A Modification of LiMn2O4 by Ionic Conductive Agent and Electronic Conductive Agent Coating

Carbon was used as electronic conductive agent, and metasilicic acid lithium (Li2SiO3) as ionic conductive agent, the two factors were investigated cooperatively. We evaluated their effect by using spherical spinel LiMn2O4 which prepared ourselves as cathode material. Then Li2SiO3/carbon surface coating on LiMn2O4 (LMO/C/LSO) which Li2SiO3 inside and carbon/Li2SiO3 coated LiMn2O4 (LMO/LSO/C) were prepared, All of materials were characterized by X-ray diffraction (XRD) and electrochemical test;spherical LiMn2O4 was characterized by scanning electron microscopy (SEM);and coated materials were characterized by transmission electron microscopy (TEM). While uncoated spinel LiMn2O4 maintained 72% of capacity in 60 cycles by the rate of 0.2C, and LMO/LSO/C showed the best electrochemical performance, 89% of the initial capacity remained after 75 cycles at 0.2C. Furthermore, the rate performance of LMO/LSO/C also improved obviously, about 30 mAh·g-1 of capacity attained at the rate of 5C, higher than LMO/C/LSO and bare LiMn2O4.

Metal-nitrogen-doped hybrid ionic/electronic conduction triple-phase interfaces for high-performance all-solid-state lithium-sulfur batteries

The point-to-point contact mechanism in all-solid-state Li-S batteries(ASSLSBs)is not as efficient as a liquid electrolyte which has superior mobility in the electrode,resulting in a slower reaction kinetics and inadequate ionic/electronic conduction network between the S(or Li_(2)S),conductive carbon,and solid-state electrolytes(SSEs)for achieving a swift(dis)charge reaction.Herein,a series of hybrid ionic/electronic conduction triple-phase interfaces with transition metal and nitrogen co-doping were designed.The graphitic ordered mesoporous carbon frameworks(TM-N-OMCs;TM=Fe,Co,Ni,and Cu)serve as hosts for Li_(2)S and Li_(6)PS_(5)Cl(LPSC)and provide abundant reaction sites on the triple interface.Results from both experimental and computational research display that the combination of Cu-N co-dopants can promote the Li-ion diffusion for rapid transformation of Li_(2)S with adequate ionic(6.73×10^(−4)S·cm^(−1))/electronic conductivities(1.77×10^(−2)S·cm^(−1))at 25℃.The as-acquired Li_(2)S/Cu-N-OMC/LPSC electrode exhibits a high reversible capacity(1147.7 mAh·g^(−1))at 0.1 C,excellent capacity retention(99.5%)after 500 cycles at 0.5 C,and high areal capacity(7.08 mAh·cm^(−2)).

Tuning the electronic conductance of REH_(x)(RE=Nd,Ce,Pr)by structural deformation

Hydride ion(H-)conductors have drawn much attention due to their potential applications in hydrideion-based devices.Rare earth metal hydrides(REH_(x))have fast H-conduction which,unfortunately,is accompanied by detrimental electron conduction preventing their application as ion conductors.Here,REH_(x)(RE=Nd,Ce,and Pr)with varied grain sizes,rich grain boundaries,and defects have been prepared by ball milling and subsequent sintering.The electronic conductivity of the ball-milled REH_(x)samples can be reduced by 2-4 orders of magnitude compared with the non-ball-milled samples.The relationship of electron conduction and miscrostructures in REH_(x)is studied and discussed based on experimental data and previously-proposed classical and quantum theories.The H-conductivity of all REH_(x)is about 10^(-4)to 10^(-3)S cm^(-1)at room temperature,showing promise for the development of H-conductors and their applications in clean energy storage and conversion.

