High-Temperature Electric Properties and X-ray Photoemission Spectra of Layered Co-Based Oxides Bi_(2-x)La_xSr_2Co_2O_(8-δ)

Layered Co-based ceramics with a nominal composition Bi2-xLaxSr2Co2O8-δ (x=0.0, 0.4, 0.8, short by BLC-222) were prepared using conventional solid state reaction method. X-ray photoemission spectroscopy (XPS) was used to investigate their electronic structures. The cobalt ions are highly mixed valences of Co3+ and Co4+. The fraction of Co4+ almost keeps unchanged with the increase of x. The O-1s photoemission spectra show that there are lattice oxygen and chemical absorbed oxygen in all the samples. The substitution of Bi3+ by La3+ results in a change from metallic-like behavior to semiconductor behavior. This abnormal phenomenon means that La3+ plays a key role in effecting the electrical transport property of BLC-222. The O-Co covalence bond is strengthened by the increase of La3+, which results in the decrease of conductivity.

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.

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.

Synthesis and highly efficient photocatalytic activity of mixed oxides derived from ZnNiAl layered double hydroxides

ZnO/NiO/ZnAl2O4 mixed-metal oxides were successfully synthesized through a hydrotalcite-like precursor route, in which appropriate amounts of metal salts solutions were mixed to obtain a new series of ZnNiAl layered double hydroxides（LDHs） as precursors, followed by calcination under different temperatures. The as-obtained samples were characterized by SEM, HRTEM, TEM, XRD, BET, TG-DTA, and UV-Vis spectra techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange（MO） under the simulated sunlight irradiation. The effects of Zn/Ni/Al mole ratio and calcination temperature on the composition, morphology and photocatalytic activity of the samples were investigated in detail. The results indicated that compared with ZnNiAl-LDHs, the mixed-metal oxide showed superior photocatalytic performance for the degradation of MO. A maximum of 97.3% photocatalytic decoloration rate within 60 min was achieved from the LDH with the Zn/Ni/Al mole ratio of 2：1：1 and the calcination temperature of 500 ℃, which much exceeded that of Degussa P25 under the same conditions. The possible mechanism of photocatalytic degradation over ZnO/NiO/ZnAl2O4 was discussed.

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.

Enhancing the stability of Ni Fe-layered double hydroxide nanosheet array for alkaline seawater oxidation by Ce doping

Electrocatalytic hydrogen production from seawater holds enormous promise for clean energy generation.Nevertheless,the direct electrolysis of seawater encounters significant challenges due to poor anodic stability caused by detrimental chlorine chemistry.Herein,we present our recent discovery that the incorporation of Ce into Ni Fe layered double hydroxide nanosheet array on Ni foam(Ce-Ni Fe LDH/NF)emerges as a robust electrocatalyst for seawater oxidation.During the seawater oxidation process,CeO_(2)is generated,effectively repelling Cl^(-)and inhibiting the formation of Cl O-,resulting in a notable enhancement in the oxidation activity and stability of alkaline seawater.The prepared Ce-Ni Fe LDH/NF requires only overpotential of 390 m V to achieve the current density of 1 A cm^(-2),while maintaining long-term stability for 500 h,outperforming the performance of Ni Fe LDH/NF(430 m V,150 h)by a significant margin.This study highlights the effectiveness of a Ce-doping strategy in augmenting the activity and stability of materials based on Ni Fe LDH in seawater electrolysis for oxygen evolution.

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.

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.

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.

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.

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.

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.

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.

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.

Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene

Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.

Recent advance on VOCs oxidation over layered double hydroxides derived mixed metal oxides

Catalytic oxidation is regarded as one of the most promising strategies for volatile organic compounds(VOCs)purification.Mixed metal oxides(MMOs),after topological transformation using layered double hydroxides(LDHs)as precursors,are extensively used as catalysts for VOCs oxidation due to their uniformity advantage.This review summarizes the developments in the LDH-derived VOCs heterogeneous catalytic oxidation over the last 10 years.Particularly,it addresses the VOCs abatement performance over MMO,noble metal/MMO,core-shell structured MMO,and integral MMO film catalysts originating from LDHs.Moreover,it highlights the water vapor effect and oxidation mechanism.This review indicates that LDH-based catalysts are a category of important VOCs oxidation materials.

