Alkali metal-carbon dioxide(Li/Na/K-CO_(2))batteries are emerging electrochemical energy storage technologies in the context of the energy crisis and the urgent demand for carbon neutrality.Alkali metal-CO_(2) batteri...Alkali metal-carbon dioxide(Li/Na/K-CO_(2))batteries are emerging electrochemical energy storage technologies in the context of the energy crisis and the urgent demand for carbon neutrality.Alkali metal-CO_(2) batteries offer a new strategy for CO_(2) fixation and utilization,and thus has been receiving considerable attention in recent years.Considerable progress has been achieved since alkali metal-CO_(2) batteries were invented,especially in terms of development of new electrode materials,and yet,research is lacking on the underlying mechanisms of the systems.This is the first typical review focusing on the electrochemical mechanisms of metal-CO_(2) batteries that summarizes the current understanding of and provides insights into the thermodynamic reaction pathways,the kinetic characteristics,and the crucial factors determining the reaction mechanisms in alkali metal-CO_(2) batteries.The review starts with the fundamental concepts of alkali metal-CO_(2) batteries,followed by a comprehensive discussion of the working mechanisms on cathodes and anodes.Moreover,the operation mechanisms of state-of-the-art electrolytes,including liquid and(quasi-)solid-state electrolytes,are also described.Finally,we identify the unsolved problems in current alkali metal-CO_(2) batteries and propose potential topics for future research.展开更多
The optimization of electrolytes and the material removal mechanisms for Cu electrochemical mechanical planarization(ECMP)at different pH values including 5-methyl-1H-benzotriazole(TTA),hydroxyethylidenediphosphoric a...The optimization of electrolytes and the material removal mechanisms for Cu electrochemical mechanical planarization(ECMP)at different pH values including 5-methyl-1H-benzotriazole(TTA),hydroxyethylidenediphosphoric acid(HEDP),and tribasic ammonium citrate(TAC)were investigated by electrochemical techniques,X-ray photoelectron spectrometer(XPS)analysis,nano-scratch tests,AFM measurements,and polishing of Cu-coated blanket wafers.The experimental results show that the planarization efficiency and the surface quality after ECMP obtained in alkali-based solutions are superior to that in acidic-based solutions,especially at pH=8.The optimal electrolyte compositions(mass fraction)are 6% HEDP,0.3% TTA and 3% TAC at pH=8.The main factor affecting the thickness of the oxide layer formed during ECMP process is the applied potential.The soft layer formation is a major mechanism for electrochemical enhanced mechanical abrasion.The surface topography evolution before and after electrochemical polishing(ECP)illustrates the mechanism of mechanical abrasion accelerating electrochemical dissolution,that is,the residual stress caused by the mechanical wear enhances the electrochemical dissolution rate.This understanding is beneficial for optimization of ECMP processes.展开更多
The corrosion failure mechanism of M152 was studied using the neutral salt-spray test to better understand the corrosion behavior of 1Cr12Ni3Mo2VN（M152）, provide a basis for the optimization of material selection, a...The corrosion failure mechanism of M152 was studied using the neutral salt-spray test to better understand the corrosion behavior of 1Cr12Ni3Mo2VN（M152）, provide a basis for the optimization of material selection, and prevent the occurrence of failure. Moreover, the mechanism was investigated using the mass loss method, polarization curves, electrochemical impedance spectroscopy（EIS）, stereology microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy（EDS）. The results show that M152 steel suffers severe corrosion, especially pitting corrosion, in a high-salt-spray environment. In the early stage of the experiment, the color of the corrosion products was mainly orange. The products then gradually evolved into a dense, brown substance, which coincided with a decrease of corrosion rate. Correspondingly, the EIS spectrum of M152 in the late test also exhibited three time constants and presented Warburg impedance at low frequencies.展开更多
