Corrigendum to“Towards a business model for second-life batteries:Barriers,opportunities,uncertainties,and technologies”[J.Energy Chem.78(2023)507–525]

In the Acknowledgments Section,please replace“Shell oil”for“TotalEnergies”.The authors would like to apologise for any inconvenience caused.For the sake of clarity(“Shell oil”should be removed and in boldblack“TotalEnergies”inserted),this section should say:The authors would like to thank Moura Batteries for the financial support.

Reviewing perovskite oxide sites influence on electrocatalytic reactions for high energy density devices

Batteries,fuel cells,and supercapacitors are electrochemical devices already on the market and still need a boost in kinetics to match the high energy density demand of applications.Perovskites have attracted the scientific community's attention in the last decade due to their electrocatalytic activity,chemical and structural properties,tunability,low cost,and scalability.Efforts have been made to understand the active sites and the operational mechanisms in perovskite oxides to shape them as an electrocatalyst in advanced energy devices.Understanding the role of perovskites is the key to engineering more controlled and efficient electrocatalysts via chemical synthesis,and there is still much to do.This review highlights the use of perovskites in different energy storage and conversion systems.The A,B,and A&B doping-site effects are analyzed to understand the opportunities and challenges related to this class of materials.In addition,the synthesis methods and the properties related to the doping site are described and summarized.

The initial stages of Li_(2)O_(2) formation during oxygen reduction reaction in Li-O_(2) batteries:The significance of Li_(2)O_(2) in charge-transfer reactions within devices

Lithium-oxygen batteries are a promising technology because they can greatly surpass the energy density of lithium-ion batteries.However,this theoretical characteristic has not yet been converted into a real device with high cyclability.Problems with air contamination,metallic lithium reactivity,and complex discharge and charge reactions are the main issues for this technology.A fast and reversible oxygen reduction reaction(ORR)is crucial for good performance of secondary batteries',but the partial knowledge of its mechanisms,especially when devices are concerned,hinders further development.From this perspective,the present work uses operando Raman experiments and electrochemical impedance spectroscopy(EIS)to assess the first stages of the discharge processes in porous carbon electrodes,following their changes cycle by cycle at initial operation.A growth kinetic formation of the discharge product signal(Li_(2)O_(2))was observed with operando Raman,indicating a first-order reaction and enabling an analysis by a microkinetic model.The solution mechanism in the evaluated system was ascribed for an equivalent circuit with three time constants.While the time constant for the anode interface reveals to remain relatively constant after the first discharge,its surface seemed to be more non-uniform.The model indicated that the reaction occurs at the Li_(2)O_(2) surface,decreasing the associated resistance during the initial discharge phase.Furthermore,the growth of Li_(2)O_(2) forms a hetero-phase between Li_(2)O_(2)/electrolyte,while creating a more compact and homogeneous on the Li_(2)O_(2)/cathode surface.The methodology here described thus offers a way of directly probing changes in surface chemistry evolution during cycling from a device through EIS analysis.

An Overview of Sequential Approximation in Topology Optimization of Continuum Structure

This paper offers an extensive overview of the utilization of sequential approximate optimization approaches in the context of numerically simulated large-scale continuum structures.These structures,commonly encountered in engineering applications,often involve complex objective and constraint functions that cannot be readily expressed as explicit functions of the design variables.As a result,sequential approximation techniques have emerged as the preferred strategy for addressing a wide array of topology optimization challenges.Over the past several decades,topology optimization methods have been advanced remarkably and successfully applied to solve engineering problems incorporating diverse physical backgrounds.In comparison to the large-scale equation solution,sensitivity analysis,graphics post-processing,etc.,the progress of the sequential approximation functions and their corresponding optimizersmake sluggish progress.Researchers,particularly novices,pay special attention to their difficulties with a particular problem.Thus,this paper provides an overview of sequential approximation functions,related literature on topology optimization methods,and their applications.Starting from optimality criteria and sequential linear programming,the other sequential approximate optimizations are introduced by employing Taylor expansion and intervening variables.In addition,recent advancements have led to the emergence of approaches such as Augmented Lagrange,sequential approximate integer,and non-gradient approximation are also introduced.By highlighting real-world applications and case studies,the paper not only demonstrates the practical relevance of these methods but also underscores the need for continued exploration in this area.Furthermore,to provide a comprehensive overview,this paper offers several novel developments that aim to illuminate potential directions for future research.

Localized-domains staging structure and evolution in lithiated graphite

Intercalation provides to the host materials a means for controlled variation of many physical/chemical properties and dominates the reactions in metal‐ion batteries.Of particular interest is the graphite intercalation compounds with intriguing staging structures,which however are still unclear,especially in their nanostructure and dynamic transition mechanism.Herein,the nature of the staging structure and evolution of the lithium(Li)‐intercalated graphite was revealed by cryogenic‐transmission electron microscopy and other methods at the nanoscale.The intercalated Li‐ions distribute unevenly,generating local stress and dislocations in the graphitic structure.Each staging compound is found macroscopically ordered but microscopically inhomogeneous,exhibiting a localized‐domains structural model.Our findings uncover the correlation between the long‐range ordered structure and short‐range domains,refresh the insights on the staging structure and transition of Li‐intercalated/deintercalated graphite,and provide effective ways to enhance the reaction kinetic in rechargeable batteries by defect engineering.

