Phase structure evolution and its effect on magnetic and mechanical properties of B-doped Sm_(2)Co_(17)-type magnets with high Fe content

The unique cellular microstructure of Fe-rich Sm_(2)Co_(17)-type permanent magnets is closely associated with the structure of the solid solution precursor.We investigate the phase structure,magnetic properties,and mechanical behavior of B-doped Sm_(2)Co_(17)-type magnets with high Fe content.The doped B atoms can diffuse into the interstitial vacancy,resulting in lattice expansion and promote the homogenization of the phase organizational structure during the solid solution treatment in theory.However,the resulting second phase plays a dominant role to result in more microtwin structures and highly ordered 2:17R phases in the solid solution stage,which inhibits the ordering transformation of 1:7H phase during aging and affects the generation of the cellular structure,and to result in a decrease in magnetic properties,yet the interface formed between it and the matrix phase hinders the movement of dislocations and enhances the mechanical properties.Hence,the precipitation of high flexural strain grain boundary phase induced by B element doping is also a new and effective way to improve the flexural strain of Sm_(2)Co_(17)-type magnets.Our study provides a new understanding of the phase structure evolution and its effect on the magnetic and mechanical properties of Sm_(2)Co_(17)-type magnets with high Fe content.

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.

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.

Structures and electrochemical hydrogen storage performance of Si added A_2B_7-type alloy electrodes

In order to ameliorate the electrochemical hydrogen storage performance of La-Mg-Ni system A2B7-type electrode alloys, a small amount of Si was added. The La0.8Mg0.2Ni3.3Co0.2Six （x=0-0.2） electrode alloys were prepared by casting and annealing. The effects of adding Si on the structure and electrochemical hydrogen storage characteristics of the alloys were investigated systematically. The results indicate that the as-cast and annealed alloys hold multiple structures, involving two major phases of （La, Mg）2Ni7 with a Ce2Ni7-type hexagonal structure and LaNi5 with a CaCu5-type hexagonal structure as well as one residual phase LaNi3. The addition of Si results in a decrease in （La, Mg）2Ni7 phase and an increase in LaNi5 phase without changing the phase structure of the alloys. What is more, it brings on an obvious effect on electrochemical hydrogen storage characteristics of the alloys. The discharge capacities of the as-cast and annealed alloys decline with the increase of Si content, but their cycle stabilities clearly grow under the same condition. Furthermore, the measurements of the high rate discharge ability, the limiting current density, hydrogen diffusion coefficient as well as electrochemical impedance spectra all indicate that the electrochemical kinetic properties of the electrode alloys first increase and then decrease with the rising of Si content.

Petrogenesis of Late Cretaceous Jiangla＇angzong I-Type Granite in Central Lhasa Terrane, Tibet, China： Constraints from Whole-Rock Geochemistry, Zircon U-Pb Geochronology, and Sr-Nd-Pb-Hf Isotopes

