High-Voltage Aqueous Zinc Batteries Achieved by Tri-functional Metallic Bipolar Electrodes

Aqueous rechargeable zinc batteries are very attractive for energy storage applications due to their low cost and high safety.However,low operating voltages limit their further development.For the first time,this work proposes a unique approach to increase the voltages of aqueous zinc batteries by using tri-functional metallic bipolar electrode with good electrochemical activity and ultrahigh electronic conductivity,which not only participates in redox reactions,but also functions as an electrical highway for charge transport.Furthermore,bipolar electrode can replace expensive ion selective membrane to separate electrolytes with different pH;thus,redox couples with higher potential in acid condition and Zn=Zn(OH)^(2-)_(4) couple with lower potential in alkaline condition can be employed together,leading to high voltages of aqueous zinc batteries.Herein,two types of metallic bipolar electrodes of Cu and Ag are utilized based on three kinds of aqueous zinc batteries:Zn–MnO_(2),Zn–I_(2),and Zn–Br_(2).The voltage of aqueous Zn–MnO_(2) battery is raised to 1.84 V by employing one Cu bipolar electrode,which shows no capacity attenuation after 3500 cycles.Moreover,the other Ag bipolar electrode can be adopted to successfully construct Zn–I_(2) and Zn–Br_(2) batteries exhibiting much higher voltages of 2.44 and 2.67 V,which also show no obvious capacity degradation for 1000 and 800 cycles,representing decent cycle stability.Since bipolar electrode can be applied in a large family of aqueous batteries,this work offers an elaborate high-voltage concept based on tri-functional metallic bipolar electrode as a model system to open a door to explore high-voltage aqueous batteries.

High quality Sb-doped SnO2 electrodes with high oxygen evolution potential prepared by in situ hydrothermal synthesis method

High quality Sb-doped SnO2 electrode, with high oxygen evolution potential of 3.0 V, was successfully synthesized on the Ti substrates by in situ hydrothermal synthesis method.

Challenges in Atomic-Scale Characterization of High-k Dielectrics and Metal Gate Electrodes for Advanced CMOS Gate Stacks

The decreasing feature sizes in complementary metal-oxide semiconductor （CMOS） transistor technology will require the replacement of SiO2 with gate dielectrics that have a high dielectric constant （high-k） because as the SiO2 gate thickness is reduced below 1.4 nm, electron tunnelling effects and high leakage currents occur in SiO2, which present serious obstacles to future device reliability. In recent years significant progress has been made on the screening and selection of high-k gate dielectrics, understanding their physical properties, and their integration into CMOS technology. Now the family of hafnium oxide-based materials has emerged as the leading candidate for high-k gate dielectrics due to their excellent physical properties. It is also realized that the high-k oxides must be implemented in conjunction with metal gate electrodes to get sufficient potential for CMOS continue scaling. In the advanced nanoscale Si-based CMOS devices, the composition and thickness of interfacial layers in the gate stacks determine the critical performance of devices. Therefore, detailed atomic- scale understandings of the microstructures and interfacial structures built in the advanced CMOS gate stacks, are highly required. In this paper, several high-resolution electron, ion, and photon-based techniques currently used to characterize the high-k gate dielectrics and interfaces at atomic-scale, are reviewed. Particularly, we critically review the research progress on the characterization of interface behavior and structural evolution in the high-k gate dielectrics by high-resolution transmission electron microscopy （HRTEM） and the related techniques based on scanning transmission electron microscopy （STEM）, including high-angle annular dark- field （HAADF） imaging （also known as Z-contrast imaging）, electron energy-loss spectroscopy （EELS）, and energy dispersive X-ray spectroscopy （EDS）, due to that HRTEM and STEM have become essential metrology tools for characterizing the dielectric gate stacks in the present and future generations of CMOS devices. In Section 1 of this review, the working principles of each technique are briefly introduced and their key features are outlined. In Section 2, microstructural characterizations of high-k gate dielectrics at atomic-scale by electron microscopy are critically reviewed by citing some recent results reported on high-k gate dielectrics. In Section 3, metal gate electrodes and the interfacial structures between high-k dielectrics and metal gates are discussed. The electron beam damage effects in high-k gate stacks are also evaluated, and their origins and prevention are described in Section 4. Finally, we end this review with personal perspectives towards the future challenges of atomic-scale material characterization in advanced CMOS gate stacks.

