Research progress of alkaline earth metal iron-based oxides as anodes for lithium-ion batteries

Anode materials are an essential part of lithium-ion batteries(LIBs),which determine the performance and safety of LIBs.Currently,graphite,as the anode material of commercial LIBs,is limited by its low theoretical capacity of 372 mA·h·g^(−1),thus hindering further development toward high-capacity and large-scale applications.Alkaline earth metal iron-based oxides are considered a promising candidate to replace graphite because of their low preparation cost,good thermal stability,superior stability,and high electrochemical performance.Nonetheless,many issues and challenges remain to be addressed.Herein,we systematically summarize the research progress of alkaline earth metal iron-based oxides as LIB anodes.Meanwhile,the material and structural properties,synthesis methods,electrochemical reaction mechanisms,and improvement strategies are introduced.Finally,existing challenges and future research directions are discussed to accelerate their practical application in commercial LIBs.

Electrochemical behavior of mesh and plate oxide coated anodes during zinc electrowinning

The catalytic performance of two oxides coated anodes （OCSs） meshes and one OCA plate was investigated in a zinc electrowinning electrolyte at 38 ℃. Their electrochemical behaviors were compared with that of a conventional Pb-0.7%Ag alloy anode. Electrochemical measurements such as cyclic voltammetric, galvanostatic, potentiodynamic, open-circuit potential （OCP） and in situ electrochemical noise measurements were considered. After 2 h of OCP test, the linear polarization shows that the corrosion current density of the Ti/（IrO2-Ta2O5） mesh electrode is the lowest （3.37μA/cm^2） among the three OCAs and shows excellent performance. Additionally, after 24 h of galvanostatic polarization at 50 mA/cm^2and 38 ℃, the Ti/MnO2mesh anode has the highest potential （1.799 V）, followed by the Ti/（IrO2-Ta2O5） plate （1.775 V） and Ti/（IrO2-Ta2O5） mesh （1.705 V） anodes. After 24 h of galvanostatic polarization followed by 16 h of decay, the linear polarization method confirms the sequence obtained after 2 h of OCP test, and the Ti/（IrO2-Ta2O5） mesh attains the lowest corrosion current density. The Ti/（IrO2-Ta2O5） mesh anode also shows better performance after 24 h of galvanostatic polarization with the overpotential lower than that of the conventional Pb-Ag anode by about 245 mV.

Layered Potassium Titanium Niobate/Reduced Graphene Oxide Nanocomposite as a Potassium‑Ion Battery Anode

With graphite currently leading as the most viable anode for potassium-ion batteries(KIBs),other materials have been left relatively underexamined.Transition metal oxides are among these,with many positive attributes such as synthetic maturity,longterm cycling stability and fast redox kinetics.Therefore,to address this research deficiency we report herein a layered potassium titanium niobate KTiNbO5(KTNO)and its rGO nanocomposite(KTNO/rGO)synthesised via solvothermal methods as a high-performance anode for KIBs.Through effective distribution across the electrically conductive rGO,the electrochemical performance of the KTNO nanoparticles was enhanced.The potassium storage performance of the KTNO/rGO was demonstrated by its first charge capacity of 128.1 mAh g^(−1) and reversible capacity of 97.5 mAh g^(−1) after 500 cycles at 20 mA g^(−1),retaining 76.1%of the initial capacity,with an exceptional rate performance of 54.2 mAh g^(−1)at 1 A g^(−1).Furthermore,to investigate the attributes of KTNO in-situ XRD was performed,indicating a low-strain material.Ex-situ X-ray photoelectron spectra further investigated the mechanism of charge storage,with the titanium showing greater redox reversibility than the niobium.This work suggests this lowstrain nature is a highly advantageous property and well worth regarding KTNO as a promising anode for future high-performance KIBs.

Lattice Boltzmann simulation study of anode degradation in solid oxide fuel cells during the initial aging process

For present solid oxide fuel cells(SOFCs),rapid performance degradation is observed in the initial aging process,and the dis-cussion of the degradation mechanism necessitates quantitative analysis.Herein,focused ion beam-scanning electron microscopy was em-ployed to characterize and reconstruct the ceramic microstructures of SOFC anodes.The lattice Boltzmann method(LBM)simulation of multiphysical and electrochemical processes in the reconstructed models was performed.Two samples collected from industrial-size cells were characterized,including a reduced reference cell and a cell with an initial aging process.Statistical parameters of the reconstructed microstructures revealed a significant decrease in the active triple-phase boundary and Ni connectivity in the aged cell compared with the reference cell.The LBM simulation revealed that activity degradation is dominant compared with microstructural degradation during the initial aging process,and the electrochemical reactions spread to the support layer in the aged cell.The microstructural and activity de-gradations are attributed to Ni migration and coarsening.

