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.

Catalytic combustion of diesel soot over K_2NiF_4-type oxides La_(2-x)K_xCuO_4

Nanostructure K2NiF4 type oxides La2-xKxCuO4 complex oxides were prepared using the Sol-Gel method, characterized by X-Ray Diffraction （XRD）, Fourier Transform Infrared （FT-IR）, and Scanning Electron Microscopy （SEM）. The catalytic activity for soot combustion was evaluated by the Temperature-Programmed Reaction （TPO） technique. The results demonstrated that the substitution quality of K^＋ for La^3＋ at the A-site would increase the catalytic activities of La2-xKxCuO4 for soot combustion greatly; the substitution quality affected the structure and catalytic activity obviously. The La1.8K0.2CuO4 complex oxides with tetrahedral structures had the best catalytic activity for soot combustion, and the ignition temperature of soot combustion was lowered from 490 to 320 ℃.

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.

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.

Catalytic Combustion of Diesel Soot over K_2NiF_4-type Oxides La_(2-x)K_xCuO_4

The K2NiF4 type oxides, La2-x KxCuO4 complex oxides with nanometric size were prepared by sol-gel method. The characters of these samples were analyzed by H2-TPR, XRD, FT-IR and SEM. The catalytic activity for soot combustion was evaluated by temperature-programmed reaction （TPO） technique. The results demonstrate that the substitution of K^＋ for La^3＋ at A-site will increase the catalytic activities of La2-xKxCuO4 to soot combustion greatly, and the substitution quantity affects the structure and catalytic activity obviously. The La1.8 K0.2 CuO4 complex oxides with tetrahedral structure has the best catalytic activity for soot removal reaction, the ignition temperature of soot combustion is decreased from 490 to 320℃.

Surface engineering of P2-type cathode material targeting long-cycling and high-rate sodium-ion batteries

The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.

聚乙二醇在Triton X-114/正辛烷/正丁醇/水反相微乳液中的增溶研究

研究了加入聚合物对Triton X-114/正辛烷/正丁醇/水组分体系相态的影响.利用次甲基蓝(MB)作为吸附探针,而以(口恶)唑烷氮氧自由基(5-doxyl stearic acid,5-DNS)作为自旋探针,研究了加入聚合物对TX-114/正辛烷/正丁醇/水反相微乳液的微结构影响.结果表明:聚合物添加使W/O微乳液区缩小,而液晶区则更靠近水一端(增溶更多水),该反相微乳液中存在三种状态水:结合水、束缚水、体相水.加入聚合物可以替代先前存在于TX-114聚氧乙烯链上的一些水分子,使其微极性减小,而且使表面活性剂分子在界面上的排列更为松散,本研究结果对探讨聚合物对W/O微乳液微结构的影响及此类体系在其它方面应用有重要意义.

Understanding Li roles in chemical reversibility of O2-type Li-rich layered cathode materials

Traditional O3-type Li-rich layered materials are attractive with ultra-high specific capacities,but suffering from inherent problems of voltage hysteresis and poor cycle performance.As an alternative,O2-type materials show the potential to improve the oxygen redox reversibility and structural stability.However,their structure-performance relationship is still unclear.Here,we investigate the correlation between the Li component and dynamic chemical reversibility of O2-type Li-rich materials.By exploring the formation mechanism of a series of materials prepared by Na/Li exchange,we reveal that insufficient Li leads to an incomplete replacement,and the residual Na in the Li-layer would hinder the fast diffusion of Li^(+).Moreover,excessive Li induces the extraction of interlayer Li during the melting chemical reaction stage,resulting in a reduction in the valence of Mn,which leads to a severe Jahn-Teller effect.Structural detection confirms that the regulation of Li can improve the cycle stability of Li-rich materials and suppress the trend of voltage fading.The reversible phase evolution observed in in-situ X-ray diffraction confirms the excellent structural stability of the optimized material,which is conducive to capacity retention.This work highlights the significance of modulating dynamic electrochemical performance through the intrinsic structure.