Metal Free Polymer/Graphite Electrode-Ferricyanides Catholyte System for MFC with High Performance

A Microbial fuel cell(MFC)with metal free polymer/graphite electrodes(150 mm×150 mm)was constructed.The electrodes with flowing channels,which were different in roughness,were designed.No additional catalyst was coated on the electrode,therefore the MFC was cheaper and possessed good durability with high performance.The effect of roughness,K3Fe(CN)6 concentration and sprayed air on the performance of the constructed MFC was investigated.Results showed that the roughness of electrode can significantly affect the performance of MFC.The power density of MFC increased by 1.56 times owing to the arithmetic mean roughness which has increased by 1.41 times.With an increasing K3Fe(CN)6 concentration,the performance of MFC also improves.The MFC with K3Fe(CN)6 only(30 mM)showed the highest power density of 1260 mW/m2,which is by 21.4 times and 1.3 times higher than those of MFCs with spraying air only(59 mW/m2)and with K3Fe(CN)6+air(1005 mW/m2),respectively.This showed that the appropriate concentration of K3Fe(CN)6 can significantly improve the power density,while the air has a negative effect when it is sprayed onto K3Fe(CN)6 catholyte.A coulombic efficiency of 34.2%and an energy efficiency of 13.3%with a COD degradation rate of 73.5%were achieved with MFC using K3Fe(CN)6 only.The overpotentials of MFC were also calculated.It can be seen that both theηohmic andηconcentration were very low as compared to theηactivation,and theηconcentration can be ignored because its effect was less than 3 mV.The theoretical calculation suggested that with an increasing conversion rate of K3Fe(CN)6,the cathode potential decreased and reached 0.31 V at a conversion rate of 0.99.While the anode behaves differently for constant pH and changeable pH as the reaction progresses,which reveals that the buffer solution and removal of protons play an important role in maintaining the anode potential.

The effect of transition metal ions (M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis polyaniline as counter electrodes in dye-sensitized solar cells

The effect of transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)) on the chemical synthesis of polyaniline(PANI) used as a platinum-free counter electrode(CE) in dye-sensitized solar cells(DSSCs) was investigated.PANI was synthesized by co-polymerization of aniline in the presence of different transition metal ions by using potassium dichromate in acidic medium. It was found that the ion doping of PANI showed a certain catalytic activity for the regeneration of traditional iodide/triiodide(I^-/I_3^-) redox couples. The power conversion efficiency(η) of PANI CEs doped with Mn^(2+),Ni^(2+),Co^(2+) (4.41%, 2.36% and 2.10%, respectively) were higher than 1.94%, the value measured for PANI CE without doping. Doping with Cu^(2+)decreased the power conversion efficiency of PANI CE(PANI-Cu^(2+) η = 1.41%). The electrical properties of the PANI, PANI-Ni^(2+), PANI-Co^(2+),PANI-Mn^(2+) and PANI-Cu^(2+) were studied by cyclic voltammetry(CV), impedance(EIS), and Tafel polarization curve. The experimental results confirmed that PANI was affected by the doping of different transition metal ions(M^(2+)=Mn^(2+),Ni^(2+),Co^(2+),Cu^(2+)). These results indicate a potential application of ion doped PANI as counter electrode in cost-effective DSSCs.

In-situ design and construction of lithium-ion battery electrodes on metal substrates with enhanced performances：A brief review

For the ever-growing demand of advanced lithium-ion batteries, it is highly desirable to grow self-supported micro-/nanostructured arrays on metal substrates as electrodes directly. The in-situ growth of electrode materials on the conducting substrates greatly simplifies the electrode fabrication process without using any binders or conductive additives. Moreover, the well-ordered arrays closely connected to the current collectors can provide direct electron transport pathways and enhanced accommodation of strains arisen from lithium ion lithiation/delithiation. This article summarizes our recent work on design and construction of lithium-ion battery electrodes on metal substrates. An aqueous solution-based process and a microemulsion-mediated process have been respectively presented to control the kinetic and thermodynamic processes for the micro-/nanostructured array growth on metal substrates, with particular attention to CuO nanorod arrays and microcog arrays successfully prepared on Cu foil substrates. They can be directly used as binder-free electrodes to build advanced lithium-ion batteries with high energy, high safety and high stability.