The Jiangla＇angzong granite in the northern part of the Central Lhasa Terrane is composed of syenogranite and adamellite. LA-ICP-MS zircon U-Pb analyses suggest that syenogranite has a weighted mean 2±6pb/23SU age of 86±1 Ma （mean square weighted deviation=0.37）, which is in accordance with the muscovite Ar-Ar age （85±1 Ma） of Cu-Au ore-bearing skarns and the zircon U-Pb age （84±1 Ma） of adamellite. This suggests that the Jiangla＇angzong magmatism and Cu-Au mineralization events took place during the Late Cretaceous. The granite contains hornblende, biotite, and pyroxene, and does not contain Al-bearing minerals, such as muscovite, cordierite, and garnet. It has high contents of SiO2 （65.10 -70.91wt%）, K20 （3.44-5.17wt%）, and total K20＋Na20 （7.13-8.15wt%）, and moderate contents of A12Oa （14.14-16.45wt%） and CaO （2.33-4.11wt%）, with a Reitman index （δ43） of 2.18 to 2.33, and A/ CNK values of 0.88 to 1.02. The P205 contents show a negative correlation with SiO2, whereas Pb contents show a positive correlation with SiO2. Th and Y contents are relatively low and show a negative correlation with the Rb contents. These characteristics suggest that the Jiangla＇angzong granite is a high K calc-alkaline metaluminous I-type granite. It is enriched in light rare earth elements （LREE） and large ion lithofile elements （LILE）, and depleted in heavy rare earth elements （HREE） and high field strength elements （HFSE）, with LREE/HREE ratios of 11.7 to 18.1. The granite has negative Eu anomalies of 0.58 to 0.94 without obvious Ce anomalies （δCe=l.00-1.04）. The relatively low initial a7Sr/a6Sr ratios of 0.7106 to 0.7179, positive ε±nt（t） values of 1.0 to 4.1, and two-stage Hf model ages （TDM2） ranging from 889 Ma to 1082 Ma, These geochemical features indicate that the granite derived from a juvenile crust. The （143Nd/144Nd）t values from the Jiangla＇angzong granite range from 0.5121 to 0.5123, its eNd（t） values range from -10.17 to -6.10, its （^206pb /^204pb）t values range from 18.683 to 18.746, its （^207pb /^204pb）t values range from 15.695 to 15.700, and its （^208pb /^204pb）t values range from 39.012 to 39.071. These data indicate that the granite was formed by melting of the upper crust with the addition of some mantle materials. We propose that the Jiangla＇angzong granite was formed during the post- collision extension of the Qiangtang and Lhasa terranes.

华南燕山期佛冈–南昆山花岗岩石成因:来自锆石微量元素、H_(2)O含量及Hf-O同位素的约束

华南地区发育大规模与稀有金属成矿相关的燕山期花岗岩,其岩石类型与成因存在诸多争议,厘清这些争议有助于理解华南地区的成矿作用。锆石是花岗岩中常见的副矿物,具有非常稳定的物理化学性质,不容易受后期地质作用影响,可以很好地保存其形成时母岩浆的地球化学信息,从而避免全岩地球化学分析的不足。本研究选取华南地区佛冈–南昆山花岗岩中的锆石进行LA-ICP-MS微量元素和Hf同位素研究,结合SIMS氧同位素和H_(2)O含量等数据,探讨佛冈岩体和南昆山岩体的岩石类型和成因。两个岩体的锆石都呈现LREE亏损、HREE富集、Eu负异常、Ce正异常,以及Zr/Hf>55、Eu/Eu~*>0.005、Hf含量低(<1.2%)等特点,明显不同于高分异I型花岗岩,指示母岩浆分异程度较低。同时,锆石的REE+Y与P含量之间的关系表明它们也不是S型花岗岩。佛冈岩体锆石较高的δ18O值(7.97‰~10.29‰)、富集的εHf(t)值(-13.6~-5.7)、较低的H_(2)O含量(核密度峰值317~412μg/g)以及较高的锆饱和温度(799~800℃)表明,佛冈花岗岩可能是源区有高比例沉积物加入的A型花岗岩。南昆山岩体也具有类似的、但变化范围更大的锆石δ18O值(6.34‰~11.11‰)、εHf(t)值(-11.1~1.1)和H_(2)O含量(297~1253μg/g)。锆石Hf-O同位素和H_(2)O含量分析结果显示,二者均具有壳幔混合的特点,其中南昆山花岗岩源区地幔物质加入比例更大。

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.