Comparative structural and electrochemical properties of mixed P2/O′3-layered sodium nickel manganese oxide prepared by sol-gel and electrospinning methods:Effect of Na-excess content

The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X-ray diffraction results of the prepared NNMO without adding Na-excess content indicate sodium loss,while the mixed phase of P2/O′3-type layered NNMO presented after adding Na-excess content.Compared with the sol-gel method,the secondary phase of NiO is more suppressed by using the electrospinning method,which is further confirmed by field emission scanning electron microscope images.N_(2) adsorption-desorption isotherms show no remarkably difference in specific surface areas between different preparation methods and Na-excess contents.The analysis of X-ray absorption near edge structure indicates that the oxidation states of Ni and Mn are+2 and+4,respectively.For the electrochemical properties,superior electrochemical performance is observed in the NNMO electrode with a low Na-excess content of 5wt%.The highest specific capacitance is 36.07 F·g^(-1)at0.1 A·g^(-1)in the NNMO electrode prepared by using the sol-gel method.By contrast,the NNMO electrode prepared using the electrospinning method with decreased Na-excess content shows excellent cycling stability of 100%after charge-discharge measurements for 300 cycles.Therefore,controlling the Na excess in the precursor together with the preparation method is important for improving the electrochemical performance of Na-based electrode materials in supercapacitors.

"114"型氧化物SrAZn_(2)GaAlO_(7)(A=Ba^(2+),Sr^(2+))的晶体结构研究

"114"型氧化物由于其独特的晶体结构与有趣的物理性质而受到了人们的广泛关注.为研究"114"化合物中A位离子的大小对结构对称性及原子占位的影响,设计合成了两个A位离子大小不同的"114"型新化合物SrAZn_(2)GaAlO_(7)(A=Ba^(2+),Sr^(2+)).粉末X射线衍射(powder X-ray diffraction,PXRD)分析结果表明,随着A位离子半径的减小,SrAZn_(2)GaAlO_(7)的结构对称性由P31c(A=Ba^(2+))降低到Pna2_(1)(A=Sr^(2+)).基于PXRD数据的Rietveld精修结果表明,SrAZn_(2)GaAlO_(7)中离子半径较小的Al3+倾向于占据三角层中的四面体间隙,而较大的Zn^(2+)/Ga^(3+)则倾向于占据Kagomé层中的四面体间隙.

P2-type layered high-entropy oxides as sodium-ion cathode materials

P2-type layered oxides with the general Na-deficient composition Na_(x)TMO_(2)(x<1,TM:transition metal)are a promising class of cathode materials for sodium-ion batteries.The open Na+transport pathways present in the structure lead to low diffusion barriers and enable high charge/discharge rates.However,a phase transition from P2 to O2 structure occurring above 4.2 V and metal dissolution at low potentials upon discharge results in rapid capacity degradation.In this work,we demonstrate the positive effect of configurational entropy on the stability of the crystal structure during battery operation.Three different compositions of layered P2-type oxides were synthesized by solid-state chemistry,Na_(0.67)(Mn_(0.55)Ni_(0.21)Co_(0.24))O_(2),Na_(0.67)(Mn_(0.45)Ni_(0.18)Co_(0.24)Ti_(0.1)Mg_(0.03))O_(2) and Na_(0.67)(Mn_(0.45)Ni_(0.18)Co_(0.18)Ti_(0.1)Mg_(0.03)Al_(0.04)Fe_(0.02))O_(2) with low,medium and high configurational entropy,respectively.The high-entropy cathode material shows lower structural transformation and Mn dissolution upon cycling in a wide voltage range from 1.5 to 4.6 V.Advanced operando techniques and post-mortem analysis were used to probe the underlying reaction mechanism thoroughly.Overall,the high-entropy strategy is a promising route for improving the electrochemical performance of P2 layered oxide cathodes for advanced sodium-ion battery applications.

A durable P2-type layered oxide cathode with superior low-temperature performance for sodium-ion batteries

To power large-scale energy storage systems,sodium-ion batteries(SIBs)must have not only high-energy density but also high performance under a low-temperature(LT)environment.P2-type manganese oxides with high specific capacity are promising cathode candidates for SIBs,but their LT applications are limitedly explored.We proposed a P2-type Na_(0.67)Ni_(0.1)Co_(0.1)Mn_(0.8)O_(2) material with outstanding LT performance prepared through reasonable structure modulation.The material offers an excellent Na^(+) diffusion coefficient(approximately 10^(−9)-10^(−7.5) cm^(2) s^(−1))at−20℃,a superior LT discharge capacity of 147.4 mA h g^(−1) in the Na half-cell system,and outstanding LT full cell performance(energy density of 358.3 W h kg^(−1)).Various characterisations and density function theory calculations results show that the solid solution reaction and pseudocapacitive feature promote the diffusion and desolvation of Na+from the bulk electrode to interface,finally achieving superior electrochemical performance at LT.

