Graphene effectively activating "dead" water molecules between manganese dioxide layers in potassium-ion battery

Aqueous potassium-ion batteries(APIBs),recognized as safe and reliable new energy devices,are considered as one of the alternatives to traditional batteries.Layered MnO_(2),serving as the main cathode,exhibits a lower specific capacity in aqueous electrolytes compared to organic systems and operates through a different reaction mechanism.The application of highly conductive graphene may effectively enhance the capacity of APIBs but could complicate the potassium storage environment.In this study,a MnO_(2) cathode pre-intercalated with K~+ions and grown on graphene(KMO@rGO) was developed using the microwave hydrothermal method for APIBs.KMO@rGO achieved a specific capacity of 90 mA h g^(-1) at a current density of 0.1 A g^(-1),maintaining a capacity retention rate of>90% after 5000 cycles at 5 A g^(-1).In-situ and exsitu characterization techniques revealed the energy-storage mechanism of KMO@rGO:layered MnO_(2)traps a large amount of "dead" water molecules during K~+ions removal.However,the introduction of graphene enables these water molecules to escape during K~+ ions insertion at the cathode.The galvanostatic intermittent titration technique and density functional theory confirmed that KMO@rGO has a higher K~+ions migration rate than MnO_(2).Therefore,the capacity of this cathode depends on the interaction between dead water and K~+ions during the energy-storage reaction.The optimal structural alignment between layered MnO_(2) and graphene allows electrons to easily flow into the external circuit.Rapid charge compensation forces numerous low-solvent K~+ions to displace interlayer dead water,enhancing the capacity.This unique reaction mechanism is unprecedented in other aqueous battery studies.

Effect of nano-oxide layers on the magnetoresistance of ultrathin permalloy films

Ta/NiFe/Ta ultrathin films with and without nano-oxide layers （NOLs） were prepared by magnetron sputtering followed by a vacuum annealing process. The influence of NOLs on the magnetoresistance （MR） ratio of ultrathin permalloy films was studied. The results show that the influence of grain size and textures on the MR ratio becomes weak when the thickness of the NiFe layer is below 15 nm. A higher MR ratio was observed for the thinner （〈 15 nm） NiFe film with NOLs. The MR ratio of a 10 nm NiFe film can be remarkably enhanced by NOLs. The enhanced MR ratio for these ultrathin films can be attributed to the enhanced specular reflection of conduction electrons.

Chemical dissolution resistance of anodic oxide layers formed on aluminum

Chemically resistant anodic oxide layers were formed on pure aluminum substrates in oxalic acid-sulphuric acid bath.Acid dissolution tests of the obtained anodic layers were achieved in accordance with the ASTM B 680-80 specifications：35mL/L 85% H3PO4＋20g/L CrO3 at 38℃.Influence of oxalic acid concentration,bath temperature and anodic current density on dissolution rate and coating ratio was examined,when the sulphuric acid concentration was maintained at 160g/L.It was found that chemically resistant and compact oxide layers were produced under low operational temperature （5℃） and high current densities （3A/dm^2）.A beneficial effect was observed concerning the addition of oxalic acid （18g/L）.The morphology and the composition of the anodic oxide layer were examined by scanning electron microscopy （SEM）,atomic force microscopy （AFM） and glow-discharge optical emission spectroscopy （GDOES）.

A novel high performance TFS SJ IGBT with a buried oxide layer

A novel high performance trench field stop （TFS） superjunction （S J） insulated gate bipolar transistor （IGBT） with a buried oxide （BO） layer is proposed in this paper. The BO layer inserted between the P-base and the SJ drift region acts as a barrier layer for the hole-carrier in the drift region. Therefore, conduction modulation in the emitter side of the SJ drift region is enhanced significantly and the carrier distribution in the drift region is optimized for the proposed structure. As a result, compared with the conventional TFS SJ IGBT （Conv-SJ）, the proposed BO-SJ IGBT structure possesses a drastically reduced on-state voltage drop （gce（on）） and an improved tradeoff between gee（on） and turn-off loss （Eoff）, with no breakdown voltage （BV） degraded. The results show that with the spacing between the gate and the BO layer Wo = 0.2 μm, the thickness of the BO layer Lo = 0.2 μm, the thickness of the drift region Ld = 90 μm, the half width and doping concentration of the N- and P-pillars Wn = Wp = 2.5μm and Nn = Np = 3 × 10^15 cm^-3, the Vce（on） and Eoff of the proposed structure are 1.08 V and 2.81 mJ/cm2 with the collector doping concentration Nc = 1 × 10^18 cm^-3 and 1.12 V and 1.73 mJ/cm2 with Nc = 5 × 10^17 cm^-3, respectively. However, with the same device parameters, the Vce（on） and Eoff for the Conv-SJ are 1.81 V and 2.88 mJ/cm2 with Nc= 1 × 10^18 cm^-3 and 1.98 V and 2.82 mJ/cm2 with Nc = 5 ×10^17 cm^-3, respectively. Meanwhile, the BV of the proposed structure and Conv-SJ are 1414 V and 1413 V, respectively.