Coral-Like Yolk–Shell-Structured Nickel Oxide/Carbon Composite Microspheres for High-Performance Li-Ion Storage Anodes

In this study, coral?like yolk–shell?structured NiO/C composite microspheres(denoted as CYS?NiO/C) were prepared using spray pyrolysis. The unique yolk–shell structure was characterized, and the formation mechanism of the structure was proposed. Both the phase separation of the polyvinylpyrrolidone and polystyrene(PS) colloidal solution and the decompo?sition of the size?controlled PS nanobeads in the droplet played crucial roles in the formation of the unique coral?like yolk–shell structure. The CYS?NiO/C microspheres delivered a reversible discharge capacity of 991 mAh g^(-1) after 500 cycles at the current density of 1.0 A g^(-1). The dis?charge capacity of the CYS?NiO/C microspheres after the 1000 th cycle at the current density of 2.0 A g^(-1) was 635 mAh g^(-1), and the capacity retention measured from the second cycle was 91%. The final discharge capacities of the CYS?NiO/C microspheres at the current densities of 0.5, 1.5, 3.0, 5.0, 7.0, and 10.0 A g^(-1) were 753, 648, 560, 490, 440, and 389 mAh g^(-1), respectively. The synergetic e ect of the coral?like yolk–shell structure with well?defined interconnected mesopores and highly conductive carbon resulted in the excellent Li+?ion storage properties of the CYS?NiO/C microspheres.

Enabling High-Performance Sodium Battery Anodes by Complete Reduction of Graphene Oxide and Cooperative In-Situ Crystallization of Ultrafine SnO_(2)Nanocrystals

The main bottleneck against industrial utilization of sodium ion batteries(SIBs)is the lack of high-capacity electrodes to rival those of the benchmark lithium ion batteries(LIBs).Here in this work,we have developed an economical method for in situ fabrication of nanocomposites made of crystalline few-layer graphene sheets loaded with ultrafine SnO_(2)nanocrystals,using short exposure of microwave to xerogel of graphene oxide(GO)and tin tetrachloride containing minute catalyzing dispersoids of chemically reduced GO(RGO).The resultant nanocomposites(SnO_(2)@MWG)enabled significantly quickened redox processes as SIB anode,which led to remarkable full anode-specific capacity reaching 538 mAh g^(−1)at 0.05 A g^(−1)(about 1.45 times of the theoretical capacity of graphite for the LIB),in addition to outstanding rate performance over prolonged charge–discharge cycling.Anodes based on the optimized SnO_(2)@MWG delivered stable performance over 2000 cycles even at a high current density of 5 A g^(−1),and capacity retention of over 70.4%was maintained at a high areal loading of 3.4 mg cm^(−2),highly desirable for high energy density SIBs to rival the current benchmark LIBs.

Soft chemical synthesis and electrochemical properties of tin oxide-based materials as anodes for lithium ion batteries

A novel soft chemical approach was developed to synthesize tin oxide-based powders. The microstructure, morphology, and electrochemical performance of the materials were investigated by X-ray diffraction, scanning electron microscope and electrochemical methods. The results show that the particles of tin oxide-based materials form an interconnected network structure like mesoporous material. The average size of the particles is about 200 nm. The materials deliver a charge capacity of more than 570 mA·h·g-1. And the capacity loss per cycle is about 0.15% after being cycled for 30 times. The good electrochemical performance indicates that tin oxide-based materials are promising anodes for lithium ion batteries.

