Insights into the Enhanced Cycle and Rate Performances of the F-Substituted P2-Type Oxide Cathodes f
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Liu, Kai↗
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Modulating the Surface Ligand Orientation for Stabilized Anionic Redox in Li‐Rich Oxide Cathodes
Abstract Anionic redox chemistry is emerging as a key concept in the development of high‐energy lithium‐ion batteries, as it enables a nearly doubled charge storage capacity, aiding the development of high‐capacity batteries. However, the anionic reactivity is frequently irreversible from charge to discharge, leading to rapid decay of the capacity and voltage of batteries over long‐term cycling. Although the possibility of controlling the anionic redox reactions by tuning the geometric and electronic structures has recently been proposed, the implementation of this strategy is still a critical challenge. Herein, a strategy is proposed to improve the anionic redox reversibility of a model anionic redox active cathode material, Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 , by tuning the surface ligand geometry via the growth of a lattice‐compatible spinel LiCoO 2 coating layer on the particle surface. Detailed local structure and first principles investigations reveal that the shape and orientation of the octahedral layer in the host lattice are modified. Accordingly, a two‐band oxygen redox behavior is triggered in the ligand‐orientation‐regulated Li‐rich cathode, leading to enhanced reversibility, and thus, remarkably improved capacity and voltage retention over cycling. This study highlights the importance of controllable ligand orientation, carving a new path for the development and design of Li‐rich cathodes in the future.
Liu, Yanchen↗
High-Entropy and Superstructure-Stabilized Layered Oxide Cathodes for Sodium-Ion Batteries
Layered transition metal oxides are appealing cathodes for sodium-ion batteries due to their overall advantages in energy density and cost. But their stabilities are usually compromised by the complicated phase transition and the oxygen redox, particularly when operating at high voltages, leading to poor structural stability and substantial capacity loss. Here, in this study, an integrated strategy combing the high-entropy design with the superlattice-stabilization to extend the cycle life and enhance the rate capability of layered cathodes is reported. It is shown that the as-prepared high-entropy Na 2/3 Li 1/6 Fe 1/6 Co 1/6 Ni 1/6 Mn 1/3 O 2 cathode enables a superlattice structure with Li/transition metal ordering and delivers excellent electrochemical performance that is not affected by the presence of phase transition and oxygen redox. It achieves a high reversible capacity (171.2 mAh g –1 at 0.1 C), a high energy density (531 Wh kg –1 ), extended cycling stability (89.3% capacity retention at 1 C for 90 cycles and 63.7% capacity retention at 5 C after 300 cycles), and excellent fast-charging capability (78 mAh g –1 at 10 C). This strategy would inspire more rational designs that can be leveraged to improve the reliability of layered cathodes for secondary-ion batteries.
25 ENERGY STORAGE↗
Effects of Calcination Conditions on the Structural and Electrochemical Behaviors of High‐Nickel, Cobalt‐Free LiNi 0.9 Mn 0.1 O 2 Cathode
Abstract Eliminating cobalt from high‐nickel layered oxide cathodes lowers the cost of lithium‐ion batteries for electric vehicles. However, cobalt‐free cathodes with high Mn 4+ and Ni 2+ contents are prone to Li/Ni mixing after synthesis, potentially compromising battery energy density, rate capability, and cycling stability. Without cobalt facilitating cation ordering in the layered structure, the degree of Li/Ni mixing in cobalt‐free cathodes depends heavily on the calcination conditions. In this study, a systematic exploration of calcination temperatures and LiOH ratio for LiNi 0.9 Mn 0.1 O 2 (NM‐90) provides detailed insights into the optimal synthesis conditions for high‐capacity cobalt‐free cathodes with extended cycle life. Surprisingly, high Li/Ni mixing does not necessarily lead to poor cycling stability whereas low Li/Ni mixing does not guarantee a long cycle life. More importantly, although excessive calcination temperature can further decrease Li/Ni mixing, it does not necessarily enhance capacity. Instead, the pernicious effects from the H2 → H3 phase transition are amplified due to a pronounced two‐phase reaction. An extensive suite of chemical and structural characterization methods uncovers a correlation between elevated calcination temperature, phase transformation, cation ordering, and capacity fading behavior: “overcooking” high‐nickel, cobalt‐free cathodes induce structural arrangement toward that of LiNiO 2 , with exacerbated lattice distortion and surface instability accelerating capacity fade.