Electrocatalytic Activity of Ni/C Electrodes Prepared by Metal Vapor Synthesis For Hydrogen Evolution in Alkaline Solution

The metal vapor synthesis (MVS) methed was used to prepare activatedcarbon supported nickel electrode. The electrocatalytic activity of the electrode forhydrogen evolution reaction(HGR) in alkaline solution was studied. Cathodicpolarization curves showed the electrocatalytic activity of Ni/C electrode prepared byMVS method was higher than that of the one prepared by conventional method.

Review on transition metal compounds based counter electrode for dye-sensitized solar cells

Commercial application of the dye-sensitized solar cells（DSCs） depends on great improvement of the power conversion efficiency and reduction of the fabrication cost. Generally, developing low cost counter electrode catalysts to replace the expensive Pt counter electrode is a feasible path to reduce the production cost of DSCs. In this review article, we summarize the recent progress on the transition metal compound based counter electrode catalysts containing carbides, nitrides, oxides, sulfides, phosphide, selenides, borides, silicide, and telluride toward the regeneration of the traditional iodide redox couple.Moreover, the benefits and drawbacks of each kind of CE catalyst are discussed and the research directions to design new counter electrode catalysts in future research are also proposed.

Uneven deposition on the Al electrode under tension strain

Structural deformation and dendrite formation, which would impact the electrochemical processes of rechargeable metal batteries, are usually observed in the high-energy density metal electrodes. Herein,we design an in-situ optical mechano-electrochemical system to study Al deposition on the Al electrode in non-aqueous Al batteries under non-uniform strain. Inhomogeneous distribution of applied strain is realized by creating an oval hole in the Al electrode. The results of the in-situ experiments suggest that the dense Al deposition, which is related to the evolution of surface morphology and increasing reactive sites, is achieved in the regions of stress concentration. The evolution of surface morphology is monitored by the in-situ tension experiments using scanning electron microscope and atomic force microscope.Besides, a qualitative mathematical model is employed to analyze the changes of the local reaction rate owing to the changed surface morphology and the cracks of oxide film under tensile stress. The results are useful to understand the Al deposition when the mechanical force is applied to the metal electrode.

Electrochemical Properties and Crystal Structure of Rare Earth AB_(3.5)-Type Alloy as Negative Electrode Material in MH-Ni Battery

The electrochemical characteristics and crystal structure of metal hydride electrode of AB_(3.5)-type alloy was studied. The electrochemical properties of the metal hydride electrode were investigated at room temperature and -30 ℃. The partial substitution of Ni by Al element causes an expansion of the lattice cell and increases the specific capacity and rate discharge ability of the alloy.

MICROSTRUCTURE AND ELECTROCHEMICAL CHARACTERISTICS OF Zr_(0.9)Ti_(0.1)(Ni_(1.1)Mn_(0.7)V_(0.2))_x METAL HYDRIDE ELECTRODE

The crystal structure, the phase composition and the electrochemical characteristics of Zr0.9Ti0.1(Ni1.1Mn0.7V0.2)x (x=0.90, 0.95, 1.00, 1.05) alloys were investigated by means of XRD, SEM, EDS and electrochemical measurements. It was shown that all alloys are multiphase with C15 Laves phase as a main phase along with C14 phase and some secondary phases. And the amounts of the C14 phase and secondary phases in the four alloys increases with decreasing x. The results indicated that the various stoichiometric ratios have great effects on the electrochemical characteristics such as the maximum discharge capacity, discharge rate capability and self-discharge properties etc. for Zr0.9Ti0.1(Ni1.1Mn0.7 V0.2)X (x=0.90, 0.95, 1.00, 1.05) alloys. The hyper-stoichiometric Zr0.9 Ti0.1(N1.1Mn0.7 V0.20)1.05 exhibits the maximum discharge capacity of 332mAh-g-1. The C14 phase and secondary phases seems to improve discharge rate capability of the alloys.