Towards a business model for second-life batteries: Barriers,opportunities, uncertainties, and technologies

Electric vehicles(EVs) and the recent pandemic outbreak give cities a new trend to primarily private and shared mobility with low noise and less air pollution.Crucial factors for the widespread of EVs are the electrical charging infrastructure,driving range,and the reduction of the cost of battery packets.For this reason,there is a massive effort from manufacturers,governments,and the scientific community to reduce battery costs and boost sustainable electrical production and distribution.Battery reuse is an alternative to reduce batteries’ costs and environmental impacts.Second-life batteries can be used in a wide variety of secondary applications.Second-life batteries can be connected with off-grid or on-grid photovoltaic and wind systems,vehicle charging stations,forklifts,and frequency control.The present work aims to analyze the main challenges imposed on the reuse of batteries,the leading technologies for their reuse,and the different types of batteries in terms of their feasibility for second-life use.The main novelty of this work is the discussion about the barriers,opportunities,uncertainties,and technologies for the second life market.Here we summarize the present state of the art in reusing lithium-ion batteries discussing technical and economic feasibility,environmental impacts,and perspectives.The results show five business models that have been proposed in the literature,three types of markets for trading second-life batteries,and the main opportunities and barriers for each actor in the battery supply chain.

In situ and operando infrared spectroscopy of battery systems:Progress and opportunities

In situ and operando infrared spectroscopies are powerful techniques to support the design of novel materials for batteries and the development of new battery systems.These techniques can support the study of batteries by identifying the formation of new species and monitoring electrochemical energy stability.However,few works have employed these techniques,which can be used to investigate various materials,including systems beyond lithium-ion technology,in the research of batteries.Therefore,this review presents a comprehensive overview focusing on the main contributions of in situ and operando infrared spectroscopy for lithium-ion batteries(LIBs)and other battery systems.These techniques can successfully identify the formation of species during the electrolyte reduction,electrode degradation,and the formation of the solid-electrolyte interphase(SEI)layer.From these outcomes,it is possible to conclude that this characterization approach should be employed as a protocol to overcome remaining issues in batteries,consequently supporting battery research.This review aims to be a guide on how infrared spectroscopy can contribute to monitoring battery systems and to lead researchers interested in applying this technique.

Designing of highly selective and high-temperature endurable RWGS heterogeneous catalysts: recent advances and the future directions

Reverse water gas shift（RWGS） reaction can be served as a pivotal stage of transitioning the abundant CO;resource into chemicals or hydrocarbon fuels, which is attractive for the CO;utilization and of eventually significance in enabling a rebuilt ecological system for unconventional fuels. This concept is appealing when the process is considered as a solution for the storage of renewable energy, which may also find a variety of potential end uses for the outer space exploration. However, a big challenge to this issue is the rational design of high temperature endurable RWGS catalysts with desirable CO product selectivity. In this work, we present a comprehensive overview of recent publications on this research topic,mainly focusing on the catalytic performance of RWGS reaction over three major kinds of heterogeneous catalysts, including supported metal catalysts, mixed oxide catalysts and transition metal carbides. The reaction thermodynamic analysis, kinetics and mechanisms are also described in detail. The present review attempts to provide a general guideline about the construction of well-performed heterogeneous catalysts for the RWGS reaction, as well as discussing the challenges and further prospects of this process.

Recent advances on quasi-solid-state electrolytes for supercapacitors

Solid-state and quasi-solid-state electrolytes have been attracting the scientific community’s attention in the last decade. These electrolytes provide significant advantages, such as the absence of leakage and separators for devices and safety for users. They also allow the assembly of stretchable and bendable supercapacitors. Comparing solid-state to quasi-solid-states, the last provides the most significant energy and power densities due to the better ionic conductivity. Our goal here is to present recent advances on quasisolid-state electrolytes, including gel-polymer electrolytes. We reviewed the most recent literature on quasi-solid-state electrolytes with different solvents for supercapacitors. Organic quasi-solid-state electrolytes need greater attention once they reach an excellent working voltage window greater than 2.5 V.Meanwhile, aqueous-based solid-state electrolytes have a restricted voltage window to less than 2 V. On the other hand, they are easier to handle, provide greater ionic conductivity and capacitance. Recent water-in-salt polymer-electrolytes have shown stability as great as 2 V encouraging further development in aqueous-based quasi-solid-state electrolytes. Moreover, hydrophilic conductive polymers have great commercial appeal for bendable devices. Thus, these electrolytes can be employed in flexible and bendable devices, favoring the improvement of portable electronics and wearable devices(376 references were evaluated and summarized here).