Aqueous proton batteries(APBs) offer a viable and attractive option in the field of affordable and sustainable energy solutions.Organic polymers are highly favored due to their environmentally friendly manufacturabili...Aqueous proton batteries(APBs) offer a viable and attractive option in the field of affordable and sustainable energy solutions.Organic polymers are highly favored due to their environmentally friendly manufacturability and malleable molecular configurations,making them suitable materials for constructing APB electrodes.Nonetheless,their currently limited capacity for proton-associated redox reactions poses a challenge to the widespread usage.Herein,we have developed a highly redox-active organic polymer(PTA) tailored for APB applications.The inclusion of dual redox-active moieties in the extended nconjugated frameworks not only enhances the redox activity and refines the electronic properties,but also ensures the high structural integrity of the PTA polymer.When used as an electrode,the PTA polymer has a notable ability to store protons,with a large capacity of 213.99 mA h g^(-1) at 1 A g^(-1) and exceptional long-term stability,as evidenced by retaining 94.6% of its initial capacity after 20,000 cycles.In situ techniques alongside theoretical calculations have unveiled efficient redox processes occurring at C=N and C=O redox-active sites within the PTA electrode upon proton uptake/removal.Furthermore,a softpackage APB device has been assembled with impressive electrochemical behaviors and excellent operational lifespan,accentuating its significant promise for real-world deployment.展开更多
Zn-based aqueous batteries(ZABs) are gaining widespread popularity due to their low cost and high safety profile. However, the application of ZABs faces significant challenges, such as dendrite growth and parasitic re...Zn-based aqueous batteries(ZABs) are gaining widespread popularity due to their low cost and high safety profile. However, the application of ZABs faces significant challenges, such as dendrite growth and parasitic reactions of metallic Zn anodes. Therefore, achieving high-energy–density ZABs necessitates addressing the fundamental thermodynamics and kinetics of Zn anodes. Various strategies are available to mitigate these challenges, with electrolyte additive engineering emerging as one of the most efficient and promising approaches. Despite considerable research in this field, a comprehensive understanding of the intrinsic mechanisms behind the high performance of electrolyte additives remains limited. This review aims to provide a detailed introduction to functional electrolyte additives and thoroughly explore their underlying mechanisms. Additionally, it discusses potential directions and perspectives in additive engineering for ZABs, offering insights into future development and guidelines for achieving high-performance ZABs.展开更多
Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in...Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in improving the energy density of NIBs.Low-voltage anode materials,however,are severely lacking in NIBs.Of all the reported insertion oxides anodes,the Na_(2)Ti_(3)O_(7) has the lowest operating voltage(an average potential of 0.3 V vs.Na^(+)/Na)and is less likely to deposit sodium,which has excellent potential for achieving NIBs with high energy densities and high safety.Although significant progress has been made,achieving Na_(2)Ti_(3)O_(7) electrodes with excellent performance remains a severe challenge.This paper systematically summarizes and discusses the physicochemical properties and synthesis methods of Na_(2)Ti_(3)O_(7).Then,the sodium storage mechanisms,key issues and challenges,and the optimization strategies for the electrochemical performance of Na_(2)Ti_(3)O_(7) are classified and further elaborated.Finally,remaining challenges and future research directions on the Na_(2)Ti_(3)O_(7) anode are highlighted.This review offers insights into the design of high-energy and high-safety NIBs.展开更多