A review on electronically conducting polymers for lithium-sulfur battery and lithium-selenium battery:Progress and prospects

Lithium-sulfur(Li-S) batteries and lithium-selenium(Li-Se) batteries,as environmental protection energy storage systems with outstanding theoretical specific capacities and high energy densities,have become the hotspots of current researches.Besides,elemental S(Se) raw materials are widely sourced and their production costs are both low,which make them considered one of the new generations of high energy density electrochemical energy storage systems with the most potential for development.However,poor conductivity of elemental S/Se and the notorious "shuttle effect" of lithium polysulfides(polyselenides) severely hinder the commercialization of Li-S/Se batteries.Thanks to the excellent electrical conductivity and strong absorption of lithium polysulfide(polyselenide) about electronically conducting polymer,some of the above thorny problems have been effectively alleviated.The review presents the fundamental studies and current development trends of common electronically conducting polymers in various components of Li-S/Se batteries,which involves polyaniline(PANI) polypyrrole(PPy),and polythiophene(PTh) with its derivatives,e.g.polyethoxythiophene(PEDOT) and poly(3,4-ethylene dioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS).Finally,the review not only summarizes the research directions and challenges facing the application of electronically conducting polymers,but also looks forward to the development prospects of them,which will provide a way for the practical use of electronically conducting polymers in Li-S/Se batteries with outstanding electrochemical properties in the short run.

Effect of ZrO_2 (9mol% Y_2O_3) coating thickness on the electronic conductivity of Mg-PSZ oxygen sensors

The ZrO2 (9mol% Y2O3) coating was prepared evenly on the surface of MgO partially stabilized zirconia (Mg-PSZ) tube (oxygen sensor probe) by dipping the green Mg-PSZ tube in a ZrO2 (9mol% Y2O3) slurry and then co-firing at 1750°C for 8 h. The double-cell method was employed to measure the electronic conductivity parameter and exam the reproducibility of the coated Mg- PSZ tube. The experimental results indicate that the good thermal shock resistance of the Mg-PSZ tube can be retained when the coating thickness is not more than 3.4 μm. The ZrO2 (9mol% Y2O3) coating reduces the electronic conductivity parameter remarka- bly, probably due to the lower electronic conductivity of Y2O,-stabilized ZrO2 than that of MgO-stabilized ZrO2. Moreover, the ZrO2 (9mol% Y2O3) coating can improve the reproducibility and accuracy of the Mg-PSZ tube significantly in the low oxygen measure- ment. The smooth surface feature and lower electronic conductivity of the coated Mg-PSZ tube should be responsible for this im- provement.

Study on Electronic Conductivity of CaO-SiO2-Al2O3-FeOx Slag System

A study on electronic conductivity of CaO-SiO2-Al2O3-FeOxslag system with Wagner polarization technique was carried out.The experimental data show that electronic conductivity is consisted of free electron conductivity and electron hole conductivity and both are related to the content of Fe3+and Fe2+.Free electron conductivity is decreasing and electron hole conductivity is increasing while Fe3+changes to Fe2+.There is a maximum electronic conductivity at some ratio of ferric ions Fe3+to total ion content.Under the experimental conditions,the electronic conductivity is in the range of 10-4—10-2S/cm.

IR, 1H NMR, Electronic Properties and Conductivity Studies of N1 ,N4-Bis（Diphme）Benzene-l,4-Diamine Chloride Zirconium （IV） [{（Ar）2NC6H5N（Ar）2}ZrCl4] （Ar = C6H5）

A range of new compounds such as N1,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6HsN（Ar）z}ZrCl4] （Ar = C6H5） complex counting the chelating amine and chloride in position trans have been prepared. Well-defined NI,N4-bis（diphenylmethlene）benzene-l,4-diamine zirconium （IV） chloride [{（Ar）2NC6H5N（Ar）2}ZrCl4] （Ar = C6H5） was obtained by stoichiometric addition of {（Ar）2NC6H5N（Ar）2} （Ar = C6H5） and {ZrC14} in ethanol at reflex temperature. IR, 1H NMR, electronic properties using hyperchem program study has been improved for this compound such as bond distance, and this compound was also defined as electric conductivity which proves to be useful for conductively compound.

Microstructure and properties of electronic packaging shell with high silicon carbide aluminum-base composites by semi-solid thixoforming

The electronic packaging shell with high silicon carbide aluminum-base composites was prepared by semi-solid thixoforming technique. The flow characteristic of the Si C particulate was analyzed. The microstructures of different parts of the shell were observed by scanning electron microscopy and optical microscopy, and the thermophysical and mechanical properties of the shell were tested. The results show that there exists the segregation phenomenon between the Si C particulate and the liquid phase during thixoforming, the liquid phase flows from the shell, and the Si C particles accumulate at the bottom of the shell. The volume fraction of Si C decreases gradually from the bottom to the walls. Accordingly, the thermal conductivities of bottom center and walls are 178 and 164 W·m-1·K-1, the coefficients of thermal expansion(CTE) are 8.2×10-6 and 12.6×10-6 K-1, respectively. The flexural strength decreases slightly from 437 to 347 MPa. The microstructures and properties of the shell show gradient distribution.