La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3)-δ−Ce_(0.8)Gd_(0.2)O_(1.9) composite electrodes as anodes in LaGaO_(3)-based direct carbon solid oxide fuel cells

Direct carbon solid oxide fuel cells(DC-SOFCs)are promising,green,and efficient power-generating devices that are fueled by solid carbons and comprise all-solid-state structures.Developing suitable anode materials for DC-SOFCs is a substantial scientific challenge.Herein we investigated the use of La_(0.75)Sr_(0.25)Cr_(0.5)Mn_(0.5)O_(3)-δ−Ce_(0.8)Gd_(0.2)O_(1.9)(LSCM−GDC)composite electrodes as anodes for La_(0.9)Sr_(0.1)Ga_(0.8)Mg_(0.2)O_(3)-δelectrolyte-based DC-SOFCs,with Camellia oleifera shell char as the carbon fuel.The LSCM−GDC-anode DC-SOFC delivered a maximum power density of 221 mW/cm^(2) at 800℃ and it significantly improved to 425 mW/cm^(2) after Ni nanoparticles were introduced into the LSCM−GDC anode through wet impregnation.The microstructures of the prepared anodes were characterized,and the stability of the anode in a DC-SOFC and the influence of catalytic activity on open circuit voltage were studied.The above results indicate that LSCM–GDC anode is promising to be applied in DC-SOFCs.

Measuring Porosity of Anodes in Solid Oxide Fuel Cell (SOFC) through Water Archimedeans Porosimetry

The present research is aimed to measure the porosity of anodes in solid oxide fuel cell through water Archimedeans method. There are various alternatives available to replace fossil fuel cells like nuclear power, wind energy, solar energy, bio fuel, and geothermal and fuel cells. Among all the alternatives of fossil fuel, one form of energy production that stands out from the rest and promises a sustainable future energy is fuel cell. Moreover, it offers many advantages in contrast to other forms of energy generation. An Archimedean approach for water immersion porosimetry is carried out. Some of the results are beyond rational limits, and given negative and sometime above 100 percent porosity. The reasons for these unacceptable results are either due to water ingress into the sample or the sample turns into buoyant due to air in the cling film. The results from Archimedean porosimetry should only be used qualitatively due to errors associated with the results. It is also noted that Archimedean porosimetry is not the ideal technique for measuring the porosity of coated samples. It is suggested that larger samples should be analyzed that will help to minimize the weighing errors.

Fabrication and performance of atmospheric plasma sprayed solid oxide fuel cells with liquid antimony anodes

A solid oxide fuel cell(SOFC)with a liquid antimony anode(LAA)is a potential energy conversion technology for the use of impurity-containing fuels.Atmospheric plasma spraying(APS)technology has become a promising LAASOFC preparation method because of its economy and convenience.In this paper,button SOFCs with different cathode materials and ratios of pore former were prepared by the APS method and were operated at 750C.The effect of the cathode structure on the electrochemical performance of the LAA-SOFCs was analyzed,and an optimized spraying method for LAA-SOFCs was developed.A tubular LAA-SOFC was prepared using the APS method based on the optimized spraying method,and a peak power of 2.5 W was reached.The tubular cell was also measured at a constant current of 2 A for 20 h and was fed with a sulfur-containing fuel to demonstrate its impurity resistance and electrode stability.

Synthesis of Cu_2O/reduced graphene oxide composites as anode materials for lithium ion batteries

A facile way was used to synthesize Cu2O/reduced graphene oxide （rGO） composites with octahedron-like morphology in aqueous solution without any surfactant. TEM images of the obtained Cu2O/rGOs reveal that the Cu2O particles and rGO distribute hierarchically and the primary Cu2O particles are encapsulated well in the graphene nanosheets. The electrochemical performance of Cu2O/rGOs is enhanced compared with bare Cu2O when they are employed as anode materials for lithium ion batteries. The Cu2O/rGO composites maintain a reversible capacity of 348.4 mA？h/g after 50 cycles at a current density of 100 mA/g. In addition, the composites retain 305.8 mA？h/g after 60 cycles at various current densities of 50, 100, 200, 400 and 800 mA/g.

Electrochemical anodic oxidation assisted fabrication of memristors

Owing to the advantages of simple structure,low power consumption and high-density integration,memristors or memristive devices are attracting increasing attention in the fields such as next generation non-volatile memories,neuromorphic computation and data encryption.However,the deposition of memristive films often requires expensive equipment,strict vacuum conditions,high energy consumption,and extended processing times.In contrast,electrochemical anodizing can produce metal oxide films quickly(e.g.10 s) under ambient conditions.By means of the anodizing technique,oxide films,oxide nanotubes,nanowires and nanodots can be fabricated to prepare memristors.Oxide film thickness,nanostructures,defect concentrations,etc,can be varied to regulate device performances by adjusting oxidation parameters such as voltage,current and time.Thus memristors fabricated by the anodic oxidation technique can achieve high device consistency,low variation,and ultrahigh yield rate.This article provides a comprehensive review of the research progress in the field of anodic oxidation assisted fabrication of memristors.Firstly,the principle of anodic oxidation is introduced;then,different types of memristors produced by anodic oxidation and their applications are presented;finally,features and challenges of anodic oxidation for memristor production are elaborated.