Electrode properties and phase composition of Ti_(0.5)Ni_(0.25)Al_(0.25) hydrogen storage alloys and theoretical simulation

Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various temperatures.Electrochemical reaction kinetic parameters were also studied with proper electrochemical techniques.The influence of the secondary corrosion reaction on the anodic linear polarization measurement was also analyzed by theoretical simulation.The results show that,proper ball-milling with nickel powders is beneficial to electrochemical performance.The theoretical simulation proves that,the existence of the side reaction can disturb the measurement of electrochemical reaction kinetic parameters.

Characteristics of multi-component Ml-based hydrogen storage alloys and their hydride electrodes

A series of multi-component M1-based hydrogen storage alloys witha cobalt atomic ratio of 0.40-0.75 were prepared. The electrochemicalproperties under different charge-discharge conditions and PCTcharaceristics measured by electrochemical method were investigated.The addition of other alloying elements for partial substitution ofCo low- ers the hydrogen equilibrium pressure and discharge capacity,but improves the cycling stability and makes the alloys keep nearlythe same rate discharge capability and high-temperature dischargecapability as those of the compared alloy. The reasons werediscussed.

Effect of the anionic composition of sulfolane based electrolytes on the performances of lithium-sulfur batteries

In lithium-sulfur batteries,cell design,specifically electrolyte design,has a key impact on the battery performance.The effect of lithium salt anion donor number(DN)(DN[PF_(6)]^(-)=2.5,DN[N(SO_(2)CF_(3))_(2)]^(-)=5.4,DN[ClO_(4)]^(-)=8.4,DN[SO_(3)CF_(3)]^(-)=16.9,and DN[NO_(3)]^(-)=21.1)on the patterns of lithium-sulfur batteries and lithium metal electrode performances with sulfola ne-based electrolytes is investigated.An increase in DN of lithium salt anions leads to an increase in the depth and rate of electrochemical reduction of sulfur and long-chain lithium polysulfides and to a decrease in those for medium-and short-chain lithium polysulfides.DN of lithium salt anions has weak effect on the discharge capacity of lithium-sulfur batteries and the Coulomb efficiency during cycling,with the exception of LiSO_(3)CF_(3)and LiNO_(3).An increase in DN of lithium salt anions leads to an increase in the cycling duration of lithium metal anodes and to a decrease in the presence of lithium polysulfides.In sulfolane solutions of LiNO_(3)and LiSO_(3)CF_(3),lithium polysulfides do not affect the cycling duration of lithium metal anodes.

Simulation of electro-slag re-melting process of 120t large ingot for nuclear power station and its application

Further research on metallic materials for the super critical rotator and the main pipe line of a nuclear power station is very important for developing the nuclear power industry. In this study, the mathematical model for 120 t large ingot was established, and the computer program ESR3D was developed to simulate the whole electro-slag re-melting (ESR) process. This includes the electrode melting, metallic droplet falling, metal pool forming, metal pool and slag pool rising and moving, installation of top crystallizer, ingot solidifying, etc. The simulated average melting rate of the electrode was in good agreement with that in practical production. The optimized parameters were used to produce 80-120 t large ingots, and the quality of the ingots satisfied the specifications of nuclear power and the super critical generating unit.

The interfacial engineering of metal electrodes for high-specific-energy and long-lifespan batteries

High-specific-energy batteries with long-lifespan are the development aspiration for energy storage applications.Metal electrodes with high specific capacity and low reduction potential are potential candidates for next-generation high-specific-energy batteries.Nevertheless,the stability of the metal electrode batteries is constantly suffered from the unstable interface issue during the plat-ing/stripping process,such as dendrite formation,dynamic evolution of solid electrolyte interphase,and other accompanied side reactions.To solve these challenges,numerous researches have been intensively studied based on the interfacial engineering of metal electrodes,including electrode configuration optimization,interfacial chemistry regulation and solid-solid interface construc-tion,and the recent progress is elaborately introduced in this paper.Nevertheless,the dendrite issues cannot be entirely prohibited in solid metal electrodes,which motivate the search for potential alternatives.Liquid-metal electrodes with completely reversible structural changes and high mass transfer rate are rendered as an effective approach to solve the dendrite problem.Therefore,the development of liquid metal electrode batteries is reviewed in this paper,in which the interfacial issues are explicated and some commendable achievements are summarized.In the end,the implementation of interfacial engineering and the development roadmap of the metal electrode batteries are prospected.