A comprehensive modification enables the high rate capability of P2-Na_(0.75)Mn_(0.67)Ni_(0.33)O_(2) for sodium-ion cathode materials

The Na^(+)/vacancy ordering can effectively affect the electrochemical behavior of P2-type cathode material.In this work we proposed an integrated strategy by attaining a high Na content,In^(3+) doping in conjunction with NaInO_(2) coating in the P2-Na_(0.75)Mn_(0.67)Ni_(0.33)O_(2) which can inhibit the sodium vacancy order,smooth the electrochemical curve,and enhance the structural stability and rate capability.A combination of X-ray diffraction analysis and DFT calculation indicate that the In(3+) ions in the Na layer serve as"pillars”to stabilize the layered structure,especially for high current density charging.The P2-Na_(0.75)Mn_(0.67)Ni_(0.33)In_(0.02)O_(2) with an impressive sodium content exhibits a remarkable reversible capacity of 109.6 mAh g^(-1),superior rate capability capacity of 79.8 mAh g^(-1)at 20 C,and 85%capacity retention after 100 cycles at 5 C.This work demonstrates an efficient approach for the comprehensive optimization of sodium ion cathode materials.

Roles of Oxygen Vacancy and Lower Valence Metallic Ion in Direct Decomposition of NO over La_（2－x）（Sr，Th）_xCuO_（4±λ）

Two systems of La_(2-x)Sr_xCuO_(4±λ) and La_(2-x)Th_xCuO_(4±λ) mixed oxides with K_2NiF_4structure were synthesized.The compositions and structures of the catalysts were characterized by means of XRD,XPS,chemical analysis and so on.The catalytic behavior for the direct decomposition of NO has been investigated.The results show that the catalytic activity is closely related to the oxygen vacancy and lower valence metallic ion in the direct decomposition of NO.The presence of oxygen vacancy is necessary for mixed oxide to have steady activity in NO decomposition.

Ln_2MO_4 cathode materials for solid oxide fuel cells

One of the major challenges to develop "intermediate temperature" solid oxide fuel cells is finding a novel cathode material, which can meet the following requirements: (1) high electronic conductivity; (2) chemical compatibility with the electrolyte; (3) a matched thermal expansion coefficient (TEC); (4) stability in a wide range of oxygen partial pressure; and (5) high catalytic activity for the oxygen reduction reaction (ORR). In this short review, a survey of these requirements for K2NiF4-type material with the formula Ln2MO4, Ln = La, Pr, Nd, Sm; M = Ni, Cu, Fe, Co, Mn, is presented. The composition-dependent TEC, electrical conductivity and oxygen transport property are considered. The Ln2MO4 materials exhibit improved chemical stability and compatibility with most of the traditional electrolytes. The complete fuel cells integrated with Ln2MO4 materials as cathodes show promising results. Furthermore, these materials are considered as cathodes of protonic ceramic fuel cell (PCFC), and/or anodes of high temperature steam electrolysis (HTSE). First results show excellent performances. The versatility of these Ln2MO4 materials is explained on the basis of structural features and the ability to accommodate oxygen non-stoichiometry.

Use of cloud point extraction for removal of nanosized copper oxide from wastewater

Triton X-114 based cloud point extraction has been demonstrated to be an advantageous approach for the recovery of nanosized copper oxide (NCO) from water. The removal of NCO was influenced by the concentrations of TX-114 and salt, incubation temperature and time, as well as solution pH. With the addition of 0.3% (w/v) Triton X-114, over 88% of the spiked NCO was removed from wastewater after incubation at 35°C for 2 h and centrifugation, whereas over 85% of NCO was recovered after incubation at 28°C for 20 h by gravity phase separation, which is economical and energy-saving. This study suggests that the cloud point extraction technique has great potential in removal of nanomaterials from wastewater.