EFFECT OF OXIDE LAYER THICKNESS OVER Al AND Al ALLOY POWDERS ON QUALITY OF THEIR EXPLOSIVE COMPACTS

Observations of microstructure of explosive compacts made of Al or Al-Li alloy powders by atomization with water,nitrogen or ultrasoic Ar gas were carried out under optical and scanning electron microscopes.The rsults indicate that super quality explosive compact can only be obtained by powders of which the thickness of the oxide layer is less than 30 nm.

The Role of Silion Oxide Layers in Luminescence of Ensembles of Silicon Quantum Dots

Based on the quantum confinement-luminescence center model, to ensembles of spherical silicon nanocrystals (nc-Si) containing two kinds of luminescence centers (LCs) in the layers surrounding the nc-Si, the relationship between the photoluminescence (PL) and the thickness of the layer is studied with the excitation energy flux density as a parameter. When there is no layer surrounding the nc-Si, the electron-heavy hole pair can only recombine inside the nc-Si, then the PL blueshift with reducing particle sizes roughly accords with the rule predicted by the quantum confinement model of Canham. When there presences a layer, some of the carriers may tunnel into it and recombine outside the nc-Si at the LCs to emit visible light. The thicker the layer is, the higher the radiative recombination rate occurred outside the nc-Si will be. When the central scale of the nc-Si is much smaller than the critical scale, the radiative recombination rate outside the nc-Si dominates, and visible PL will be possible for some nc-Si samples with big average radius, greater than 4 nm, for example. When there is only one kind of LC in the layer, the PL peak position does not shift with reducing particle sizes. All these conclusions are in accord with the experimental results. When there are two or more kinds of LCs in the layer, the PL peak position energy and intensity swing with reducing particle sizes.

Influence of Warm Oxide Layer on Wettability and Contact Angle for Heat Transport Devices

Recently, high heat density has become a problem in electronic devices. Therefore, high heat-transfer efficiency is required in copper heat exchangers. Improvement ofwettability is reported to improve the heat-transfer efficiency. In previous studies, copper oxide layer improves the wettability. In this study, we focus on a copper oxide layer produced under warm conditions （from 200 to 300 ℃）, which are suitable oxidation conditions for improving wettability. Experimental results showed that the surface of the specimens was covered by the oxidation layer and took on a black color. Furthermore, the wettability was improved by the warm copper oxide layer. While, the surface roughness was approximately constant to each warm oxidized specimen. Whereat, the warm oxide layer was observed by SEM （sanning electron microscope）. The results from SEM observations showed that the warm copper oxide layer consisted of stacks and combinations of nanoscopic warm oxidation particles. Thus, the warm oxidation layer has nanoscopic surface asperities. It is seemed that these nanoscopic asperities improved the wettability.

High‑Entropy Layered Oxide Cathode Enabling High‑Rate for Solid‑State Sodium‑Ion Batteries

Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instability,making it difficult to achieve high performance solid-state sodium-ion batteries.Herein,the high-entropy design and Li doping strategy alleviate lattice stress and enhance ionic conductivity,achieving high-rate performance,air stability and electrochemically thermal stability for Na_(0.95)Li_(0.06)Ni_(0.25)Cu_(0.05)Fe_(0.15)Mn_(0.49)O_(2).This cathode delivers a high reversible capacity(141 mAh g^(−1)at 0.2C),excellent rate capability(111 mAh g^(−1)at 8C,85 mAh g^(−1)even at 20C),and long-term stability(over 85%capacity retention after 1000 cycles),which is attributed to a rapid and reversible O3–P3 phase transition in regions of low voltage and suppresses phase transition.Moreover,the compound remains unchanged over seven days and keeps thermal stability until 279℃.Remarkably,the polymer solid-state sodium battery assembled by this cathode provides a capacity of 92 mAh g^(−1)at 5C and keeps retention of 96%after 400 cycles.This strategy inspires more rational designs and could be applied to a series of O3 cathodes to improve the performance of solid-state Na-ion batteries.

