In-situ investigation of atmospheric corrosion behavior of bronze under thin electrolyte layers using electrochemical technique

The atmospheric corrosion behavior of bronze under thin electrolyte layer （TEL） with different thicknesses was monitored using cathodic polarization curves, open circuit potential （OCP） and electrochemical impedance spectroscopy （EIS）. Cathodic polarization result indicates that the cathodic limiting current density increases with decreasing the TEL thickness. EIS result shows that the corrosion rate increases with decreasing the TEL thickness at the initial stage because the corrosion is dominated by the cathodic process, whereas after long immersion time, the corrosion degree with the TEL thickness is in the sequence of 150 μm 〉 310 μm〉 10μm ≈ bulk solution 〉 57 μm. The measurements of OCP and EIS present in-situ electrochemical corrosion information and their results are in good agreement with that of physical characterizations.

An overview of electrochemical,non-electrochemical and analytical approaches for studying corrosion in magnesium and its alloys

Corrosion is a pervasive phenomenon affecting materials across a multitude of scales,from the atomic to the macroscopic.This review paper presents a comprehensive examination of the methodologies employed in the analysis of magnesium corrosion,including electrochemical,non-electrochemical and analytical approaches,emphasizing the need for a diverse array of analytical tools to understand the complex interplay between corrosion,microstructure,and the dissolution mechanisms of magnesium alloys.The research showcases the utility of specific tools like SEM/EDS and SKPFM for targeted site analysis,while XPS and FTIR provide a broader perspective on specimen surfaces.The paper also discusses the value of in-situ analysis techniques,which allow for the real-time observation of corrosion processes,offering a dynamic view of the emergence and evolution of corrosion products.These in-situ methods stand in contrast to ex-situ analyses,which only permit post-experimental evaluation.By highlighting the capabilities of various analytical tools,from those that reveal surface layer details to those that probe deeper structures,and from those that detect primary elements to those that trace minute quantities of impurities,this study underscores the intricate nature of corrosion and the critical role of advanced analytical techniques in fostering a deeper understanding of material degradation.The findings advocate for the increased application of in-situ analysis in magnesium corrosion research,as it provides a more immediate and accurate depiction of corrosion dynamics,potentially leading to more effective corrosion prevention and control strategies.

Corrosion Measurements of Reinforcing Steel by Different Electrochemical Techniques

Electrochemical techniques of the corrosion measurements of reinforcing steeI in concrete have been evaluated. These techniques include half-cell potential measurements, impressed voltage method, impressed current method and potentiostatic polarization technique. The results of corrosion behaviour of the steel in both 5%NaCl and 5%MgSO4 show that each electrochemical technique provides some information about the condition of the steel bar or the corrosivity of the environment being evaluated, yet none provides a complete data regarding the corrosion resistance of reinforcing steel in aggressive media

Study of Corrosion Resistance of Laser Welded Au-Pd-Ag-In Alloy Using Electrochemical Techniques

The aim of this work was to evaluate the corrosion resistance of AuPdAgIn alloy, submitted to laser beam welding, in 0.9% NaCl solution, using electrochemical techniques. Measures of the open circuit potential (OCP) versus time were applied to electrochemical experiments, as well as potentiodynamic direct scanning (PDS) and electrochemical impedance spectroscopy (EIS) on AuPdAgIn alloy, submitted to laser beam welding in 0.9% NaCl solution. Some differences observed in the microstructure can explain the results obtained for corrosion potential, Ecorr, and corrosion resistance, Rp. EIS spectra have been characterized by distorted capacitive components, presenting linear impedance at low frequencies, including a non-uniform diffusion. The area of the laser weld presented corrosion potential slightly superior when compared to the one of the base metal. The impedance results suggest the best resistant corrosion behavior for laser weld than base metal region. This welding process is a promising alternative to dental prostheses casting.

