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.

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.

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.

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.

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%）.

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.

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.

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℃.

Magnetic properties and resistivity of a 2:17-type SmCo magnet doped with ZrO_(2)

In order to counteract the demagnetization caused by eddy current loss,widespread attention has been devoted to increasing the resistivity of permanent magnets.We prepared 2:17-type Sm Co magnets doped with different ZrO_(2)contents and investigated the influence of the ZrO_(2)content on the magnetic properties and resistive anisotropism.The results showed that not only was the resistivity of the magnet improved,but,in addition,the coercivity of the magnet was significantly increased.The microstructure was studied with TEM,which showed that ZrO_(2)doping was able to cause a decrease in the lamellar phase density and the growth of cellular structures.The increased grain boundaries and Sm_(2)O_(3)phases were favorable to the improvement of resistivity.The decrease of the lamellar phases caused a narrowing of the resistive anisotropism.The additional Cu in the center of the cellular boundaries was the main reason for the enhancement of Hcj.However,an excessive amount caused an increase of the Zr_6(Fe Co)_(23)phase and a deterioration of the cellular structure,thereby leading to a decrease in coercivity.

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.

Passivation and dissociation of P_(b)-type defects at a-SiO_(2)/Si interface

It is well known that in the process of thermal oxidation of silicon,there are P_(b)-type defects at amorphous silicon dioxide/silicon(a-SiO_(2)/Si)interface due to strain.These defects have a very important impact on the performance and reliability of semiconductor devices.In the process of passivation,hydrogen is usually used to inactivate P_(b)-type defects by the reaction P_(b)+H_(2)→P_(b)H+H.At the same time,P_(b)H centers dissociate according to the chemical reaction P_(b)H→P_(b)+H.Therefore,it is of great significance to study the balance of the passivation and dissociation.In this work,the reaction mechanisms of passivation and dissociation of the P_(b)-type defects are investigated by first-principles calculations.The reaction rates of the passivation and dissociation are calculated by the climbing image-nudged elastic band(CI-NEB)method and harmonic transition state theory(HTST).By coupling the rate equations of the passivation and dissociation reactions,the equilibrium density ratio of the saturated interfacial dangling bonds and interfacial defects(P_(b),P_(b)0,and P_(b)1)at different temperatures is calculated.

Designing a P2-type cathode material with Li in both Na and transition metal layers for Na-ion batteries

P2-type layered oxides have been considered as promising cathode materials for Na-ion batteries,but the capac-ity decay resulting from the Na+/vacancy ordering and phase transformation limits their future large-scale applica-tions.Herein,the impact of Li-doping in different layers on the structure and electrochemical performance of P2-type Na_(0.7)Ni_(0.35)Mn_(0.65)O_(2) is investigated.It can be found that Li ions successfully enter both the Na and transition metal layers.The strategy of Li-doping can improve the cycling stability and rate capability of P2-type layered oxides,which promotes the development of high-performance Na-ion batteries.

THE VALUE OF M_2-TYPE PYRUVATE KINASE IMMUNOASSAY IN THE DIAGNOSIS OF HEPATOCARCINOMA

By using Fab'-enzyme labelled immuno absorbent assay (ELISA) with sensitivity of picogram (10-12 g or pg) level, the M-type pyruvate kinase (M-PyK) in plasma was determined in 47 cases of normal healthy adult and 26 cases of hepatocellular carcinoma (HCC) patient. It was found that the upper limits of normal male and female were 1.1 and 1.4 ng/ml (expressed as M2-PyK) respectively. The plasma M-PyK in HCC patients was significant increased to above 5 times of average normal level, the positive rate was about 95%. In 6 cases of subclinical small hepatocarcinoma and 7 cases of HCC patient with normal serum alpha-fetal protein level, the mean plasma M-PyK value was also increased. Whereas the plasma M-PyK level in acute or chronic hepatitis and other benign diseases were normal. After the HCC being resected, the plasma M-PyK returned to normal, but increased again in the cases of recurrent hepatocarcinoma, suggesting that the increased M-PyK in the plasma of HCC patient was criginated from M2-type PyK in HCC tissue. Therefore, plasma M-PyK may become a new micro-level index of hepatocarcinoma.

Impacts of Melt Spinning and Element Substitution on Electrochemical Characteristics of the La–Mg–Ni-based A₂B₇-Type Alloys

The partial substitution of Zr for La has been performed in order to ameliorate the electrochemical hydrogen storage performances of La–Mg–Ni based A2B7-type electrode alloys. The melt spinning technology was used to prepare the La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1 (x=0, 0.05, 0.1, 0.15, 0.2) electrode alloys. The impacts of the melt spinning and the substituting La with Zr on the structures and the electrochemical hydrogen storage characteristics of the alloys were systemically investigated. The analysis of XRD and TEM reveals that the as-cast and spun alloys have a multiphase structure, composing of two main phases (La, Mg)2Ni7 and LaNi5 as well as a residual phase LaNi2. The electrochemical measurement indicates that both the substitution of Zr for La and the melt spinning ameliorate the electrochemical cycle stability of the alloys dramatically. Furthermore, the high rate discharge ability (HRD) of the as-spun (10 m/s) alloys notably declines with growing the amount of Zr substitution, while it first augments and then falls for the (x=0.1) alloy with rising the spinning rate.