Phase engineering of Ni-Mn binary layered oxide cathodes for sodiumion batteries

Nickel-manganese binary layered oxides with high working potential and low cost are potential candidates for sodium-ion batteries,but their electrochemical properties are highly related to compositional diversity.Diverse composite materials with various phase structures of P3,P2/P3,P2,P2/O3,and P2/P3/O3 were synthesized by manipulating the sodium content and calcination conditions,leading to the construction of a synthetic phase diagram for Na_(x)Ni_(0.25)Mn_(0.75)O_(2)(0.45≤x≤1.1).Then,we compared the electrochemical characteristics and structural evolution during the desodiation/sodiation process of P2,P2/P3,P2/03,and P2/P3/O3-Na_(x)Ni_(0.25)Mn_(0.75)O_(2).Among them,P2/P3-Na0.75Ni0.25Mn0.75O2exhibits the best rate capability of 90.9 mA h g^(-1)at 5 C,with an initial discharge capacity of 142.62 mA h g^(-1)at 0.1 C and a capacity retention rate of 78.25%after 100 cycles at 1 C in the voltage range of 2-4.3 V.The observed superior sodium storage performance of P2/P3 hybrids compared to other composite phases can be attributed to the enhanced Na^(+)transfer dynamic,reduction of the Jahn-teller effect,and improved reaction reversibility induced by the synergistic effect of P2 and P3 phases.The systematic research and exploration of phases in Na_(x)Ni_(0.25)Mn_(0.75)O_(2)provide new sights into high-performance nickel-manganese binary layered oxide for sodium-ion batteries.

Mg/Fe site-specific dual-doping to boost the performance of cobalt-free nickle-rich layered oxide cathode for high-energy lithium-ion batteries

Layer-type LiNi0.9Mn0.1O2is promising to be the primary cathode material for lithium-ion batteries(LIBs)due to its excellent electrochemical performance.Unfortunately,the cathode with high nickel content suffers from severely detrimental structural transformation that causes rapid capacity attenuation.Herein,site-specific dual-doping with Fe and Mg ions is proposed to enhance the structural stability of LiNi0.9Mn0.1O2.The Fe3+dopants are inserted into transition metal sites(3b)and can favorably provide additional redox potential to compensate for charge and enhance the reversibility of anionic redox.The Mg ions are doped into the Li sites(3a)and serve as O_(2)^(-)-Mg^(2+)-O_(2)^(-)pillar to reinforce the electrostatic cohesion between the two adjacent transition-metal layers,which further suppress the cracking and the generation of harmful phase transitions,ultimately improving the cyclability.The theoretical calculations,including Bader charge and crystal orbital Hamilton populations(COHP)analyses,confirm that the doped Fe and Mg can form stable bonds with oxygen and the electrostatic repulsion of O_(2)^(-)-O_(2)^(-)can be effectively suppressed,which effectively mitigates oxygen anion loss at the high delithiation state.This dual-site doping strategy offers new avenues for understanding and regulating the crystalline oxygen redox and demonstrates significant potential for designing high-performance cobalt-free nickel-rich cathodes.

Surface encapsulation of layered oxide cathode material with NiTiO_(3) for enhanced cycling stability of Na-ion batteries

In Na-ion batteries,O3-type layered oxide cathode materials encounter challenges such as particle cracking,oxygen loss,electrolyte side reactions,and multi-phase transitions during the charge/discharge process.This study focuses on surface coating with NiTiO_(3) achieved via secondary heat treatment using a coating precursor and the surface material.Through in-situ x-ray diffraction(XRD)and differential electrochemical mass spectrometry(DEMS),along with crystal structure characterizations of post-cycling materials,it was determined that the NiTiO_(3) coating layer facilitates the formation of a stable lattice structure,effectively inhibiting lattice oxygen loss and reducing side reaction with the electrolyte.This enhancement in cycling stability was evidenced by a capacity retention of approximately 74%over 300 cycles at 1 C,marking a significant 30%improvement over the initial sample.Furthermore,notable advancements in rate performance were observed.Experimental results indicate that a stable and robust surface structure substantially enhances the overall stability of the bulk phase,presenting a novel approach for designing layered oxide cathodes with higher energy density.

Cationic ordering transition in oxygen-redox layered oxide cathodes

Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.

Recent progress in Ni-rich layered oxides and related cathode materials for Li-ion cells

Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.

Achieving structurally stable O3-type layered oxide cathodes through site-specific cation-anion co-substitution for sodium-ion batteries

O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.

Cycling performance of layered oxide cathode materials for sodium-ion batteries

Layered oxide is a promising cathode material for sodium-ion batteries because of its high-capacity,high operating voltage,and simple synthesis.Cycling performance is an important criterion for evaluating the application prospects of batteries.However,facing challenges,including phase transitions,ambient stability,side reactions,and irreversible anionic oxygen activity,the cycling performance of layered oxide cathode materials still cannot meet the application requirements.Therefore,this review proposes several strategies to address these challenges.First,bulk doping is introduced from three aspects:cationic single doping,anionic single doping,and multi-ion doping.Second,homogeneous surface coating and concentration gradient modification are reviewed.In addition,methods such as mixed structure design,particle engineering,high-entropy material construction,and integrated modification are proposed.Finally,a summary and outlook provide a new horizon for developing and modifying layered oxide cathode materials.

