Designing Novel Sulphate-based Ceramic Materials as Insertion Host Compounds for Secondary Batteries

Rechargeable batteries have propelled the wireless revolution and automobiles market over the past 25 years. Developing better batteries with improved energy density demands unveiling of new cathode ceramic materials with suitable diffusion channels and open framework structure. In this pursuit of achieving higher energy density, one approach is to realize enhanced redox voltage of insertion of ceramic compounds. This can be accomplished by incorporating highly electronegative anions in the cathode ceramics. Building on this idea, recently various sulphate- based compounds have been reported as high voltage cathode materials. The current article highlights the use of sulphate (SO4) based cathodes to realize the highest ever Fe3+/Fe2+ redox potentials in Li-ion batteries (LiFeSO4F fluorosulphate: 3.9V vs Li/Li+) and Na-ion batteries (Na2Fe2(SO4)(3) polysulphate: 3.8V vs Na/Na+). These sulphate-based cathode ceramic compounds pave way for newer avenues to design better batteries for future applications.

Effect of applied pressure on densification of monolithic ZrCx ceramic by reactive hot pressing

The effect of applied pressure on reactive hot pressing (RHP) of zirconium (Zr):graphite (C) in molar ratios of 1:0.5, 1:0.67, 1:0.8, and 1:1 was studied at 1200 degrees C for 60 min. The relative density achievable increased with increasing pressure and ranged from 99% at 4 MPa for ZrC0.5 to 93% for stoichiometric ZrC at 100 MPa. The diminishing influence of pressure on the final density with increasing stoichiometry is attributed to two causes: the decreasing initial volume fraction of the plastically deforming Zr metal which leads to the earlier formation of a contiguous, stress shielding carbide skeleton and the larger molar volume shrinkage during reaction which leads to pore formation in the final stages. A numerical model of the creep densification of a dynamically evolving microstructure predicts densities that are consistent with observations and confirm that the availability of a soft metal is primarily responsible for the achievement of such elevated densification during RHP. The ability to densify nonstoichiometric compositions like ZrC0.5 at pressures as low as 4 MPa offers an alternate route to fabricating dense nonstoichiometric carbides.

Primary and rechargeable zinc-air batteries using ceramic and highly stable TiCN as an oxygen reduction reaction electrocatalyst

Primary and secondary zinc-air batteries based on ceramic, stable, one dimensional titanium carbonitride (TiCN) nanostructures are reported. The optimized titanium carbonitride composition by density functional theory reveals their good activity towards the oxygen reduction reaction (ORR). Electrochemical measurements show their superior performance for the ORR in alkaline media coupled with favourable kinetics. The nanostructured TiCN lends itself amenable to be used as an air cathode material in primary and rechargeable zinc-air batteries. The battery performance and cyclability are found to be good. Further, we have demonstrated a gel-based electrolyte for rechargeable zinc-air batteries based on a TiCN cathode under ambient, atmospheric conditions without any oxygen supply from a cylinder. The present cell can work at current densities of 10-20 mA cm(2) (app. 10 000 mA g(-1) of TiCN) for several hours (63 h in the case of 10 mA cm(-2)) with a charge retention of 98%. The low cost, noble metal-free, mechanically stable and corrosion resistant TiCN is a very good alternative to Pt for metal-air battery chemistry.

Ab initio pair potentials at metal-ceramic interfaces

A systematic approach is proposed to obtain the interfacial interatomic potentials. By inverting ab initio adhesive energy curves for the metal-MgO ceramic interfaces, We derive interfacial potentials between Ag and O2-, Ag and Mg2+, Al and O2-, Al and Mg2+. The interfacial potentials, obtained from this method, demonstrate general features of bondings between metal atoms and ceramic ions.

Microscale mechanics for metal thin film delamination along ceramic substrates

The metal thin film delamination along metal/ceramic interface in the case of large scale yielding is studied by employing the strain gradient plasticity theory and the material microscale effects are considered. Two different fracture process models are used in this study to describe the nonlinear delamination phenomena for metal thin films. A set of experiments have been done on the mechanism of copper films delaminating from silica substrates, based on which the peak interface separation stress and the micro-length scale of material, as well as the dislocation-free zone size are predicted.