Lee, Steven↗
Engineering Na‐Rich P2‐Type Layered Oxides Through Li/Ti Dual Doping for Oxygen Redox Activation and Superior Structural Stability
Sodium layered oxides Na x MO 2 (x ≤ 1 and M = transition metal ions) have gained significant interest as sodium-ion battery (NIB) cathodes owing to their high operating voltages and potential for higher energy density compared with polyanion and Prussian blue–type cathodes. However, their practical applications are often hindered by the irreversible structural transitions leading to capacity fading during cycling. The nature and substitution of transition metal ions define the material properties and electrochemical performance. In this study, through comprehensive electrochemical characterization combined with multi-scale structural and spectroscopical analyses, we demonstrate the synergistic impacts of Lithium and Titanium doping, which not only increases overall capacity by boosting cation and anion cooperative redox contributions but also improves the rate capability and cycling stability. Specifically, Li + doping enhances the available sodium inventory for extraction, while Ti 4+ disrupts Na + /vacancy ordering at lower voltages (< 4 V) and mitigates the detrimental P2→OP4/O2 phase transition during cycling. The combined effect of Lithium and Titanium doping promotes more charge localization on Oxygen, which activates reversible lattice oxygen redox reactions at elevated voltages, contributing additional capacity beyond conventional cationic redox. This work provides crucial insights into the design of high-performance, high-capacity P2-type layered cathode materials for sodium-ion batteries.
36 MATERIALS SCIENCE↗
Realizing Complete Solid-Solution Reaction in High Sodium Content P2-Type Cathode for High-Performance Sodium-Ion Batteries
P2-type layered oxides suffer from an ordered Na + /vacancy arrangement and P2→O2/OP4 phase transitions, leading them to exhibit multiple voltage plateaus upon Na + extraction/insertion. The deficient sodium in the P2-type cathode easily induces the bad structural stability at deep desodiation states and limited reversible capacity during Na + de/insertion. These drawbacks cause poor rate capability and fast capacity decay in most P2-type layered oxides. In this work, to address these challenges, a novel high sodium content (0.85) and plateau-free P2-type cathode-Na 0.85 Li 0.12 Ni 0.22 Mn 0.66 O 2 (P2-NLNMO) was developed. The complete solid-solution reaction over a wide voltage range ensures both fast Na + mobility (10 -11 to 10 -10 cm 2 s -1 ) and small volume variation (1.7%). Furthermore, the high sodium content P2-NLNMO exhibits a higher reversible capacity of 123.4 mAhg -1 , superior rate capability of 79.3 mAhg -1 at 20 C, and 85.4% capacity retention after 500 cycles at 5 C. The sufficient Na and complete solid-solution reaction are critical to realizing high-performance P2-type cathodes for sodium-ion batteries.
25 ENERGY STORAGE↗
Vacancy-Enabled O3 Phase Stabilization for Manganese-Rich Layered Sodium Cathodes
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99 GENERAL AND MISCELLANEOUS↗
Understanding the Effects of Bi Modification on the Properties of Ni-Rich Cathodes
With the skyrocketing market demands for energy storage, lithium ions batteries (LIB) with higher energy density are urgently needed. Cathodes play a critical role in determining the energy density of LIB, and the most popular one is Ni-rich cathode due to its high capacity. However, due to the fast structural degradation, Ni-rich cathode materials should be further modified to achieve higher stability. Herein, we introduce bismuth ions in LiNi 0.83 Co 0.11 Mn 0.06 O 2 cathodes by adding Bi 2 O 3 during sintering to optimize the specific capacity and cycle stability. By adding 0.1% mol Bi, the Li + diffusion and structural stability are effectively optimized, leading to improved electrochemical performances. Further, the modified sample delivers much higher specific capacity (222.9 mAhg -1 , 0.05 C) than unmodified sample (204 mAhg -1 , 0.05 C). Meanwhile, the specific capacity of optimized sample after 100 cycles at 0.33 C is 27.75 mAhg -1 higher than that of unmodified sample. Therefore, this work demonstrates that Bi modification can be regarded as a possible solution to optimizing the electrochemical performance of Ni-rich cathodes.