Electrochemical Hydrogen Storage Performances of the Si Added La-Mg-Ni-based A_2B_7-type Electrode Alloys for Ni/MH Battery Application

The casting and annealing technologies were applied to fabricate the La0.8Mg0.2Ni3.3Co0.2Six （x = 0-0.2） electrode alloys. The effects of Si content and annealing temperature on the structure and electrochemical performances of the alloys were investigated systematically. The analyses of XRD and SEM show that all the alloys possess a multiphase structure, involving two main phases （La, Mg）2Ni7 and LaNi5 as well as a residual phase LaNi3. The addition of Si brings on an evident increase in the LaNi5 phase and a decrease in the （La, Mg）2Ni7 phase, without altering the main phase component of the alloy, which also makes the lattice constants and cell volumes of the alloy enlarged. Likewise, the annealing treatment engenders the same action on the lattice constants and cell volumes as adding Si. Simultaneously, it gives rise to the variation of the phase abundance and the coarsening of the alloy grains. The electrochemical measurements indicate that the addition of Si ameliorates the cycle stability of the as-cast and annealed alloys significantly, but impairs their discharge capacities clearly. Similarly, the annealing treatment makes a positive contribution to the cycle stability of the alloy evidently, and the discharge capacity of the alloy shows a maximum value with annealing temperature rising. Furthermore, the high rate discharge ability （HR） first augments and then declines with the rising of Si content and annealing temperature.

Structure and Electrochemical Properties of A_2B_7-Type La-Mg-Ni Hydrogen Storage Alloys

Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is great, resulting in a linear decrease of the unit cell parameters of main phases and increase of hydrogen absorption/desorption plateau as Mg content increases. Electrochemical measurements show that as the Mg content increases, the discharge capacity of alloy electrodes first increases and then decreases. The cyclic stability presents a deteriorative trend. La1.4Mg0.6 Ni7 alloy electrode exhibits the maximum electrochemical discharge capacity （378 mAh·g^-1）, and the La1.6Mg0.4Ni7 alloy electrode shows the best cyclic stability （S270 = 81%）.

XPS Study of the Oxygen on A_2BO_4-type Compounds-A New Discovery of O_(1S) Peaks

By means of XPS, a new O1s peak which reflects the lattice oxygen on A_2BO_4-typecompounds is discovered, suggesting that the lattice oxygen might have two energy states on thistype of material.

Novel Halophyte EREBP/AP2-type DNA Binding Protein Improves Salt Tolerance in Transgenic Tobacco

EREBP/AP2-type proteins are members of a large DNA binding protein (DBP) family found in plants. Some members like APETALA2 and AtDREB/CBF can regulate flower development and response to environmental stresses, respectively. To characterize transcription factors involved in plant responses to salt stress, we constructed cDNA library from salt-treated halophyte (Atriplex hortensis) and isolated a novel gene encoding EREBP/AP2-type protein from this library. This cDNA contained an ORF of 723 bp and a long 3'-Untranslated-Region (UTR) of 655 bp. The deduced amino acid sequence showed one conserved DNA binding domain of EREBP/AP2, thus the corresponding gene was named AhDREB1 with a calculated molecular mass of 26.1 kD. AhDREB1 under the control of CaMV 35S promoter was then transformed into tobacco and nine independent transgenic lines were obtained and subjected to long term salt stress. The results suggested that overexpression of AhDREB1 improved the salt tolerance in transgenic tobacco through functioning as a regulatory molecule in response to salt stress. Analysis of Arabidopsis genome in database resulted in dozens of EREBP/AP2-type homologous proteins, of which seven members showed high similarity to AhDREB1. Secondary structure analysis predicted similar arrangement of a-helix in their DNA binding domains.

First-principles investigations of structural, mechanical, electronic and optical properties of U_3Si_2-type AlSc_2Si_2 under high pressure

The structural, elastic, electronic and optical properties for U3Si2-type AlSc2Si2 compound under pressure were systematically investigated by using the first-principles calculations. The values of elastic constants and elastic moduli indicate that AlSc2Si2 keeps mechanical stability under high pressure. The mechanical properties of AISc2Si2 are compared with those of Al3Sc. The results indicate that AlSc2Si2 is harder than AI3Sc. Anisotropic constant AU and 3D curved surface of elastic moduli predict that AISc2Si2 is obviously anisotropic under pressure. The electronic structure of AlSc2Si2 exhibits metallic character and the metallicity decreases with the elevated pressure. In addition, optical properties as a function of pressure were calculated and analyzed. The present work provides theoretical support for further experimental work and industrial applications.