New layered metal oxides as positive electrode materials for room-temperature sodium-ion batteries

In order to achieve better Na storage performance, most layered oxide positive electrode materials contain toxic and expensive transition metals Ni and/or Co, which are also widely used for lithium-ion batteries. Here we report a new quaternary layered oxide consisting of Cu, Fe, Mn, and Ti transition metals with O3-type oxygen stacking as a positive electrode for room-temperature sodium-ion batteries. The material can be simply prepared by a high-temperature solidstate reaction route and delivers a reversible capacity of 94 m Ah/g with an average storage voltage of 3.2 V. This paves the way for cheaper and non-toxic batteries with high Na storage performance.

Overwhelming low ammonia escape and low temperature denitration efficiency via MnOx-decorated two-dimensional MgAl layered double oxides

Low temperature catalysts are attracting increasing attention in the selective catalytic reduction(SCR)of NO with NH3.Mn Ox-decorated Mg Al layered double oxide(Mn/Mg Al-LDO)was synthesized via a facile fast pour assisted co-precipitation(FP-CP)process.Compared to the Mn/Mg Al-LDO obtained via slow drop assisted coprecipitation(SD-CP)method,the Mn/Mg Al-LDO(FP-CP)has excellent activity.The Mn/Mg Al-LDO(FP-CP)catalyst was shown to possess a high NO conversion rate of 76%-100%from 25 to 150℃,which is much better than the control Mn/Mg Al-LDO(SD-CP)(29.4%-75.8%).In addition,the Mn/Mg Al-LDO(FP-CP)offered an enhanced NO conversion rate of 97%and a N2selectivity of 97.3%at 100℃;the NO conversion rate was 100%and the N2selectivity was 90%at 150℃with a GHSV of 60,000 h^-1.The Mn/Mg Al-LDO(FP-CP)catalyst exhibited a smaller fragment nano-sheet structure(sheet thickness of 7.23 nm).An apparent lattice disorder was observed in the HRTEM image confirming the presence of many defects.The H2-TPR curves show that the Mn/Mg Al-LDO(FP-CP)catalyst has abundant reducing substances.Furthermore,the enhanced surface acidity makes the NH3concentration of the Mn/Mg Al-LDO(FP-CP)catalyst lower than 100 ml·m^-3after the reaction from 25 to 400℃.This can effectively reduce the ammonia escape rate in the SCR reaction.Thus,the Mn/Mg Al-LDO(FP-CP)catalyst has potential applications in stationary industrial installations for environmentally friendly ultra-low temperature SCR.

Tuning exsolution of nanoparticles in defect engineered layered perovskite oxides for efficient CO_(2) electrolysis

Solid oxide electrolysis cell(SOEC) could be a potential technology to afford chemical storage of renewable electricity by converting water and carbon dioxide.In this work,we present the Ni-doped layered perovskite oxides,(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2) with n=5,8,and 12(LSTNn) for application as catalysts of CO_(2) electrolysis with the exsolution of Ni nanoparticles through a simple in-situ growth method.It is found that the density,size,and distribution of exsolved Ni nanoparticles are determined by the number of n in LSTNn due to the different stack structures of TiO_6 octahedra along the c axis.The Ni doping in LSTNn significantly improved the electrochemical activity by increasing oxygen vacancies,and the Ni metallic nanoparticles afford much more active sites.The results show that LSTNn cathodes can successfully be manipulated the activity by controlling both the n number and Ni exsolution.Among these LSTNn(n=5,8,and 12),LSTN8 renders a higher activity for electrolysis of CO_(2) with a current density of 1.50A cm^(-2)@2.0 V at 800℃ It is clear from these results that the number of n in(La_(4)Sr_(n-4))_(0.9)Ti_(0.9n)Ni_(0.1n)O_(3n+2)with Ni-doping is a key factor in controlling the electrochemical performance and catalytic activity in SOEC.