25 ENERGY STORAGE↗
Exposure History and its Effect Towards Stabilizing Li Exchange Across Disordered Rock Salt Interfaces
Abstract The application of lithium rich disordered rock salts (DRX) as cathode materials has greatly expanded the materials space for high energy density cathodes. These materials are able to consistently achieve capacities higher than via a complex percolation based intercalation mechanism. Most current DRX materials face significant capacity fade when cycled over an extended period. One of the factors responsible for this could be deleterious side effect of interface reactions between the electrode and electrolyte at high voltage. We aim to focus on one aspect of this interaction, i.e the effect of exposure to electrolyte on the surface and its effect on the electrochemical properties of (LMNOF) powder. LMNOF was systematically treated in an electrolyte solution for varying periods of time at an elevated temperature. Treated samples exhibit surface layer modification (removal of F rich surface layer), leading to a 10 % improvement in the capacity retention behavior of LMNOF. Surface and bulk based measurements indicate an increase in disorder and gradual removal of F and Li. All of these processes mimic an aging process similar to cycling. This a priori formed interface allows for increased stability with respect to retention of capacity and oxygen loss.
Satish, Rohit↗
A Dendrite-Resistant Sodium/Porous-Carbon Anode for Solid-State Batteries – Strategies and Challenges for Low-Pressure Operation
Sodium solid-state batteries (Na-SSB) have gained interest recently due to the abundance of Na over Li, but they still tend to fail due to dendrites under practical current densities and cycling capacities. To overcome this, Na-SSBs are frequently tested with impractically high applied pressure. In this work, a porous carbon interfacial layer is utilized in conjunction with Na-ß”-Al2O3 solid electrolytes to enable Na-cycling at milder cell pressures. This sodium/porous carbon layer enables improved solid-state Na cycling in symmetric cells, up to a current density of 10 mA cm-2 at 25 °C. Cycling up to 1 mAh cm-2 is challenging with low pressure, but 1 mAh cm-2 capacity can be reliably cycled at 1 mA cm-2 at an elevated temperature of 60 °C in symmetric cells. Finally, the evolution of the interface and sodium/carbon anode is evaluated with cryogenic ion-milling and cross-sectional imaging revealing that, depending on testing temperature, pressure, current density, and capacity, void formation, Na-extraction from porous carbon, delamination of the porous carbon matrix, or a combination of these occurs at the interface between Na-metal and BASE. Despite this, excellent dendrite resistance is achieved, and a full-cell design utilizing a Na-transition metal oxide cathode is still able to achieve an areal capacity of ~ 2.7 mAh cm-2 at 0.125 mA cm-2. This work demonstrates an alternative pathway toward a Na-metal anode for Na-SSBs without the requirement of excessive stack pressure.
low-cost↗
Adsorption of methylene blue by bismuth impregnated biochar of different biomass materials: pore structure and surface chemistry characteristics
Abstract In this study, three different types of biochar (biomass materials were beech wood, corncob, and bamboo) were loaded with bismuth to form bismuth impregnated biochars (named respectively as Bi@WBC, Bi@CBC, and Bi@BBC) to investigate their properties (pore structure and surface chemistry characteristics) on methylene blue (MB) removal capacities. Three bismuth impregnated biochars made from different biomass materials were ranked for their adsorption capacity of MB as follows: Bi@WBC > Bi@CBC > Bi@BBC, in which Bi@WBC showed the largest Langmuir adsorption capacity of 178.59 mg g −1 . While the specific surface area (SSA) and pore volume of Bi@WBC were the largest (accounting for 477.74 m 2 g −1 and 0.15 cm 3 g −1 , respectively), according to the FTIR and XPS results, Bi@WBC (72.3%) exhibited a higher proportion of BiO bonds than the Bi@CBC (52.3%) and Bi@BBC (48.4%) did. Conclusively, the rich porous structure and surface functional groups of Bi@WBC affected the adsorption capacity of MB, and the chemical adsorption provided the main contribution. © 2022 Society of Chemical Industry (SCI).