Electronic Transport of Uranium Mononitride

We investigated the electronic heat capacity, thermal conductivity, and resistivity of UN using Quantum Espresso and EPW code. GGA, PBEsol functional was used. The calculated electronic heat coefficient was found to be significantly reduced (0.0176 J⋅mol-1⋅K-2 versus 0.0006 J⋅mol-1⋅K-2) when the non-local hybrid functional (B3LYP) was used. Furthermore, we calculated electrical resistivity using a very transparent Ziman’s formula for metals with the Eliashberg transport coupling function as implemented in EPW code for non-spin-polarized calculations. The number of mobile electrons in UN, as a function of temperature, was derived from the ratio of the calculated resistivity and available experimental data. The electronic thermal conductivity was evaluated from the calculated electronic resistivity via Wiedemann-Franz law with the number of mobility electrons (nav) incorporated (averaged over the temperature range 300 K - 1000 K). Both the electronic thermal conductivity and resistivity, as calculated using newly evaluated nav, compare well with experimental data at ~700 K, but to reproduce the observed trend as a function of temperature, the number of mobile electrons must decrease with the temperature as evaluated.

In Situ-Constructed Li_(x)MoS_(2)with Highly Exposed Interface Boosting High-Loading and Long-Life Cathode for All-Solid-State Li-S Batteries

As the persistent concerns regarding sluggish reaction kinetics and insufficient conductivities of sulfur cathodes in all-solid-state Li-S batteries(ASSLSBs),numerous carbon additives and solid-state electrolytes(SSEs)have been incorporated into the cathode to facilitate ion/electron pathways around sulfur.However,this has resulted in a reduced capacity and decomposition of SSEs.Therefore,it is worth exploring neotype sulfur hosts with electronic/ionic conductivity in the cathode.Herein,we present a hybrid cathode composed of few-layered S/MoS_(2)/C nanosheets(<5 layers)that exhibits high-loading and long-life performance without the need of additional carbon additives in advanced ASSLSBs.The multifunctional MoS_(2)/C host exposes the abundant surface for intimate contacting sites,in situ-formed LixMoS_(2)during discharging as mixed ion/electron conductive network improves the S/Li2S conversion,and contributes extra capacity for the part of active materials.With a high active material content(S+MoS_(2)/C)of 60 wt%in the S/MoS_(2)/C/Li_(6)PS_(5)Cl cathode composite(the carbon content is only~3.97 wt%),the S/MoS_(2)/C electrode delivers excellent electrochemical performance,with a high reversible discharge capacity of 980.3 mAh g^(-1)(588.2 mAh g^(-1)based on the whole cathode weight)after 100 cycles at 100 mA g^(-1).The stable cycling performance is observed over 3500 cycles with a Coulombic efficiency of 98.5%at 600 mA g^(-1),while a high areal capacity of 10.4 mAh cm^(-2)is achieved with active material loading of 12.8 mg cm^(-2).

Investigating Stability Properties for Transition Metal Carbonate Precursors Using Universal Cluster Expansion Technique(UNCLE)as Cathodes for Li-Ion Batteries

The universal cluster expansion technique was used in this study to determine the binary phase diagrams for the transition metal carbonate precursors MCO3(M:Mn,Ni,Co).The use of mixed cathode materials in lithium-ion batteries such as NMC(Ni,Mn and Co)formulations,is a strategic approach to optimize performance,enhance safety and address cost and environmental considerations in the rapidly evolving field of energy storage.This study focuses on the cost issue related to lithium ion batteries by investigating the manganese rich NMC since manganese is more abundant and cost-effective.We doped MnCO3 with nickel and doped MnCO3 with cobalt then ran cluster expansion calculations to generate binary phases.The binary phase diagrams generated indicated that doping MnCO3 with nickel favours the Mn-rich side,while doping MnCO3 with cobalt favours 50%Mn-rich and 50%Co-rich.We further extracted the most stable structures from both binary diagrams and determined their electronic,mechanical and vibrational stabilities using DFT(density functional theory)calculations within the LDA(local gradient approximation)with Hubbard parameter(U).The electronic properties revealed that both materials are semiconductors due to their narrow energy band gap obtained while the mechanical properties showed that structures are mechanically stable since their necessary conditions for trigonal and triclinic systems were satisfied.