Effect of the microstructure of Al 7050-T7451 on anodic oxide formation in sulfuric acid

The effect of the microstructure of an Al 7050-T7451 substrate on the anodic oxide formation in sulfuric acid was studied in this article. The microstructure of the substrate was assessed by optical microscope （OM） and transmission electron microscope （TEM）. The surface and cross-section morphologies of the oxide films were examined by scanning electron microscope （SEM）. The chemical composition of intermetallic particles in the alloys and films was investigated using energy dispersive spectroscope （EDS）. The roles of intermetallic phases and grain or subgrain boundaries on the oxide film formation were researched using the potentiodynamic and potentiostatic polarization technique in sulfuric acid solution. The results show that the transition of coarse intermetallic particles or grain （subgrain） boundaries at the surface of Al alloys can be characterized by potentiodynamic polarization curves. The surface and cross-section micrographs of the anodic layer seem to preserve the microstructure of the substrate. Large cavities in the anodic films are caused by the preferential dissolution of coarse AItCuMg particles and the entrance of Cu-rich remnants into the electrolyte during anodizing. The Al7Cu2Fe particles tend to be occluded in the oxide layer or lose from the oxide surface because of peripheral trenching. Small pores in the films are induced by the dissolution of precipitates in grain or subgrain boundaries. The film surface of recrystallized grain bodies is smooth and homogeneous.

Fabrication and characterization of anodic oxide films on a Ti-10V-2Fe-3Al titanium alloy

Anodic oxide films of the titanium alloy Ti-10V-2Fe-3Al in ammonium tartrate electrolyte without hydrofluoric acid or fluoride were fabricated. The morphology, components, and microstructure of the films were characterized by scanning electron microscopy （SEM）, X-ray photoelectron spectroscopy （XPS）, X-ray diffraction （XRD）, and Raman spectroscopy. The results showed that the films were thick, uniform, and nontransparent. Such films exhibited sedimentary morphology, with a thickness of about 3 μm, and the pore diameters of the deposits ranged from several hundred nanometers to 1.5 μm. The films were mainly titanium dioxide. Some coke-like deposits, which may contain or be changed by OH, NH, C-C, C-O, and C=O groups, were doped in the films. The films were mainly amorphous with a small amount of anatase and rutile phase.

Progress and challenges of carbon-fueled solid oxide fuel cells anode

Carbon-fueled solid oxide fuel cells(CF-SOFCs)can electrochemically convert the chemical energy in carbon into electricity,which demonstrate both superior electrical efficiency and fuel utilisation compared to all other types of fuel cells.However,using solid carbon as the fuel of SOFCs also faces some challenges,the fluid mobility and reactive activity of carbon-based fuels are much lower than those of gaseous fuels.Therefore,the anode reaction kinetics plays a crucial role in determining the electrochemical performance of CF-SOFCs.Herein,the progress of various anodes in CF-SOFCs is reviewed from the perspective of material compositions,electrochemical performance and microstructures.Challenges faced in developing high performance anodes for CF-SOFCs are also discussed.

Chemical dissolution resistance of anodic oxide layers formed on aluminum

Chemically resistant anodic oxide layers were formed on pure aluminum substrates in oxalic acid-sulphuric acid bath.Acid dissolution tests of the obtained anodic layers were achieved in accordance with the ASTM B 680-80 specifications：35mL/L 85% H3PO4＋20g/L CrO3 at 38℃.Influence of oxalic acid concentration,bath temperature and anodic current density on dissolution rate and coating ratio was examined,when the sulphuric acid concentration was maintained at 160g/L.It was found that chemically resistant and compact oxide layers were produced under low operational temperature （5℃） and high current densities （3A/dm^2）.A beneficial effect was observed concerning the addition of oxalic acid （18g/L）.The morphology and the composition of the anodic oxide layer were examined by scanning electron microscopy （SEM）,atomic force microscopy （AFM） and glow-discharge optical emission spectroscopy （GDOES）.