Li, Peiyi↗
Water-Pillared Sodium Vanadium Bronze Nanowires for Enhanced Rechargeable Magnesium Ion Storage
Owing to the advantages of high safety, low cost, high theoretical volumetric capacities, and environmental friendliness, magnesium-ion batteries (MIBs) have more feasibility for large-scale energy storage compared to lithium-ion batteries. However, lack of suitable cathode materials due to sluggish kinetics of magnesium ion is one of the biggest challenges. Herein, water-pillared sodium vanadium bronze nanowires (Na 2 V 6 O 16 ·1.63H 2 O) are reported as cathode material for MIBs, which display high performance in magnesium storage. The hydrated sodium ions provide excellent structural stability. The charge shielding effect of lattice water enables fast Mg 2+ diffusion. It exhibits high specific capacity of 175 mAh g -1 , long cycle life (450 cycles), and high coulombic efficiency (≈100%). At high current density of 200 mA g -1 , the capacity retention is up to 71% even after 450 cycles (compared to the highest capacity), demonstrating excellent long-term cycling performance. The nature of charge storage kinetics is explored. Furthermore, a highly reversible structure change during the electrochemical process is proved by comprehensive electrochemical analysis. The remarkable electrochemical performance makes Na 2 V 6 O 16 ·1.63H 2 O a promising cathode material for low-cost and safe MIBs.
36 MATERIALS SCIENCE↗
High Interfacial-Energy and Lithiophilic Janus Interphase Enables Stable Lithium Metal Anodes
The stability of solid electrolyte interphase (SEI) layers is critical for developing lithium (Li) metal batteries. However, the fabrication of stable SEI layers is plagued by un-controlled structures, properties, and functions. In this work a controllable design of an ordered LiF-rich and lithiophilic hybrid Janus interphase (LiF-HJI) is reported using organic fluorination reagent as a functional SEI precursor. The LiF-HJI with a lower crystalline LiF layer and an upper Li organosulfide layer provides high interfacial energy with the Li metal and strong Li-ion affinity, allows homogenous Li-ion distribution, fast and uniform Li-ion transport, and excellent mechanical and passivation properties, enabling stable Li metal anodes under harsh conditions, such as high deposition capacities (6 mA h cm -2 ), current densities (10 mA cm -2 ), and rates (5 C). Stable LiF-HJI@Li greatly improves cycling stability and capacity retention (80.1% after 300 cycles) of Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 cells at a commercial-level areal capacity (≈4.2 mA h cm -2 ). Even under a lean-electrolyte condition of 3 g Ah -1 , 80% capacity retention can be maintained after 100 cycles, demonstrating excellent cycling performance under such harsh conditions.
25 ENERGY STORAGE↗
Anionic‐Based Layered Oxide Cathodes with High Electrochemical Performance through Dual‐Site Substitutions for Sodium‐Ion Batteries
Mn-rich layered oxide cathodes with anionic redox promise high energy density for sodium-ion batteries (SIBs) due to ultra-high capacity derived from both Mn and O redox couples. Nevertheless, instability of the reactions that lead to poor electrochemical stability hinders the cathodes from practical applications. Here, the Al and Zn dual-site substitution strategy is proposed to enhance electrochemical performance. Here, the designed cathode, Na 0.73 Zn 0.03 Li 0.25 Mn 0.76 Al 0.01 O 2 (AlZn), delivers a high discharge capacity of 242 mAh g −1 with an impressive rate capability (162 mAh g −1 at 1000 mA g −1 ) and excellent capacity retention (89.69% over 150 cycles). In addition, full-cell SIB based on AlZn coupled with hard carbon exhibits a high energy density of 317 Wh kg −1 (based on both cathode and anode mass) and a reasonable capacity retention of 80.8% after 250 cycles. Revealed by advanced investigations, the synergy of robust Al–O in TM layers and O–Zn–O pillars in Na layers helps alleviate severe inactive spinel/rock-salt phase transformation and intragranular cracks in the AlZn cathode. This consequently leads to greatly enhanced electrochemical performance over the pristine cathode. This work provides insight into improving electrochemical properties of anionic-redox-based layered oxides by Al/Zn co-substitutions toward high-energy SIBs.
25 ENERGY STORAGE↗
Toward MBenes Battery Electrode Materials: Layered Molybdenum Borides for Li-Ion Batteries
Lithium-ion and sodium-ion batteries (LIBs and SIBs) are crucial in our shift toward sustainable technologies. In this work, the potential of layered boride materials (MoAlB and Mo 2 AlB 2 ) as novel, high-performance electrode materials for LIBs and SIBs, is explored. It is discovered that Mo 2 AlB 2 shows a higher specific capacity than MoAlB when used as an electrode material for LIBs, with a specific capacity of 593 mAh g -1 achieved after 500 cycles at 200 mA g -1 . It is also found that surface redox reactions are responsible for Li storage in Mo 2 AlB 2 , instead of intercalation or conversion. Moreover, the sodium hydroxide treatment of MoAlB leads to a porous morphology and higher specific capacities exceeding that of pristine MoAlB. When tested in SIBs, Mo 2 AlB 2 exhibits a specific capacity of 150 mAh g -1 at 20 mA g -1 . These findings suggest that layered borides have potential as electrode materials for both LIBs and SIBs, and highlight the importance of surface redox reactions in Li storage mechanisms.