Cadmium was replaced by zinc in ammoniacal system using an electrically enhanced method under ultrasonic waves.Five main influencing factors were investigated by a single-factor experiment to determine the optimum par...Cadmium was replaced by zinc in ammoniacal system using an electrically enhanced method under ultrasonic waves.Five main influencing factors were investigated by a single-factor experiment to determine the optimum parameters.Cyclic voltammetry and linear sweep voltammetry were applied to investigating the reaction mechanism of electrically enhanced cementation of cadmium on a zinc plate.The optimum parameters were a temperature of 35℃,a cathode-to-anode area ratio of 1:2,an anode current density of 15 A/m2,an ultrasonic frequency of 40 kHz a reaction time of 6 h and an ultrasonic power of 100 W.The extraction rate was 99.21%,and the production of byproduct“floating sponge cadmium”was inhibited.The analysis of the cyclic voltammetry and linear sweep voltammetry diagrams showed that ultrasonic waves can promote and accelerate the replacement reaction,decrease the voltage requirement of the electrically enhanced replacement reaction,and change the reaction steps.In addition,increasing the temperature and ultrasonic power can promote and accelerate electrically enhanced replacement reactions and decrease the electric potential requirement.展开更多
The co-extraction behavior of galena-pyrolusite in a sodium chloride solution and the electrochemical mechanism of this process were investigated,and some factors affecting the leaching rate of Pb and Mn were optimize...The co-extraction behavior of galena-pyrolusite in a sodium chloride solution and the electrochemical mechanism of this process were investigated,and some factors affecting the leaching rate of Pb and Mn were optimized.The results show that all the factors such as the concentration of NaCl,HCl and pyrolusite ore,reaction time,temperature,adding times of HCl,affect the leaching rate of Pb.The main affecting factors are the concentration of NaCl,reaction time and temperature.The Tafel polarization curves and EIS plots of the galena and pyrolusite in the NaCl solution demonstrate that during the oxidation process of galena mineral electrode,film forms on the galena surface,which prevents galena from deeper oxidation.However,the film resistance can be greatly reduced in the presence of sodium chloride,thus promoting the reaction rate of galena.展开更多
Four protic ionic liquids(ILs)were synthesized via a one-step method by using benzotriazole(BTA)and benzimidazole as cations,and benzenesulfonic acid and 2-naphthalenesulfonic acid(NSA)as anions.These ILs were used as...Four protic ionic liquids(ILs)were synthesized via a one-step method by using benzotriazole(BTA)and benzimidazole as cations,and benzenesulfonic acid and 2-naphthalenesulfonic acid(NSA)as anions.These ILs were used as green corrosion inhibitors for brass specimens in a nitric acid solution.The structure of the protic ILs was characterized by 1H-NMR,13C-NMR,and FT-IR spectroscopy.The effects of the IL structure,IL concentration,acid concentration,and corrosion time on the surface morphology of brass specimens and the inhibition efficiency(η%)of ILs were investigated by the weight loss method combined with SEM and EDS spectroscopy.Polarization curves and impedance spectroscopy were used to analyze the electrochemical corrosion inhibition mechanism of ILs.Results showed that IL synthesis was a proton transfer process,and the proton of the–SO3H group on NSA was deprived by BTA.IL[BTA][NSA],which had a high charge density and large conjugateπband,was the most effective inhibitor for brass corrosion.Theη%of[BTA][NSA]decreased with the increase in acid concentration and corrosion time,which showed an increment with the increase in[BTA][NSA]concentration.The higher theη%of[BTA][NSA]is,the smoother the surface of the brass specimens is,and the smaller the undistributed area of Cu element will be.Corrosion inhibiting mechanism from electrochemical analysis indicated that the addition of[BTA][NSA]increased the polarization resistance of the brass electrode significantly and suppressed both anodic and cathodic reactions.展开更多
Abstract The electrochemical reaction mechanism and electrocrystaUization process of tungsten in the NaCl- KCl-NaF-WO3 molten salt were investigated at 973 K （700℃） by means of cyclic voltammetry, chronopotentiomet...Abstract The electrochemical reaction mechanism and electrocrystaUization process of tungsten in the NaCl- KCl-NaF-WO3 molten salt were investigated at 973 K （700℃） by means of cyclic voltammetry, chronopotentiometry, and chronoamperometry techniques. The results show that the electrochemical reaction process of tungsten in the NaCl-KCl-NaF-WO3 molten salt system is a quasireversible process mix-controlled by ion diffusion rate and electron transport rate. Tungsten ion in this system is reduced to W（0） in two steps. The electrocrystallization process of tungsten is found to be an instantaneous, hemispheroid three-dimensional nucleation process and the tungsten ion diffusion coefficient of 2.361 × 10^-4 cm2.s^-1 is obtained at experimental conditions.展开更多