The fracture energy of metal fibre reinforced ceramic composites (MFCs)

A model is presented for prediction of the fracture energy of ceramic-matrix composites containing dispersed metallic fibres. It is assumed that the work of fracture comes entirely from pull-out and/or plastic deformation of fibres bridging the crack plane. Comparisons are presented between these predictions and experimental measurements made on a commercially-available composite material of this type, containing stainless steel (304) fibres in a matrix predominantly comprising alumina and alumino-silicate phases. Good agreement is observed, and it's noted that there is scope for the fracture energy levels to be high (~20kJm-2). Higher toughness levels are both predicted and observed for coarser fibres, up to a practical limit for the fibre diameter of the order of 0.5mm. Other deductions are also made concerning strategies for optimisation of the toughness of this type of material. © 2010 Elsevier Ltd.

Damage development in an armor ceramic under quasi-static indentation

The objective of the present study is to assess the capabilities of a recently developed mechanism-based model for inelastic deformation and damage in structural ceramics. In addition to conventional lattice plasticity, the model accounts for microcrack growth and coalescence as well as granular flow following comminution. The assessment is made through a coupled experimental/computational study of the indentation response of a commercial armor ceramic. The experiments include examinations of subsurface damage zones along with measurements of residual surface profiles and residual near-surface stresses. Extensive finite element computations are conducted in parallel. Comparisons between experiment and simulation indicate that the most discriminating metric in the assessment is the spatial extent of subsurface damage following indentation. Residual stresses provide additional validation. In contrast, surface profiles of indents are dictated largely by lattice plasticity and thus provide minimal additional insight into the inelastic deformation resulting from microcracking or granular flow. A satisfactory level of correlation is obtained using property values that are either measured directly or estimated from physically based arguments, without undue reliance on adjustable (nonphysical) parameters. © 2011 The American Ceramic Society.

Growth Mechanism And Corrosion Behavior Of Ceramic Coatings On Aluminum Produced By Autocontrol Ac Pulse Peo

Ceramic coatings are produced on aluminum alloy by autocontrol AC pulse Plasma Electrolytic Oxidation (PEO) with stabilized average current. Transient signal gathering system is used to study the current, voltage, and the transient wave during the PEO process. SEM, OM, XRD and EDS are used to study the coatings evolution of morphologies, composition and structure. TEM is used to study the micro profile of the outer looser layer and inner compact layer. Polarization test is used to study the corrosion property of PEO coatings in NaCl solution. According to the test results, AC pulse PEO process can be divided into four stages with different aspects of discharge phenomena, voltage and current. The growth mechanism of AC PEO coating is characterized as anodic reaction and discharge sintering effect. PEO coating can increase the corrosion resistance of aluminum alloy by one order or two; however, too long process time is not necessarily needed to increase the corrosion resistance. In condition of this paper, PEO coating at 60 min is the most protective coating for aluminum alloy substrate. (C) 2008 Elsevier B.V. All fights reserved.

Interface Fracture Property Of Peo Ceramic Coatings On Aluminum Alloy

This paper combines the four-point bending test, SEM and finite element method to study the interface fracture property of PEO coatings on aluminum alloy. The interface failure mode of the coating on the compression side is revealed. The ceramic coating crack firstly along the 45 degrees to the interface, then the micro crack in the coating deduces the interface crack. The plastic deformation observed by SEM shows excellent adhesion property between the coating and substrate. The plastic deformation in the substrate is due to the interfacial crack extension, so the interface crack mode of PEO coatings is ductile crack. The results of FEM show that the compression strength is about 600 MPa. (C) 2008 Elsevier B.V. All rights reserved.

Peeling Experiments Of Ductile Thin Films Along Ceramic Substrates - Critical Assessment Of Analytical Models

Two types of peeling experiments are performed in the present research. One is for the Al film/Al2O3 substrate system with an adhesive layer between the film and the substrate. The other one is for the Cu film/Al2O3 substrate system without adhesive layer between the film and the substrate, and the Cu films are electroplated onto the Al2O3 substrates. For the case with adhesive layer, two kinds of adhesives are selected, which are all the mixtures of epoxy and polyimide with mass ratios 1:1.5 and 1:1, respectively. The relationships between energy release rate, the film thickness and the adhesive layer thickness are measured during the steady-state peeling process. The effects of the adhesive layer on the energy release rate are analyzed. Using the experimental results, several analytical criteria for the steady-state peeling based on the bending model and on the two-dimensional finite element analysis model are critically assessed. Through assessment of analytical models, we find that the cohesive zone criterion based on the beam bend model is suitable for a weak interface strength case and it describes a macroscale fracture process zone case, while the two-dimensional finite element model is effective to both the strong interface and weak interface, and it describes a small-scale fracture process zone case. (C) 2007 Elsevier Ltd. All rights reserved.