Two Types of Granites in the Western Yangtze Block and Their Implications for Regional Tectonic Evolution： Constraints from Geochemistry and Isotopic Data

In the western Yangtze Block, widespread Mesoproterozoic to Neoproterozoic rocks are the key to understanding the Precambrian tectonic-magmatic evolution of the region. However, their petrogenesis and tectonic setting are still controversial. In this paper, zircon U-Pb ages, Sm-Nd isotopic and whole-rock geochemical data are reported from selected fresh samples in the southern Dechang county, southwestern China, in order to constrain their emplacement age and magma source, as well as their petrogenesis and tectonic setting. They are mainly composed of biotite monzogranite, monzonitic granite, biotite granodiorites, and quartz diorite. Two ages of 1055 ± 43 Ma and 837.6 ± 3.8 Ma were obtained through zircon U-Pb dating by LA-ICP-MS and LA-MC-ICP-MS, respectively. According to their major element compositions, the Grenville-age granites are peraluminous calc-alkaline series calcic S-type granite. In contrast, the mid-Neoproterozoic granites are metaluminous calc-aikaline series alkalic I-type granite. Furthermore, the S-type granites are enriched in LREEs relative to HREEs with （La/Yb）N ratios of 3.85-18.56 and underwent major fractionation with strongly negative Eu anomalies （Eu/Eu＊ = 0.38-0.66）. In the MORB-normalized trace element variation diagram, all the samples are enriched in Ce and large ion lithophile elements such as Rb, Th, and K, and depleted in high field strength elements such as Nb, and Ti, with negative Sr and Ti anomalies. The I-type granites are enriched in LREEs with slight negative Eu anomalies （Eu/Eu＊= 0.83-0.93）. They are characterized by the enrichment of highly incompatible elements （such as K, Rb, Ba, Th） and LREEs, relative to MORB. Neodymium isotopic data show that the S-type granites display 143Nd/144Nd values of 0.51241-0.51256, and have eNa （t = 1055 Ma） values of （-3.29） to （-3.81）. Calculated tDM ages yield values from 1.87 to 1.91 Ga with the tDM.2stg ages of 1.86 to 1.9 Ga. The I-type granites have 143Nd/144Nd ratios between 0.51192 and 0.51195, corresponding to initial eNd （t = 837 Ma） values of 1.22 to 5.63. Calculated tDM ages yield values from 1.0 to 1.38 Ga and the tDM.2stg ages yield values from 0.99 to 1.06 Ga. The S-type granites are distinguished as syn-collision granite, whereas the I-type granites were formed as arc magmas according to the Rb-（Yb＋Ta） and R1-R2 tectonic discrimination diagrams. To conclude, there are two types of spatially associated granite, the Mesoproterozoic S-type granite which were derived from re- melting of upper crustal mudstone and/or clastics and resulted from the convergence of two continental plates, and the mid-Neoproterozoic I-type granite which formed in continental arc and resulted from mantle-derived magma mixed crust material, in the western Yangtze Block. Furthermore, we suggest that collision between the Yangtze and Cathaysia blocks occurred at about 1055 Ma, and caused the S- type granite. The I-type granite related to the subduction of oceanic lithosphere eastward underneath the Yangtze Block in the mid-Neoproterozoic.

Chronological Constraints on Late Paleozoic Collision in the Southwest Tianshan Orogenic Belt, China: Evidence from the Baleigong Granites