25 ENERGY STORAGE↗
Enhancing the Reaction Kinetics and Stability of Co‐Free Li‐Rich Cathode Materials via a Multifunctional Strategy
Co-free Li-rich layered oxides (CFLLOs) with anionic redox activity are among the most promising cathode materials for high-energy-density and low-cost lithium-ion batteries (LIBs). However, irreversible oxygen release often causes severe structural deterioration, electrolyte decomposition, and the formation of unstable cathode-electrolyte interface (CEI) film with high impedance. Additionally, the elimination of cobalt elements further deteriorates the reaction kinetics, leading to reduced capacity and poor rate performance. Here, in this study, a multifunctional strategy is proposed, incorporating Li 2 MnO 3 phase content regulation, micro-nano structure design, and heteroatom substitution. The increased content of Li 2 MnO 3 phase enhances the capacity through oxygen redox. The smaller nanoscale primary particles induce greater tensile strain and introduce more grain boundaries, thereby improving the reaction kinetics and reactivity, while the larger micron-sized secondary particles help to reduce interfacial side reactions. Furthermore, Na⁺ doping modulates the local coordination environment of oxygen, stabilizing both the anion framework and the crystal structure. As a result, the designed cathode exhibits enhanced rate performance, delivering a capacity of 158 mAh g⁻¹ at 5.0 C and improved cyclic stability, with a high capacity retention of 99% after 400 cycles at 1.0 C. This multifunctional strategy holds great promise for advancing the practical application of CFLLOs in next-generation LIBs.
Co-free Li-rich layered oxide↗
Tuning working potential of silicon-phosphorus anode via microstructure control for high-energy lithium-ion batteries
The primary research on anode materials of lithium-ion batteries have been focused on increasing the specific capacity, while the working potential that is also closely related to the practical energy density of batteries has been paid much less attention. In this paper, starting from micrometer-sized silicon and black phosphorus, we have reported a high-energy silicon-phosphorus/carbon anode (denoted as mSPC) via a high-energy ball milling process, which demonstrates an average discharge working potential of 0.3 volts versus lithium, together with a high reversible capacity of > 2000 mAh/g, high initial coulombic efficiency of 84%, excellent cycle stability, and superior rate capability up to 15 A/g. Furthermore, in situ focused-ion-beam scanning electron microscopy reveals that the volume change of the mSPC anode during repeated (de) lithiation is effectively alleviated. In contrast, starting from nanometer-sized silicon, the resulted anode (denoted as nSPC) not only presents a lower reversible capacity (~1200 mAh/g), but also exhibits a higher charge/discharge working potential, leading to reduced energy density. Our results indicate the importance of composition/structure control in tailoring the working potential and specific capacity of alloying-type anodes towards high-energy lithium-ion batteries.
25 ENERGY STORAGE↗
Potential impacts of climate change on wind and solar electricity generation in Texas
Wind and solar energy sources are climate and weather dependent, therefore susceptible to a changing climate. in this paper, we quantify the impacts of climate change on wind and solar electricity generation under high concentrations of greenhouse gases in Texas. We employ mid-twenty-first century climate projections and a high-resolution numerical weather prediction model to generate weather variables in the future and produce wind and solar generation time series. We find that mid-twenty-first century projections based on five global climate models agree on the multiyear average increases across Texas in direct normal irradiance, global horizontal irradiance, surface air temperature, and 100-m wind speed of up to 5%, 4%, 10%, and 1%, respectively. These changes lead to multiyear average relative changes across Texas of -0.6 to + 2.5% and of + 1.3 to + 3.5% in solar and wind capacity factors, respectively, with significant regional, seasonal, and diurnal differences. Areas with low solar resource show an increase in solar capacity factors but reductions in wind capacity factors. Areas with high solar resource show reductions in solar capacity factors. The spatial and temporal differences in our results highlight the importance of using high-resolution data sets to study the potential impacts of climate change on wind and solar power.
14 SOLAR ENERGY↗