CNTs@S composite as cathode for all-solid-state lithium-sulfur batteries with ultralong cycle life

The main challenges in development of traditional liquid lithium-sulfur batteries are the shuttle effect at the cathode caused by the polysulfide and the safety concern at the Li metal anode arose from the dendrite formation.All-solid-state lithium-sulfur batteries have been proposed to solve the shuttle effect and prevent short circuits.However,solid-solid contacts between the electrodes and the electrolyte increase the interface resistance and stress/strain,which could result in the limited electrochemical performances.In this work,the cathode of all-solid-state lithium-sulfur batteries is prepared by depositing sulfur on the surface of the carbon nanotubes(CNTs@S)and further mixing with Li10GeP2S12 electrolyte and acetylene black agents.At 60℃,CNTs@S electrode exhibits superior electrochemical performance,delivering the reversible discharge capacities of 1193.3,959.5,813.1,569.6 and 395.5 mAhg^-1 at the rate of 0.1,0.5,1,2 and 5 C,respectively.Moreover,the CNTs@S is able to demonstrate superior high-rate capability of 660.3 mAhg^-1 and cycling stability of 400 cycles at a high rate of 1.0 C.Such uniform distribution of the CNTs,S and Li10GeP2S12 electrolyte increase the electronic and ionic conductivity between the cathode and the electrolyte hence improves the rate performance and capacity retention.

ABSTRACTS——From Journal of Iron and Steel Research(in Chinese)

The electrochemical nature of reaction between melt and slag in a closed system was worked out. Experimental results demonstrated that both the rate and reaction extent increase when the electronic conductor or voltage was applied between melt and slag. The bigger the contact area of the conductor with melts is, the faster the reaction rate is. With the increase of applied voltage which is beneficial for electron's migration between metal and slags, the rate and extent of reaction increase.

Study on rare earth electrolyte of SDC-LSGM

Ce0.85Sm0.15O1.925 （SDC） and La0.9Sr0.1Ga0.5Mg0.2O2.85 （LSGM） were synthesized using Glycine-Nitrate Process （GNP）, and the composite electrolytes were prepared by mixing SDC and LSGM. An X-ray diffraction pattern indicated that the mixture of SDC and LSGM consisted of their original phases after heating at 1450 ℃ for 10 h. The electronic conductivity of SDC-LSGM composite electrolytes were measured by direct current polarization method using Hebb-Wagner ion blocking cell at 700-800 ℃ in the oxygen partial pressure range of 104-10-20 MPa and compared with the results of SDC. Typical polarization curves, which were theoretically predicted, were observed on all the samples. The slopes of lgσe-lgPo2 plot for all the composite electrolytes agreed with the theoretically predicted value of-1/4 at some intermediate oxygen partial pressures and -1/6 at low oxygen partial pressure. The electronic conductivity of SDC-LSGM composite electrolytes decreased with the increase in LSGM content, whereas the ionic transport number ti of all the samples increased with the increase in LSGM content.

Architecture engineering of carbonaceous anodes for high-rate potassium-ion batteries

The limited lithium resource in earth's crust has stimulated the pursuit of alternative energy storage technologies to lithium-ion battery.Potassium-ion batteries(KIBs)are regarded as a kind of promising candidate for large-scale energy storage owing to the high abundance and low cost of potassium resources.Nevertheless,further development and wide application of KIBs are still challenged by several obstacles,one of which is their fast capacity deterioration at high rates.A considerable amount of effort has recently been devoted to address this problem by developing advanced carbonaceous anode materials with diverse structures and morphologies.This review presents and highlights how the architecture engineering of carbonaceous anode materials gives rise to high-rate performances for KIBs,and also the beneficial conceptions are consciously extracted from the recent progress.Particularly,basic insights into the recent engineering strategies,structural innovation,and the related advances of carbonaceous anodes for high-rate KIBs are under specific concerns.Based on the achievements attained so far,a perspective on the foregoing,and proposed possible directions,and avenues for designing high-rate anodes,are presented finally.