Developing artificial solid-state interphase for Li metal electrodes:recent advances and perspective

The failure of Li metal anodes can be attributed to their unstable electrode/electrolyte interface,especially the continuous formation of solid electrolyte interphase(SEI)and dendrite growth.To address this challenge,scholars proposed the construction of artificial SEI(ASEI)as a promising strategy.The ASEI mainly homoge-nizes the distribution of Li+,mitigates dendrite growth,facilitates Li+diffusion,and protects the Li metal anode from electrolyte erosion.This review comprehensively summarizes the recent progress in the construction of ASEI layers in terms of their chemical composition.Fundamental understanding of the mechanisms,design principles,and functions of the main components are analyzed.We also propose future research directions to facilitate the in-depth study of ASEI and its practical applications in Li metal batteries.This review offers perspectives that will greatly contribute to the design of practical Li metal electrodes.

Degradation Behavior of Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

The degradation mechanism of electrochemical performance of sealed type nickel/metal hydride batteries was investigated. The results indicate that the degradation behavior of Ni/MH battery is not only owing to the lack of electrolyte, but also the deterioration of the active materials on the positive and negative electrodes of Ni/MH batteries. Scanning electron micrographs (SEM), X ray diffraction (XRD) and laser granularity analyses are presented. The particle pulverization and oxidation during charge/discharge are identified as the main causes for deterioration of the negative and positive electrode in nickel/metal hydride batteries, as well as the cross section cracking of both anode and cathode.

Modeling, Simulation and Control of Pulsed DE-GMA Welding Process for Joining of Aluminum to Steel

Joining of aluminum to steel has attracted significant attention from the welding research community,automotive and rail transportation industries.Many current welding methods have been developed and applied,however,they can not precisely control the heat input to work-piece,they are high costs,low efficiency and consist lots of complex welding devices,and the generated intermetallic compound layer in weld bead interface is thicker.A novel pulsed double electrode gas metal arc welding（Pulsed DE-GMAW）method is developed.To achieve a stable welding process for joining of aluminum to steel,a mathematical model of coupled arc is established,and a new control scheme that uses the average feedback arc voltage of main loop to adjust the wire feed speed to control coupled arc length is proposed and developed.Then,the impulse control simulation of coupled arc length,wire feed speed and wire extension is conducted to demonstrate the mathematical model and predict the stability of welding process by changing the distance of contact tip to work-piece（CTWD）.To prove the proposed PSO based PID control scheme’s feasibility,the rapid prototyping experimental system is setup and the bead-on-plate control experiments are conducted to join aluminum to steel.The impulse control simulation shows that the established model can accurately represent the variation of coupled arc length,wire feed speed and the average main arc voltage when the welding process is disturbed,and the developed controller has a faster response and adjustment,only runs about 0.1 s.The captured electric signals show the main arc voltage gradually closes to the supposed arc voltage by adjusting the wire feed speed in 0.8 s.The obtained typical current waveform demonstrates that the main current can be reduced by controlling the bypass current under maintaining a relative large total current.The control experiment proves the accuracy of proposed model and feasibility of new control scheme further.The beautiful and smooth weld beads are also obtained by this method.Pulsed DE-GMAW can thus be considered as an alternative method for low cost,high efficiency joining of aluminum to steel.

Mechanism of RE on the Electrochemical Properties of Multicomponent Hydrogen Storage Alloys of RENi^5 Type

The electrochemical properties of RE(NiCoMnTi) 5 hydrogen storage alloy with different composition of rare earth(RE=La 1-x-y-z Ce x Nd y Pr z ) components were systematically examined To display the effect of rare earth elements on the electrode properties, the comprehensive electrochemical property graphs including the discharge capacity, high dischargeability and cycling life of alloy electrode vs quasi ternary rare earth composition of multicomponent alloys were drawn by first dividing the component elements into two groups with fixed ratios between the two groups and then using a computer program for engineering graphics By the optimizaiton of the La∶Ce∶Nd∶Pr ratio, the alloy RE(NiCoMnTi) 5 shows a maximum capacity of 290 mAh/g and good cycling stability The higher capacity was due to the larger unit cell volume of the alloy with RE=La 0 4 Ce 0 1 Nd 0 3 Pr 0 2 , as determined by X ray diffraction analysis