Photoelectrochemical seawater oxidation with metal oxide materials:Challenges and opportunities

Photocatalytic water oxidation is a crucial counter-electrode reaction in the process of photoelectrochemical energy conversion.Despite its importance,challenges remain in effectively and sustainably converting water to oxygen,particularly with readily available and inexpensive electrolyte solutions such as seawater.While metal oxide materials have demonstrated their advantages in promoting efficiency by reducing overpotential and improving light utilization,stability remains limited by corrosion in multicomponent seawater.In this paper,we reviewed the relationship between four basic concepts including photoelectrochemistry,metal oxide,water oxidation and seawater to better understand the challenges and opportunities in photoelectrochemical(PEC)seawater oxidation.To overcome these challenges,the advances in material design,interfacial modification,local environment control and reactor design have been further reviewed to benefit the industrial PEC seawater oxidation.Noticeably,we demonstrate engineered layered metal oxide electrodes and cell structures that enable powerful and stable seawater oxidation.We also outline and advise on the future direction in this area.

Reduced Graphene Oxide-Wrapped FeS_2 Composite as Anode for High-Performance Sodium-Ion Batteries

Iron disulfide is considered to be a potential anode material for sodium-ion batteries due to its high theoretical capacity. However, its applications are seriously limited by the weak conductivity and large volume change, which results in low reversible capacity and poor cycling stability.Herein, reduced graphene oxide-wrapped FeS_2(FeS_2/rGO)composite was fabricated to achieve excellent electrochemical performance via a facile two-step method. The introduction of rGO effectively improved the conductivity,BET surface area, and structural stability of the FeS_2 active material, thus endowing it with high specific capacity, good rate capability, as well as excellent cycling stability. Electrochemical measurements show that the FeS_2/rGO composite had a high initial discharge capacity of 1263.2 mAh gg^(-1) at 100 mA gg^(-1) and a high discharge capacity of 344 mAh gg^(-1) at 10 A gg^(-1), demonstrating superior rate performance. After 100 cycles at 100 mA gg^(-1),the discharge capacity remained at 609.5 mAh g^(-1), indicating the excellent cycling stability of the FeS_2/rGO electrode.

Phenol Wastewater Degradation by Electrocatalytic Oxidation with RuO_2-IrO_2-SnO_2/Ti Anodes in the High Gravity Field

A novel high gravity multi-concentric cylinder electrodes-rotating bed(MCCE-RB) was developed for the electrocatalytic degradation of phenol wastewater in order to enhance the mass transfer with the self-made RuO_2-IrO_2-SnO_2/Ti anodes. The influences of electric current density, inlet liquid circulation flowrate, high gravity factor, sodium chloride concentration,and initial pH value on phenol degradation efficiency were investigated, with the optimal operating conditions determined. The results showed that under the optimal operating conditions covering a current density of 35 mA/cm^2, an inlet liquid circulation flowrate of 48 L/h, a high gravity factor of 20, a sodium chloride concentration of 8.5 g/L, an initial pH value of 6.5, a reaction time of 100 min, and an initial phenol concentration of 500 mg/L, the efficiency for removal of phenol reached 99.7%, which was improved by 10.4% as compared to that achieved in the normal gravity field. The tendency regarding the change in efficiency for removal of phenol, total organic carbon(TOC), and chemical oxygen demand(COD)over time was studied. The intermediates and degradation pathway of phenol were deduced by high performance liquid chromatography(HPLC).

Morphology and growth of porous anodic oxide films on Ti-10V-2Fe-3Al in neutral tartrate solution

Porous anodic oxide films were fabricated galvanostatically on titanium alloy Ti-10V-2Fe-3Al in ammonium tartrate solution with different anodizing time.Scanning electron microscopy(SEM) and field emission scanning electron microscopy(FE-SEM) were used to investigate the morphology evolution of the anodic oxide film.It is shown that above the breakdown voltage,oxygen is generated with the occurrence of drums morphology.These drums grow and extrude,which yields the compression stress.Subsequently,microcracks are generated.With continuous anodizing,porous oxides form at the microcracks.Those oxides grow and connect to each other,finally replace the microcrack morphology.The depth profile of the anodic oxide film formed at 1 800 s was examined by Auger electron spectroscopy(AES).It is found that the film is divided into three layers according to the molar fractions of elements.The outer layer is incorporated by carbon,which may come from electrolyte solution.The thickness of the outer layer is approximately 0.2-0.3 μm.The molar fractions of elements in the intermediate layer are extraordinarily stable,while those in the inner layer vary significantly with sputtering depth.The thicknesses of the intermediate layer and the inner layer are 2 μm and 1.0-1.5 μm,respectively.Moreover,the growth mechanism of porous anodic oxide films in neutral tartrate solution was proposed.