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.

Association Between Pain Catastrophizing and Central Sensitization Among Patients With Severe Knee Osteoarthritis Awaiting Primary Total Knee Arthroplasty.

Total knee arthroplasty (TKA) is among the most successful types of surgery for the treatment of knee osteoarthritis (OA). However, nearly 20% of patients report unexpected pain after surgery. Recently, some studies have proposed that pain after TKA is related to pain catastrophizing (PC) and central sensitization (CS). However, there is no study comparing PC and CS for the same patient with knee OA requiring TKA. Thus, the goal of this study was to confirm the association between PC and CS among patients with knee OA awaiting primary TKA. This study was conducted with the clinical data of 153 patients collected between July 2019 and February 2021. Both PC and CS were evaluated with the Pain Catastrophizing Scale (PCS) and the Central Sensitizing Inventory (CSI). Patients with PCS scores higher than 30 were classified as high-level catastrophizing. Patients with CSI scores higher than 40 were classified as central sensitized. The distribution of PC and CS levels was confirmed, and the correlation between PC and CS was analyzed. A significant correlation was found between PCS and CSI scores, with Pearson's correlation coefficient of 0.606. Participants with high-level catastrophizing were 2.07 times more likely to belong to the central sensitized group compared with those who did not show high-level catastrophizing. Participants in the central sensitized group were 3.02 times more likely to belong to the high-level catastrophizing group than those who were not central sensitized. In conclusion, many patients with knee OA awaiting primary TKA had high-level catastrophizing, and a significant association was found between PC and CS. [Orthopedics. 2022;45(4):197-202.].

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.

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.

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.

A 4†V Li-Ion Battery using All-Spinel-Based Electrodes.

Boosting the performance of rechargeable lithium-ion batteries (LIBs) beyond the state-of-the-art is mandatory toward meeting the future energy requirements of the consumer mass market. The replacement of conventional graphite anodes with conversion-type metal-oxide anodes is one progressive approach toward achieving this goal. Here, a LIB consisting of a highcapacity spinel NiMn2 O4 anode and a high-voltage spinel LiNi0.5 Mn1.5 O4 cathode was proposed. Polyhedral-shaped NiMn2 O4 powder was prepared from a citrate precursor via the sol-gel method. Electrochemical tests showed that the NiMn2 O4 in a half-cell configuration could deliver reversible capacities of 750 and 303 mAh g-1 at 0.1 and 3 C rates. Integrating the NiMn2 O4 anode into a full-cell configuration provided an estimated energy density of 506 Wh kg-1 (vs. cathode mass) upon 100 cycles and excellent cycling performance over 150 cycles at the 0.1 C rate, which can be considered promising in terms of satisfying the demands for high energy densities in large-scale applications.

Self-Rearrangement of Silicon Nanoparticles Embedded in Micro-Carbon Sphere Framework for High-Energy and Long-Life Lithium-Ion Batteries.

Despite its highest theoretical capacity, the practical applications of the silicon anode are still limited by severe capacity fading, which is due to pulverization of the Si particles through volume change during charge and discharge. In this study, silicon nanoparticles are embedded in micron-sized porous carbon spheres (Si-MCS) via a facile hydrothermal process in order to provide a stiff carbon framework that functions as a cage to hold the pulverized silicon pieces. The carbon framework subsequently allows these silicon pieces to rearrange themselves in restricted domains within the sphere. Unlike current carbon coating methods, the Si-MCS electrode is immune to delamination. Hence, it demonstrates unprecedented excellent cyclability (capacity retention: 93.5% after 500 cycles at 0.8 A g-1), high rate capability (with a specific capacity of 880 mAh g-1 at the high discharge current density of 40 A g-1), and high volumetric capacity (814.8 mAh cm-3) on account of increased tap density. The lithium-ion battery using the new Si-MCS anode and commercial LiNi0.6Co0.2Mn0.2O2 cathode shows a high specific energy density above 300 Wh kg-1, which is considerably higher than that of commercial graphite anodes.

Study on the Electrochemical Reaction Mechanism of NiFe2O4 as a High-Performance Anode for Li-Ion Batteries.

Nickel ferrite (NiFe2O4) has been previously shown to have a promising electrochemical performance for lithium-ion batteries (LIBs) as an anode material. However, associated electrochemical processes, along with structural changes, during conversion reactions are hardly studied. Nanocrystalline NiFe2O4 was synthesized with the aid of a simple citric acid assisted sol-gel method and tested as a negative electrode for LIBs. After 100 cycles at a constant current density of 0.5 A g-1 (about a 0.5 C-rate), the synthesized NiFe2O4 electrode provided a stable reversible capacity of 786 mAh g-1 with a capacity retention greater than 85%. The NiFe2O4 electrode achieved a specific capacity of 365 mAh g-1 when cycled at a current density of 10 A g-1 (about a 10 C-rate). At such a high current density, this is an outstanding capacity for NiFe2O4 nanoparticles as an anode. Ex-situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) were employed at different potential states during the cell operation to elucidate the conversion process of a NiFe2O4 anode and the capacity contribution from either Ni or Fe. Investigation reveals that the lithium extraction reaction does not fully agree with the previously reported one and is found to be a hindered oxidation of metallic nickel to nickel oxide in the applied potential window. Our findings suggest that iron is participating in an electrochemical reaction with full reversibility and forms iron oxide in the fully charged state, while nickel is found to be the cause of partial irreversible capacity where it exists in both metallic nickel and nickel oxide phases.

Coating lithium titanate with nitrogen-doped carbon by simple refluxing for high-power lithium-ion batteries.

Nitrogen-doped carbon is coated on lithium titanate (Li4Ti5O12, LTO) via a simple chemical refluxing process, using ethylenediamine (EDA) as the carbon and nitrogen source. The process incorporates a carbon coating doped with a relatively high amount of nitrogen to form a conducting network on the LTO matrix. The introduction of N dopants in the carbon matrix leads to a higher density of C vacancies, resulting in improved lithium-ion diffusion. The uniform coating of nitrogen-doped carbon on Li4Ti5O12 (CN-LTO) enhances the electronic conductivity of a CN-LTO electrode and the corresponding electrochemical properties of the cell employing the electrode. The results of our study demonstrate that the CN-LTO anode exhibits higher rate capability and cycling performance over 100 cycles. From the electrochemical tests performed, the specific capacity of CN-LTO electrode at higher rates of 20 and 50 C are found to be 140.7 and 82.3 mAh g(-1), respectively. In addition, the CN-Li4Ti5O12 anode attained higher capacity retention of 100% at 1 C rate after 100 cycles and 92.9% at 10 C rate after 300 cycles.