The Baleigong granites, located in the western part of the southwestern Tianshan Orogen(Kokshanyan region, China), records late Paleozoic magmatism during the late stages of convergence between the Tarim Block and the Central Tianshan Arc Terrane. We performed a detailed geochronological and geochemical study of the Baleigong granites to better constrain the nature of collisional processes in the Southwest Tianshan Orogen. The LA-ICP-MS U-Pb zircon isotopic analyses indicate that magmatism commenced in the early Permian(~282 Ma). The granite samples, which are characterized by high contents of SiO2(67.68-69.77 wt%) and Al2O3(13.93-14.76 wt%), are alkali-rich and Mg-poor, corresponding to the high-K calc-alkaline series. The aluminum saturation index(A/CNK) ranges from 0.93 to 1.02, indicating a metaluminous to slightly peraluminous composition. Trace element geochemistry shows depletions in Nb, Ta, and Ti, a moderately negative Eu anomaly(δEu=0.40-0.56), enrichment in LREE, and depletion in HREE((La/Yb)N=7.46-11.78). These geochemical signatures are characteristic of an I-type granite generated from partial melting of a magmatic arc. The I-type nature of the Baleigong granites is also supported by the main mafic minerals being Fe-rich calcic hornblende and biotite. We suggest that the high-K, calc-alkaline I-type granitic magmatism was generated by partial melting of the continental crust, possibly triggered by underplating by basaltic magma. These conditions were likely achieved in a collisional tectonic setting, thus supporting the suggestion that closure of the South Tianshan Ocean was completed prior to the Permian and was followed(in the late Paleozoic) by collision between the Tarim Block and the Central Tianshan Arc Terrane.

Petrogenesis of Kejie Granite in the Northern Changning-Menglian Zone, Western Yunnan: Constraints from Zircon U-Pb Geochronology, Geochemistry and Hf Isotope

The Kejie pluton is located in the north of the Changning-Menglian suture zone. The rock types are mainly biotite-granite. Zircon LA-ICP-MS U-Pb dating indicates that the Kejie pluton emplaced at about 80-77 Ma, Late Cretaceous. The Kejie pluton samples are characterized by high SiO2 （71.68%-72.47%）, K2O （4.73%-5.54%）, total alkali （K2O ＋ Na2O = 8.21%-8.53%）, K2O/Na2O ratios （1.36-1.94） and low P2O5 （0.13%-0.17%）, with A/CNK of 1.025-1.055; enriched in U, Th, and K, depleted in Ba, Nb, St, Ti, P and Eu. They are highly fractionated, slightly peraluminous 1-type granite. The two samples of the Kejie pluton give a large variation of εHf（t） values （-5.04 to 1.96） and Hf isotope crustal model ages of 1.16-1.5 Ga. Zircon Hf isotopes and zircon saturation temperatures of whole-rock （801℃-823℃） show that the mantle-derived materials maybe have played a vital role in the generation of the Kejie pluton. The Kejie pluton was most likely generated in a setting associated with the eastward subduction of the neo-Tethys ocean, where intrusion of mantle wedge basaltic magmas in the crust caused the anatexis of the latter, forming hybrid melts, which subsequently experienced high-degree fractional crystallization.

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 ℃.

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.

Effect of cobalt content on electrochemical performance of La-Mg-Ni system (Ce_2Ni_7-type) electrode alloys

In order to improve the cyclic stability of La-Mg-Ni system （Ce2Ni7-type） alloy electrode, small amount of Co was added in La0.75Mg0.25Ni3.5 alloy. The effect of Co on electrochemical performance and microstructure of the alloys were investigated in detail. XRD results showed that the alloys had multiphase structure composed of （La, Mg）2Ni7, LaNi5 and small amount of LaNi2 phases. The discharge capacity of the alloys first increased and then decreased with increasing Co content. At a discharge current density of 900 mA/g, the HRD of the alloy electrodes increased from 81.3% （x=0） to 89.2 % （x=0.2）, and then reduced to 87.8 % （x=0.6）. After 60 charge/discharge cycles, the capacity retention rate of the alloys enhanced from 52.67% to 61.32%, and the capacity decay rate of the alloys decreased from 2.60 to 2.05 mAh/g per cycle with increasing Co content. The obtained results by XPS and XRD showed that the fundamental reasons for the capacity decay of the La-Mg-Ni system （Ce2Ni7-type） alloy electrodes were corrosion and oxidation as well as passivation of Mg and Lain alkaline solution.

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℃.