Hydrogen Permeation Properties of Perovskite-type BaCe_(0.9)Mn_(0.1)O_(3-δ)Dense Ceramic Membrane

The electrical conduction properties of dense BaCe0.9Mn0.1O3-d (BCM10) membrane were investigated in the temperature range of 600-900oC. High ionic and electronic conductivities at elevated temperatures make BCM10 a potential ceramic material for hydrogen separation. Hydrogen permeation through BCM10 membranes was studied using a high- temperature permeation cell. Little hydrogen could be detected at the sweep side. However, appreciable hydrogen can permeate through BCM10 membrane coated with porous platinum black, which shows that the process of hydrogen permeation through BCM10 membranes was controlled by the catalytic decomposition and recomposition of hydrogen on the surfaces of BCM10 membranes.

Preparation and characteristic of NASICON ceramics

Hot-pressed sintering was employed to prepare the sodium super ionic conductor (Na1+xZr2SixP3-xO12, 1.8≤x≤2.2) ceramics and compare with the sample obtained from normal-press sintering. The phase formation, density, and conductivity of the hot-press sintered and the normal-press sintered samples were investigated in detail. Results show that the density of NASICON ceramics and the degree of crystallization can be improved by hot-press process efficiently. The density of the sample sintered by normal sintering is obviously lower than that sintered by hot press. XRD analysis indicates all the hot press sintered samples contain mainly monoclinic NASICON and no ZrO2 phase was found. The ionic conductivity of normal-press sintered sample is much lower than that of hot-press sintered sample. When the composition is close to Na3Zr2Si2PO12, the dc conductivities of the hot press sintered samples were in the order of 10-3 S·cm-1. The variation of the ac conductivity with frequency in the high frequency region agrees with the power law feature of σ(ω)∝ωn(0<n<1).

Influence of Conductivity of Slag on Decarburization Reaction

By altering the electrochemical properties of slag, the decarburization reaction of Fe3+-based slag withFe-C droplet was studied. The results showed that a lot of free electrons and holes exist in the slag containing transition metal oxides (such as TiO2 and Fe2O3). So electronic conduction in the slag increases. Finally, it led to the increment of the decarburization reaction rate between slag and Fe-C droplet, and mass fraction of carbon remaining indroplet decreases to a lower level.

Understanding De-protonation Induced Formation of Spinel Phase in Li-rich Layered Oxides for Improved Rate Performance

Constructing layered-spinel composites is important to improve the rate performance of lithium-rich layered oxides.However,up to now,the effect of microstructure of composites on the rate performance has not been well investigated.In this study,a series of samples were prepared by a simple protonation and de-protonation for the pristine layered material(LiMnNiCoO)obtained by sol-gel method.The characterizations of XRD,Raman and oxidation-reduction potentials of charge-discharge curves demonstrated that these samples after de-protonation are layered-spinel composites.When these composites were tested as a cathode of lithium-ion batteries,the sample treated with 0.1 M of nitric acid exhibited higher discharge capacities at each current density than that of other composites.The outstanding rate performance is attributed to the high concentration of conduction electron resulting from the low average valence state(44.2%of Ni)as confirmed by its high conductivity(1.124×10??mat39800Hz)and ambient temperature magnetic susceptibility(8.40×10emu/Oe?mol).This work has a guiding significance for the synthesis of high rate performance of lithium battery cathode materials.

Discrete Model of Plasticity and Failure of Crystalline Materials

Within the framework of a discrete model of the nuclei of linear and planar defects, the variational principles of sliding in translational and rotational plasticity, fracture by separation (cleavage) and shear (shearing) in crystalline materials are considered. The analysis of mass transfer fluxes near structural kinetic transitions of slip bands into cells, cells into fragments of deformation origin, destruction by separation and shear for fractal spaces using fractional Riemann-Liouville derivatives, local and global criteria of destruction is carried out. One of the possible schemes of the crack initiation and growth mechanism in metals is disclosed. It is shown that the discrete model of plasticity and fracture does not contradict the known dislocation models of fracture and makes it possible to abandon the kinetic concept of thermofluctuation rupture of interatomic bonds at low temperatures.