With the advent of flexible/wearable electronic devices,flexible lithium-ion batteries(LIBs)have attracted significant attention as optimal power source candidates.Flexible LIBs with good flexibility,mechanical stabil...With the advent of flexible/wearable electronic devices,flexible lithium-ion batteries(LIBs)have attracted significant attention as optimal power source candidates.Flexible LIBs with good flexibility,mechanical stability,and high energy density are still an enormous challenge.In recent years,many complex and diverse design methods for flexible LIBs have been reported.The design and evaluation of ideal flexible LIBs must take into consideration both mechanical and electrochemical factors.In this review,the recent progress and challenges of flexible LIBs are reviewed from a mechano-electrochemical perspective.The recent progress in flexible LIB design is addressed concerning flexible material and configuration design.The mechanical and electrochemical evaluations of flexible LIBs are also summarized.Furthermore,mechano-electrochemical perspectives for the future direction of flexible LIBs are also discussed.Finally,the relationship between mechanical loading and the electrode process is analyzed from a mechano-electrochemical perspective.The evaluation of flexible LIBs should be based on mechano-electrochemical processes.Reviews and perspectives are of great significance to the design and practicality of flexible LIBs,which is contributed to bridging the gap between laboratory exploration and practical applications.展开更多
The cyclic plastic straining electrode technique has been used to investigate the transient electrochemical behaviour of Fe-26Cr1Mo stainless steel in 1M H2SO4 solution at a passive potential.The influence of plastic ...The cyclic plastic straining electrode technique has been used to investigate the transient electrochemical behaviour of Fe-26Cr1Mo stainless steel in 1M H2SO4 solution at a passive potential.The influence of plastic strain amplitude and plastic strain rate on the dissolution current response was analysed. The experimental results showed that the transient current was dependent on the competitive process of the surface film rupture and repassivation of the new surface. The high plastic strain amplitude and the high plastic strain rate caused a change of electrochemical activity of specimen surface. In the condition of low strain amplitude and strain rate, the characteristics of current response was mainly relative tp the process of new surface repassivation.The competition kinetics has been analysed through the comparison of plastic strain rate and repassivating rate展开更多
At present,developing a simple strategy to effectively solve the shackles of volume expansion,poor conductivity and interface compatibility faced by Si-C anode in lithium batteries(LIBs)is the key to its commercializa...At present,developing a simple strategy to effectively solve the shackles of volume expansion,poor conductivity and interface compatibility faced by Si-C anode in lithium batteries(LIBs)is the key to its commercialization.Here,low-cost nano-Si powders were prepared from Si-waste of solar-cells by sanding treatment,which can effectively reduce the commercialization cost for Si-C anode.Furthermore,micro-nano structured Gr@Si/C/TiO_(2) anode materials with graphite(Gr)as the inner core,TiO_(2)-doped and carbon-coated Si as the outer coating-layer,were synthesized at kilogram-scale per milling batch.Comprehensive characterization results indicate that TiO_(2)-doped carbon layer can improve the interface compatibility with the electrolyte,further promote the reduction of electrode polarization,and finally enhance the battery performance for the Gr@Si/C/TiO_(2) anodes.Accordingly,Gr@Si/C/TiO_(2) composites can output excellent LIB performance,especially with high initial coulombic efficiency(ICE)of 82.51%and large average reversible capacity of~810 mA h g^(-1) at 0.8 A g^(-1) after 1000 cycles.Moreover,Gr@Si/C/TiO_(2)‖NCM811 pouch full cells deliver impressive performance especially with high energy density of~489.3 W h kg^(-1) based on the total weight of active materials,suggesting its promising application in the high performance LIBs.展开更多