A Review of In‑Situ Techniques for Probing Active Sites and Mechanisms of Electrocatalytic Oxygen Reduction Reactions

Electrocatalytic oxygen reduction reaction(ORR)is one of the most important reactions in electrochemical energy technologies such as fuel cells and metal–O2/air batteries,etc.However,the essential catalysts to overcome its slow reaction kinetic always undergo a complex dynamic evolution in the actual catalytic process,and the concomitant intermediates and catalytic products also occur continuous conversion and reconstruction.This makes them difficult to be accurately captured,making the identification of ORR active sites and the elucidation of ORR mechanisms difficult.Thus,it is necessary to use extensive in-situ characterization techniques to proceed the real-time monitoring of the catalyst structure and the evolution state of intermediates and products during ORR.This work reviews the major advances in the use of various in-situ techniques to characterize the catalytic processes of various catalysts.Specifically,the catalyst structure evolutions revealed directly by in-situ techniques are systematically summarized,such as phase,valence,electronic transfer,coordination,and spin states varies.In-situ revelation of intermediate adsorption/desorption behavior,and the real-time monitoring of the product nucleation,growth,and reconstruction evolution are equally emphasized in the discussion.Other interference factors,as well as in-situ signal assignment with the aid of theoretical calculations,are also covered.Finally,some major challenges and prospects of in-situ techniques for future catalysts research in the ORR process are proposed.

In-situ/operando characterization techniques in lithium-ion batteries and beyond

Nowadays,in-situ/operando characterization becomes one of the most powerful as well as available means to monitor intricate reactions and investigate energy-storage mechanisms within advanced batteries.The new applications and novel devices constructed in recent years are necessary to be reviewed for inspiring subsequent studies.Hence,we summarize the progress of in-situ/operando techniques employed in rechargeable batteries.The members of this large family are divided into three sections for introduction,including bulk material,electrolyte/electrode interface and gas evolution.In each part,various energy-storage systems are mentioned and the related experimental details as well as data analysis are discussed.The simultaneous strategies of various in-situ methods are highlighted as well.Finally,current challenges and potential solutions are concluded towards the rising influence and enlarged appliance of in-situ/operando techniques in the battery research.

Effect of N-doping-derived solvent adsorption on electrochemical double layer structure and performance of porous carbon

N-doped porous carbon has been extensively investigated for broad electrochemical applications.The performance is significantly impacted by the electrochemical double layer(EDL),which is material dependent and hard to characterize.Limited understanding of doping-derived EDL structure hinders insight into the structure-performance relations and the rational design of high-performance materials.Thus,we analyzed the mass and chemical composition variation of EDL within electrochemical operation by electrochemical quartz crystal microbalance,in-situ X-ray photoelectron spectroscopy,and time-offlight secondary ion mass spectrometry.We found that N-doping triggers specifically adsorbed propylene carbonate solvent in the inner Helmholtz plane(IHP),which prevents ion rearrangement and enhances the migration of cations.However,this specific adsorption accelerated solvent decomposition,rendering rapid performance degradation in practical devices.This work reveals that the surface chemistry of electrodes can cause specific adsorption of solvents and change the EDL structure,which complements the classical EDL theory and provide guidance for practical applications.

In-situ/operando techniques to identify active sites for thermochemical conversion of CO_(2) over heterogeneous catalysts

The catalytic conversion of CO_(2) to fuels or chemicals is considered to be an effective pathway to mitigate the greenhouse effect. To develop new types of efficient and durable catalysts, it is critical to identify the catalytic active sites, surface intermediates, and reaction mechanisms to reveal the relationship between the active sites and catalytic performance. However, the structure of a heterogeneous catalyst usually dynamically changes during reaction, bringing a great challenge for the identification of catalytic active sites and reaction pathways. Therefore, in-situ/operando techniques have been employed to real-time monitor the dynamic evolution of the structure of active sites under actual reaction conditions to precisely build the structure–function relationship. Here, we review the recent progress in the application of various in-situ/operando techniques in identifying active sites for catalytic conversion of CO_(2) over heterogeneous catalysts. We systematically summarize the applications of various optical and X-ray spectroscopy techniques, including Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XAS), in identifying active sites and determining reaction mechanisms of the CO_(2) thermochemical conversion with hydrogen and light alkanes over heterogeneous catalysts. Finally, we discuss challenges and opportunities for the development of in-situ characterization in the future to further enlarge the capability of these powerful techniques.

Zeolite-mediated hybrid Cu^(+)/Cu~0 interface for electrochemical nitrate reduction to ammonia

The electrocatalytic conversion of reactive nitrogen species to ammonia is a promising strategy for efficient NH_(3) synthesis.In this study,we reveal that the hybrid Cu^(+)/Cu~0 interface is catalytically active for electrochemical ammonia synthesis from nitrate reduction.To maintain the hybrid Cu^(+)/Cu~0 state at negative reaction potentials,hydrophilic zeolite is used to modify Cu/Cu_(2)O electrocatalyst,which demonstrates an impressive NH_(3) production rate of 41.65 mg h^(-1) cm^(-2)with ~100% Faradaic efficiency of ammonia synthesis at-0.6 V vs.RHE.In-situ Raman spectroscopy unveil the high activity originates from the zeolite reconstruction at the electrode–electrolyte interface,which protects the valence state of Cu~0/Cu^(+) site under negative potential and promotes electrochemical activity towards NH_(3) synthesis.