Insights into the Ti^(4+) doping in P2-type Na_(0.67)Ni_(0.33)Mn_(0.52)Ti_(0.15)O_(2) for enhanced performance of sodium-ion batteries

Due to the sodium abundance and availability,sodium-ion batteries(SIBs)have the potential to meet the worldwide growing demand of electrical energy storage.P2-type sodium transition-metal layer oxides with a high energy density are considered as the most promising cathode materials for SIBs.We present here a detailed study of the enhanced rate capability and cyclic stability of the Ti-doped Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)cathode material.The combined analysis of ex-situ X-ray absorption fine structure(XAFS)spectroscopy,aberration-corrected high resolution transmission electron microscopy(AB-HRTEM)and X-ray diffraction(XRD)show that the strong Ti–O bond in the transition metal layers stabilizes the local structure,destroy the Na+-vacancy ordering and arrest the irreversible multiphase transformation that occurs during the intercalation/deintercalation process.Actually,Na_(0.67)Ni_(0.33)Mn_(0.52)Ti_(0.15)O_(2)exhibits a reversible capacity of 89.6 mA h g^(-1)even at 5 C,an excellent cyclability with 88.78%capacity retention after 200 cycles at 0.5 C.This study provides a better understanding in optimization of the design of high-energy cathode materials based on titanium doped layered oxides for SIBs.

P2-type Na0.67Co0.35Ti0.20Mn0.44La0.01O2 cathode material with high-rate capability for sodium-ion batteries

The substitution of elements has attracted great interest to enhance the electrochemical properties of sodium-ion batteries(SIBs).Herein,the P2-Na0.67Co0.35Ti0.20Mn0.45-xLaxO2 electrode samples were prepared via a solid-state route.The effect of La3+substitution was researched as high-rate SIBs cathode.The Na0.67Co0.35Ti0.20Mn0.44La0.01O2 exhibits a superior initial specific capacity of 162.7 and 125.9 mA h/g after50 cycles at 0.1 C rate,and the initial specific discharge capacity of 115.2 mA h/g with 60.6%capacity retention after 100 cycles at 1 C In addition,the Na0.67Co0.35Ti0.20Mn0.44La0.01O2 sample shows an excellent rate capacity of 91.9 and 60.4 mA·h/g with 46.9%and 50.9%capacity retentions even at 8 C and 10 C rate after100 cycles,respectively.The promising La-substituted P2-type Na0.67Co0.35Ti0.20Mn0.45-xLaxO2 material provides a new strategy for designing high-rate performance of SIBs.

A Ca-substituted air-stable layered oxide cathode material with facilitated phase transitions for high-performance Na-ion batteries

Cost-efficient and high-performance cathodes play a crucial role in the advancement of grid-sc ale sodium-ion batteries(SIBs).As promising high-capacity cathode materials for SIBs,O_(3)-type Na-based layered transition metal oxides constantly experience inadequate air stability and complex phase transitions.Herein,a comprehensive investigation was conducted to explore the impact of Ca substitution on both the electrochemical performance and structural stability of O_(3)-Na_(1-2x)Ca_xNi_(0.25)Fe_(0.5)Mn_(0.25)O_(2)(x=0.0.02 and 0.05)that is proposed.With proper Ca content,O_(3)-type Na_(0.96)Ca_(0.02)-Ni_(0.25)Fe_(0.5)Mn_(0.25)O_(2)can deliver a reversible capacity of122.1 mAh·g^(-1)at 10 mA·g^(-1),with capacity retention of83.4%after 200 cycles at 50 mA·g^(-1)and good rate capability.Its air sensitivity is investigated,and its potential as the Na host in full cells has been studied.In situ X-ray diffraction reveals the facilitated O_(3)-P_(3)-O_(3)phase transitions of such cathode during the whole electrochemical reaction.Such a simple and effective strategy may reveal a new avenue for high-stable O_(3)-type cathodes and promote the practical applications of SIBs.

New DySrAlO_4 Compound Synthesis and Formation Process Correlations for LnSrAlO_4(Ln=Nd,Gd,Dy) Series

For the first time, DySrA104 of K2NiF4-type structure was synthesized. The parameters of DySrA104 ele- mentary unit cell are determined as follows： a = 0.368 （4） nm, c = 1.229 （2） nm, V = 0.166 （4） nm3. The research of the complex aluminates ZnSrA104 （Ln = Nd, Gd, Dy） solid-state process demonstrated the change of the formation mecha- nism among LnSrA104 （Ln = Nd, Gd, Dy） series from DySrA104 oxide. The performed analysis provided a possibility to realize why chemists couldn＇t get DySrA104 for a long period of time.