Characterization of porous cobalt hexacyanoferrate and activated carbon electrodes under dynamic polarization conditions in a sodium-ion pseudocapacitor

We report here the activated carbon and cobalt hexacyanoferrate composite,which is applied as the electrode materials in symmetric supercapacitors containing a 1.0 M Na_(2)SO_(4) aqueous electrolyte.This novel material combines high specific surface area and electrochemical stability of activated carbon with the redox properties of cobalt hexacyanoferrate,resulting in maximum specific capacitance of 329 F g^(-1) with large voltage working window of 2.0 V.Electrochemical studies indicated that cobalt hexacyanoferrate introduces important pseudocapacitive properties accounting for the overall charge-storage process,especially when I<0.5 A g^(-1).At lower gravimetric currents(e.g.,0.05 A g^(-1))and up to 1.0 V,the presence of cobalt hexacyanoferrate improves the specific energy for more than 300%.In addition,to better understanding the energy storage process we also provided a careful investigation of the electrode materials under dynamic polarization conditions using the in situ Raman spectroscopy and synchrotron light Xray diffraction techniques.Interesting complementary findings were obtained in these studies.We believe that this novel electrode material is promising for applications regarding the energy-storage process in pseudocapacitors with long lifespan properties.

Raman probing carbon&aqueous electrolytes interfaces and molecular dynamics simulations towards understanding electrochemical properties under polarization conditions in supercapacitors

Raman probing of carbon electrode and electrolyte under dynamic conditions is performed here using different aqueous electrolytes to elucidate the fundamental events occurring in electrochemical supercapacitor during charge–discharge processes.The areal capacitance ranges from 1.54 to 2.31μF cm^(-2)μm and it is determined using different techniques.These findings indicate that the Helmholtz capacitance governs the overall charge-storage process instead of the space charge(quantum)capacitance commonly verified for HOPG electrodes in the range of~3 to 7μF cm^(-2).Molecular dynamics simulations are employed to elucidate the origin of the reversible Raman spectral changes during the charge–discharge processes.A correlation is verified between the reversible Raman shift and the surface excesses of the different ionic species.A theoretical framework is presented to relate the effect of the applied potential on the Raman shift and its correlation with the surface ionic charge.It is proposed that the Raman shift is governed by the interaction of solvated cations with graphite promoted by polarization conditions.It is the first time that a comparative study on different aqueous electrolyte p H and cation ion size has been performed tracking the Raman spectra change under dynamic polarization conditions and contrasting with comprehensive electrochemistry and dynamic molecular simulations studies.This study shines lights onto the charge-storage mechanism with evidence of Kohn anomaly reduction in the carbon electrode during the reversible adsorption/desorption and insertion/extraction of ionic species.

In situ Observation of Li Deposition-Induced Cracking in Garnet Solid Electrolytes

Lithium(Li)penetration through solid electrolytes(SEs)induces short circuits in Li solid-state batteries(SSBs),which is a critical issue that hinders the development of high energy density SSBs.While cracking in ceramic SEs has been often shown to accompany Li penetration,the interplay between Li deposition and cracking remains elusive.Here,we constructed a mesoscale SSB inside a focused ion beam-scanning electron microscope(FIB-SEM)for in situ observation of Li deposition-induced cracking in SEs at nanometer resolution.Our results revealed that Li propagated predominantly along transgranular cracks in a garnet Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO).Cracks appeared to initiate from the interior of LLZTO beneath the electrode surface and then propagated by curving toward the LLZTO surface.The resulting bowl-shaped cracks resemble those from hydraulic fracture caused by high fluid pressure on the surface of internal cracks,suggesting that the Li deposition-induced pressure is the major driving force of crack initiation and propagation.The high pressure generated by Li deposition is further supported by in situ observation of the flow of filled Li between the crack flanks,causing crack widening and propagation.This work unveils the dynamic interplay between Li deposition and cracking in SEs and provides insight into the mitigation of Li dendrite penetration in SSBs.

Direct observation of the CO_(2) formation and C–H consumption of carbon electrode in an aqueous neutral electrolyte supercapacitor by in-situ FTIR and Raman

Electrical double-layer capacitors(EDLCs)consist of energy storage devices that present high-power and moderate energy density.The electrolyte and electrode physicochemical properties are crucial for improving their overall energy storage capabilities.Therefore,the stability of the EDLCs’materials is the primary focus of this study.Since energy storage depends on the specific capacitance,and also on the square of the maximum capacitive cell voltage(UMCV).Thus,electrodes with high specific surface area(SSA)and electrolytes with excellent electrochemical stability are commonly reported in the literature.Aqueous electrolytes are safer and green devices compared to other organic-based solutions.On the other hand,their UMCVis reduced compared to other electrolytes(e.g.,organic-based and ionic liquids).In this sense,spanning the UMCVfor aqueous-based electrolytes is a’hot topic’research.Unfortunately,the lack of protocols to establish reliable UMCVvalues has culminated in the publishing of several conflicting results.Herein,we confirm that multiwalled carbon nanotubes(MWCNTs)housed in cells degrade and produce CO_(2) under abusive polarisation conditions.It is probed by employing electrochemical techniques,in-situ FTIR and in-situ Raman spectroscopies.From these considerations,the current study uses spectro-electrochemical techniques to support the correct determination of the electrode and electrolyte stability conditions as a function of the operating electrochemical parameters.