Insight into the Electrochemical Behaviors of NCM811|SiO-Gr Pouch Battery through Thickness Variation

LiNi0.8Co0.1Mn0.1O2(NCM811)|SiOx-graphite(SiO-Gr.)battery chemistry is of intensive attention because its achievable practical energy density is approaching impressively 300 Wh Kg^(-1).However,it still suffers rapid capacity fades during repeated cycles,both chemical,electrochemical and mechanical irreversibility contribute.A comprehensive understanding behind the fading behavior of the cell chemistry is required before fully realize the benefits of this chemistry.Herein,the in-situ thickness variation is introduced as a diagnostic technique and is performed on 5-55 Ah NCM811|SiO-Gr cells.With the help of Li reference electrode and in-situ X-ray diffraction device,the correspondence between thickness variation and the electrode potential is carefully investigated.Firstly,the NCM811|SiO-Gr cell is characterized with the maximum cell thickness at around 80%state-of-charge(SOC)in the discharge process,rather than at 100%SOC.Secondly,the electrochemical behaviors during rate charge/discharge are diagnosed,and a Li platting signal is resolved from thickness variation profile at 2C.This work confirms that the thickness monitoring is a nondestructive and informative complement to conventional diagnostic techniques for failure analysis of pouch cells.

Dynamic phase transition behavior of a LiMn_(0.5)Fe_(0.5)PO_(4) olivine cathode material for lithium-ion batteries revealed through in-situ X-ray techniques

LiMn_(0.5)Fe_(0.5)PO_(4) has attracted great interest due to its good electrochemical performance and higher operating voltages.This has led to a greater than 30 percent higher energy density than for commercial Li Fe PO4 olivine cathodes.Understanding the phase transition behaviors and kinetics of this material will help researchers to design and develop next generation cathodes for Li-ion batteries.In this study,we investigated non-equilibrium phase transition behaviors in a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material during charge–discharge processes by varying current rates(C-rates)using synchrotron in-situ X-ray techniques.These methods included wide angle X-ray scattering(in-situ WAXS)and X-ray absorption spectroscopy(in-situ XAS).The WAXS spectra indicate that the phase transition of LiMn_(0.5)Fe_(0.5)PO_(4) material at slow C-rates is induced by a two-phase reaction.In contrast,at a high C-rate(5 C),the formation of an intermediate phase upon discharge is clearly observed.Concurrently,the oxidation numbers of the redox reactions of Fe^(2+)/Fe^(3+)and Mn^(2+)/Mn^(3+)were evaluated using in-situ XAS.This combination of synchrotron in-situ X-ray techniques gives clear insights into the non-equilibrium phase transition behavior of a LiMn_(0.5)Fe_(0.5)PO_(4) cathode material.This new understanding will be useful for further developments of this highly promising cathode material for practical commercialization.

Techniques for in-situ stress measurement at great depth

Reliable information of in--situ stress state is necessary for the design andconstruction of most important rock projects. As most rock projects are getting deeper and deeper,traditional techniques of in--situ stress measurement are not very suitable. The current techniquesof in--situ stress measurement and their insufficiency for use at great depth are analyzed. Somebasic ideas of the development of new techniques and the improvement of current techniques for useat great depth are provided.

In-situ electrochemical surface-enhanced Raman spectroscopy in metal/polyelectrolyte interfaces

Polyelectrolyte becomes more and more popular in electrocatalysis.The understanding of electrode/polyelectrolyte interfaces at the molecular level is important for guiding further the polyelectrolyte-based electrocatalysis.Herein,we demonstrate an in-situ surface-enhanced Raman spectroscopic method by using a three-electrode spectroelectrochemical cell towards characterizing the electrode/polyelectrolyte interfaces.The Ag/AgCl and Ag/Ag_(2)O electrodes are used as the reference electrode in the acidic and the alkaline systems,respectively.The working electrode is made of a transparent carbon thin film which loads the electrocatalysts.The applications of this method are demonstrated through the in-situ characterizations of the p-methylthiophenol adsorbed on the Au and Pt and the electrochemical oxidation of Au on polyelectrolyte membranes.The potential-dependent spectral features of these two systems show that this method is a powerful tool for investigating the electrode/polyelectrolyte interfaces in electrocatalysis.