Lowering Sodium-Storage Lattice Strains of Layered Oxide Cathodes by Pushing Charge Transfer on Anions

Due to a high energy density,layered transition-metal oxides have gained much attention as the promising sodium-ion batteries cathodes.However,they readily suffer from multiple phase transitions during the Na extraction process,resulting in large lattice strains which are the origin of cycledstructure degradations.Here,we demonstrate that the Na-storage lattice strains of layered oxides can be reduced by pushing charge transfer on anions(O^(2-)).Specifically,the designed O3-type Ru-based model compound,which shows an increased charge transfer on anions,displays retarded O3-P3-O1 multiple phase transitions and obviously reduced lattice strains upon cycling as directly revealed by a combination of ex situ X-ray absorption spectroscopy,in situ X-ray diffraction and geometric phase analysis.Meanwhile,the stable Na-storage lattice structure leads to a superior cycling stability with an excellent capacity retention of 84%and ultralow voltage decay of 0.2 mV/cycle after 300 cycles.More broadly,our work highlights an intrinsically structure-regulation strategy to enable a stable cycling structure of layered oxides meanwhile increasing the materials’redox activity and Nadiffusion kinetics.

Dependence of Initial Capacity Irreversibility on Oxygen Framework Chemistry in Li-Rich Layered Cathode Oxides

The undesirable capacity loss after first cycle is universal among layered cathode materials,which results in the capacity and energy decay.The key to resolving this obstacle lies in understanding the effect and origin of specific active Li sites during discharge process.In this study,focusing on Ah-level pouch cells for reliability,an ultrahigh initial Coulombic efficiency(96.1%)is achieved in an archetypical Li-rich layered oxide material.Combining the structure and electrochemistry analysis,we demonstrate that the achievement of high-capacity reversibility is a kinetic effect,primarily related to the sluggish Li mobility during oxygen reduction.Activating oxygen reduction through small density would induce the oxygen framework contraction,which,according to Pauli repulsion,imposes a great repulsive force to hinder the transport of tetrahedral Li.The tetrahedral Li storage upon deep oxygen reduction is experimentally visualized and,more importantly,contributes to 6%Coulombic efficiency enhancement as well as 10%energy density improvement for pouch cells,which shows great potentials breaking through the capacity and energy limitation imposed by intercalation chemistry.

Designing ultrastable P2/O3-type layered oxides for sodium ion batteries by regulating Na distribution and oxygen redox chemistry

P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.

Inhibiting Voltage Decay in Li-Rich Layered Oxide Cathode:From O3-Type to O2-Type Structural Design

Li-rich layered oxide(LRLO)cathodes have been regarded as promising candidates for next-generation Li-ion batteries due to their exceptionally high energy density,which combines cationic and anionic redox activities.However,continuous voltage decay during cycling remains the primary obstacle for practical applications,which has yet to be fundamentally addressed.It is widely acknowledged that voltage decay originates from the irreversible migration of transition metal ions,which usually further exacerbates structural evolution and aggravates the irreversible oxygen redox reactions.Recently,constructing O2-type structure has been considered one of the most promising approaches for inhibiting voltage decay.In this review,the relationship between voltage decay and structural evolution is systematically elucidated.Strategies to suppress voltage decay are systematically summarized.Additionally,the design of O2-type structure and the corresponding mechanism of suppressing voltage decay are comprehensively discussed.Unfortunately,the reported O2-type LRLO cathodes still exhibit partially disordered structure with extended cycles.Herein,the factors that may cause the irreversible transition metal migrations in O2-type LRLO materials are also explored,while the perspectives and challenges for designing high-performance O2-type LRLO cathodes without voltage decay are proposed.

Behaviors of Oxide Layer at Interface between Semi-solid Filler Metal and Aluminum Matrix Composites during Vibration

The joint interface between semi-solid Zn-Al filler metal and SiCp/Al composites with applying vibration for different time was examined. With increasing vibrating time, the oxide layer was disrupted prior at the centre to the periphery of the interface. And the solid grains near the centre of interface in semi-solid filler metal aggregated into two solid regions and compressed the composites during vibration; the solid grains near the periphery of interface moved toward the edge and scraped the composites during vibration. The models of disrupting oxide layer under the vibration condition were developed. At the centre of interface, the oxide layer was tore and stripped during the solid grains in the semi-solid filler metal depressing the composites with a very high compressive stress. At the periphery of interface, the oxide layer was cut and stripped into the filler metal during the solid grains scraping the interface.