial Coulombic efficiencies in both Li-ion and Na-ion batteries. Moreover, the hybrid delivers excellent rate-capability (symmetric and asymmetric) performance and remarkable reversible discharge capacities, even at high current rates, realizing ultradurable cycles in both applications. The findings of this investigation are expected to offer insights into the design and application of layered materials in various devices.
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, â¼0.04C) 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.
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 â¼40% 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 â¼100 times relative to that of the γ-phase, which is in agreement with the experiments.
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.
For the realization of sodium-ion batteries (SIBs), high-performance anode materials are urgently required with the advantages of being low-cost and environment-friendly. In this work, layered-type NaVO3 is prepared by the simple solid-state route with a rod-like morphology and used as an anode material for SIBs. The NaVO3 electrode exhibits a high specific capacity of 196 mA h g-1 during the first cycle and retains a capacity of 125 mA h g-1 at the 80th cycle with a high Coulombic efficiency of >99%, demonstrating high reversibility. The sodium diffusion coefficient in NaVO3 is measured using electrochemical impedance spectroscopy (1.368 × 10-15 cm2 s-1), the galvanostatic intermittent titration technique (1.15715 × 10-13 cm2 s-1), and cyclic voltammetry (2.7935 × 10-16 cm2 s-1). Furthermore, the reaction mechanism during the sodiation/desodiation process is investigated using in situ X-ray diffraction and X-ray absorption near the edge structure analysis, which suggests the formation of an amorphous-like phase and reversible redox reaction of V4+ â V5+, respectively.