Research Surveys of Electrochemical Sensors for in-situ Determining Hydrogen in Steels

The principle, construction and application of two types of electrochemical sensors-amperometric and potentiometric are surveyed. Both types of sensors are very sensitive to changes in temperature. The accuracy of hydrogen measurement depends on both the precision of sensors developed and the reliable technique of installation and security of sensors. The two types of sensors have been used for in-situ determining hydrogen permeated in steels owing to a corrosive reaction, a hydrogen gas circumstance at elevated temperatures and high pressure or also a pretreatment process such as pickling and plating process, etc.

Measurement of Concentration Distribution of Electrogenerated Etchant Using an Electrochemical Probe Technique

An electrochemical probe measurement system for detecting an electrogenerated etchant in solution is developed.Concentration distribution of electrogenerated etchant bromine as close as 8 micrometer to the surface of macrodisk is studied quantitatively.

IN-SITU DISTANCE RESOLVED OPTICALLY TRANSPARENT THIN-LAYER MICROSCOPIC FTIR SPECTROELECTROCEMISTRY.ESTIMATION OF THE ELECTROCHEMICAL CONCENTRATION-DISTANCE PROFILE

An in-situ optically transparent thin-layer microscopic FTIR spectroelectro- chemical cell was constructed.Using this cell,we characterize a concentration-distance profile in the electrochemical diffusion thin-layer by in-situ adjusting the focal point at different distances to the electrode surface.

Effect of Rapid Quenching on Microstructures and Electrochemical Performances of La_2Mg(Ni_(0.85)Co_(0.15))_9M_(0.1)(M=B, Cr) Hydrogen Storage Alloys

The La-Mg-Ni-system （PuNi3-type） La2Mg （Ni0.85 Co0.15 ）9M0.1 （ M = B, Cr） hydrogen storage etectrode alloys were prepared by casting and rapid quenching. The electrochemical performances and microstructures of the as-cast and quenched alloys were determined and measured. The effects of rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The obtained results show that the alloys are composed of the （La, Mg） Ni3 phase （PuNi3-type structure） and the LaNi5 phase, as well as the small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast alloy containing boron, and the Ni2B phase in the alloy nearly disappears after rapid quenching. The relative amount of each phase in the alloys depends on the quenching rate. The rapid quenching technique can greatly improve the electrochemical performance of the alloy, and the effect of rapid quenching on the activation performances of the alloys is minor. Rapid quenching enhances the cycle stability of the alloy, and the cycle life of the alloy increases with the increase of the quenching rate.

Decoding lithium batteries through advanced in situ characterization techniques

Given the energy demands of the electromobility market,the energy density and safety of lithium batteries(LBs)need to be improved,whereas its cost needs to be decreased.For the enhanced performance and decreased cost,more suitable electrode and electrolyte materials should be developed based on the improved understanding of the degradation mechanisms and structure–performance correlation in the LB system.Thus,various in situ characterization technologies have been developed during the past decades,providing abundant guidelines on the design of electrode and electrolyte materials.Here we first review the progress of in situ characterization of LBs and emphasize the feature of the multi-model coupling of different characterization techniques.Then,we systematically discuss how in situ characterization technologies reveal the electrochemical processes and fundamental mechanisms of different electrode systems based on representative electrode materials and electrolyte components.Finally,we discuss the current challenges,future opportunities,and possible directions to promote in situ characterization technologies for further improvement of the battery performance.

Electrochemical deposition of Mg(OH)_(2)/GO composite films for corrosion protection of magnesium alloys

Mg(OH)_(2)/graphene oxide(GO)composite film was electrochemical deposited on AZ91D magnesium alloys at constant potential.The characteristics of the Mg(OH)_(2)/GO composite film were investigated by scanning electron microscope(SEM),energy-dispersive X-ray spectrometry(EDS),X-ray diffractometer(XRD)and Raman spectroscopy.It was shown that the flaky GO randomly distributed in the composite film.Compared with the Mg(OH)_(2)film,the Mg(OH)_(2)/GO composite film exhibited more uniform and compact structure.Potentiodynamic polarization tests revealed that the Mg(OH)_(2)/GO composite film could significantly improve the corrosion resistance of Mg(OH)_(2)film with an obvious positive shift of corrosion potential by 0.19 V and a dramatic reduction of corrosion current density by more than one order of magnitude.