Occurrence of anionic redox with absence of full oxidation to Ru^(5+) in high-energy P2-type layered oxide cathode

The anionic redox has been widely studied in layered-oxide-cathodes in attempts to achieve highenergy-density for Na-ion batteries(NIBs).It is known that an oxidation state of Mn^(4+) or Ru^(5+) is essential for the anionic reaction of O^(2-)/O~-to occur during Na^(+) de/intercalation.However,here,we report that the anionic redox can occur in Ru-based layered-oxide-cathodes before full oxidation of Ru^(4+)/Ru^(5+).Combining studies using first-principles calculation and experimental techniques reveals that further Na^(+) deintercalation from P2-Na_(0.33)[Mg_(0.33)Ru_(0.67)]O_(2) is based on anionic oxidation after 0.33 mol Na^(+) deintercalation from P2-Na_(0.67)[Mg_(0.33)Ru_(0.67)]O_(2) with cationic oxidation of Ru^(4+)/Ru^(4.5+).Especially,it is revealed that the only oxygen neighboring 2Mg/1 Ru can participate in the anionic redox during Na^(+) de/intercalation,which implies that the Na-O-Mg arrangement in the P2-Na_(0.33)[M9_(0.33)Ru_(0.67)]O_(2) structure can dramatically lower the thermodynamic stability of the anionic redox than that of cationic redox.Through the O anionic and Ru cationic reaction,P2-Na_(0.67)[Mg_(0.33)Ru_(0.67)]O_(2) exhibits not only a large specific capacity of~172 mA h g^(-1) but also excellent power-capability via facile Na^(+) diffusion and reversible structural change during charge/discharge.These findings suggest a novel strategy that can increase the activity of anionic redox by modulating the local environment around oxygen to develop high-energy-density cathode materials for NIBs.

Unexpected Li displacement and suppressed phase transition enabling highly stabilized oxygen redox in P3-type Na layered oxide cathode

Oxygen redox is considered a new paradigm for increasing the practical capacity and energy density of the layered oxide cathodes for Na-ion batteries. However, severe local structural changes and phase transitions during anionic redox reactions lead to poor electrochemical performance with sluggish kinetics.Here, we propose a synergy of Li-Cu cations in harnessing the full potential of oxygen redox, through Li displacement and suppressed phase transition in P3-type layered oxide cathode. P3-type Na_(0.7)[Li_(0.1)Cu_(0.2)Mn_(0.7)]O_(2) cathode delivers a large specific capacity of ~212 mA h g^(-1)at 15 mA g^(-1). The discharge capacity is maintained up to ~90% of the initial capacity after 100 cycles, with stable occurrence of the oxygen redox in the high-voltage region. Through advanced experimental analyses and first-principles calculations, it is confirmed that a stepwise redox reaction based on Cu and O ions occurs for the charge-compensation mechanism upon charging. Based on a concrete understanding of the reaction mechanism, the Li displacement by the synergy of Li-Cu cations plays a crucial role in suppressing the structural change of the P3-type layered material under the oxygen redox reaction, and it is expected to be an effective strategy for stabilizing the oxygen redox in the layered oxides of Na-ion batteries.

Multidimensional Hybrid Architecture Encapsulating Cobalt Oxide Nanoparticles into Carbon Nanotube Branched Nitrogen-Doped Reduced Graphene Oxide Networks for Lithium–Sulfur Batteries

Lithium–sulfur batteries(LSBs)are regarded as promising candidates for the next-generation energy storage devices owing to their high-theoretical capacity(1675 mAh g^(−1))and affordable cost.However,several limitations of LSBs such as the lithium polysulfide shuttle,large volume expansion,and low electrical conductivity of sulfur need to be resolved for practical applications.To address these limitations,herein,a multidimensional architectured hybrid(Co@CNT/nG),where Co_(3)O_(4) nanoparticles are encapsulated into threedimensional(3D)porous N-doped reduced graphene oxide interconnected with carbon nanotube(CNT)branches,is synthesized through a simple pyrolysis method.The synergistic effect achieved through the homogeneously distributed and encapsulated Co_(3)O_(4) nanoparticles,the interconnected CNT branches,and the 3D hierarchical porous structure and N-doping of Co@CNT/nG significantly suppresses the shuttle effect of lithium polysulfides and enhances the conversion redox kinetics for the improved sulfur utilization.We validate this effect through various measurements including symmetric cells,Li_(2)S nucleation,shuttle currents,Tafel slopes,diffusion coefficients,and post-mortem analyses.Importantly,Co@CNT/nG-70S-based LSB cells achieve a high-specific capacity of 1193.1 mAh g^(−1) at 0.1 C and a low capacity decay rate of 0.030%per cycle for 700 cycles at 5 C,delivering a high areal capacity of 5.62 mAh cm^(−2) even with a loading of 6.5 mg cm^(−2).

Structural and electrochemical stabilization enabling high-energy P3-type Cr-based layered oxide cathode for K-ion batteries

Layered-type transition metal(TM)oxides are considered as one of the most promising cathodes for K-ion batteries because of the large theoretical gravimetric capacity by low molar mass.However,they suffer from severe structural change by de/intercalation and diffusion of K^(+)ions with large ionic size,which results in not only much lower reversible capacity than the theoretical capacity but also poor power capability.Thus,it is important to enhance the structural stability of the layered-type TM oxides for outstanding electrochemical behaviors under the K-ion battery system.Herein,it is investigated that the substitution of the appropriate Ti^(4+)contents enables a highly enlarged reversible capacity of P3-type KxCrO_(2) using combined studies of first-principles calculation and various experiments.Whereas the pristine P3-type KxCrO_(2) just exhibits the reversible capacity of∼120 mAh g^(−1) in the voltage range of 1.5-4.0 V(vs.K^(+)/K),the∼0.61 mol K^(+)corresponding to∼150 mAh g^(−1) can be reversible de/intercalated at the structure of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) under the same conditions.Furthermore,even at the high current density of 788 mA g^(−1),the specific capacity of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) is∼120 mAh g^(−1),which is∼81 times larger than that of the pristine P3-type KxCrO_(2).It is believed that this research can provide an effective strategy to improve the electrochemical performances of the cathode materials suffered by severe structural change that occurred during charge/discharge under not only K-ion battery system but also other rechargeable battery systems.

Numerical analysis of clamping pressure during carton clamp handling of heavyweight corrugated packages

In order to determine the theoretical minimum clamping pressure required in carton clamp handling of heavyweight corrugated package(HCP)such as large packages or unitized agricultural product packages,a numerical model of clamping pressure was developed.To develop the model,the dynamic load factor was measured at the handling test course which was designed on the basis of actual handling environment of the target HCP.Also,the static-frictional coefficients between the HCPs and between the HCP and a rubber contact pad of carton clamp arm were analyzed.The main factors in the developed numerical model of clamping pressure were the handling load weight and the effective contact area of the carton clamp arm.In addition,field tests were performed to validate the theoretical minimum clamping pressure calculated from the model.Averaged slip distance from the single package and two packages handling was estimated as a 3.2 mm through field test,and it is expected that the 3.2 mm slip distance will be acceptable for a safe operation in the handling environment.The suggested analytical approach with the numerical model can be a useful means for estimating the clamping pressure of the carton clamps used to handle the HCP.