Supercapacitors are electrochemical energy storage devices with great potential applications.Mean-while,the oxygen evolution reaction(OER)determines the efficiency of some electrochemical energy conversions.This study...Supercapacitors are electrochemical energy storage devices with great potential applications.Mean-while,the oxygen evolution reaction(OER)determines the efficiency of some electrochemical energy conversions.This study aims at constructing,exploring,and optimizing Ramsdellite-MnO_(2)@NiCoAl-LDH@CC(R-MNCA@CC)composites.The effect of microstructure and Al role on the performance is investigated when R-MNCA@CC was used as supercapacitor electrode material and OER catalyst.Coral-like R-MNCA@CC in-situ growth composites were synthesized by a two-step hydrothermal method.R-MNCA@CC-2(molar ratio of Ni:Co:Al is 1:1:1)performs the best with the largest specific capacitance,1,742 F/g at 1 A/g,increased by 797%and 1,489%compared to that of NiCoAl-LDH and Ramsdellite-MnO_(2).The capacitance retention rate of the R-MNCA@CC-2//AC@CC supercapacitor is 80.1%after 5,000 cycles at 0.8 A/g.The overpotential for driving an OER to reach 10 m/cm^(2)is only 276 mV,which is lower than that of commercial IrO_(2)(300 mV).Noteworthy,we propose a view that is“competing to trigger redox re-action”of electrochemical active sites in LDH during electrochemical processes derived from a discrepancy between theory and experimental results.展开更多
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,...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.展开更多
Ammonium vanadate with bronze structure(NH_(4)V_(4)O_(10))is a promising cathode material for zinc-ion batteries due to its high specific capacity and low cost.However,the extraction of NH^(+)_(4) at a high voltage du...Ammonium vanadate with bronze structure(NH_(4)V_(4)O_(10))is a promising cathode material for zinc-ion batteries due to its high specific capacity and low cost.However,the extraction of NH^(+)_(4) at a high voltage during charge/discharge processes leads to irreversible reaction and structure degradation.In this work,partial NH^(+)_(4) ions were pre-removed from NH_(4)V_(4)O_(10) through heat treatment;NH_(4)V_(4)O_(10) nanosheets were directly grown on carbon cloth through hydrothermal method.Defi-cient NH_(4)V_(4)O_(10)(denoted as NVO),with enlarged interlayer spacing,facilitated fast zinc ions transport and high storage capacity and ensured the highly reversible electrochemical reaction and the good stability of layered structure.The NVO nanosheets delivered a high specific capac-ity of 457 mAh g^(−1) at a current density of 100 mA g^(−1) and a capacity retention of 81%over 1000 cycles at 2 A g^(−1).The initial Coulombic efficiency of NVO could reach up to 97%compared to 85%of NH_(4)V_(4)O_(10) and maintain almost 100%during cycling,indicating the high reaction reversibility in NVO electrode.展开更多
A new hydrometallurgical process based on the methanesulfonic acid system was proposed to extract the bismuth efficiently from by-products of lead smelting.The bismuth extraction process included electrorefining,oxida...A new hydrometallurgical process based on the methanesulfonic acid system was proposed to extract the bismuth efficiently from by-products of lead smelting.The bismuth extraction process included electrorefining,oxidation leaching,and electrodeposition.The optimum conditions of the bismuth extraction process were determined by a single-factor test.The bismuth plate with a purity of 99.8%was obtained under the optimum conditions.Cyclic voltammetry and linear sweep voltammetry were applied to investigating the cathode reaction mechanism of electrorefining.The results show that lead deposition,bismuth deposition,and hydrogen evolution occur at the cathode,and the reactions of metals deposition are irreversible and diffusion-controlled.In addition,decreasing the temperature and acidity can improve the purity of the cathodic product(lead powder)in the electrorefining process.展开更多
The excellent energy storage performance of covalent sulfur-carbon material has gradually attracted great interest. However, in the electrochemical sodium storage process, the bond evolution mechanism remains an elusi...The excellent energy storage performance of covalent sulfur-carbon material has gradually attracted great interest. However, in the electrochemical sodium storage process, the bond evolution mechanism remains an elusive topic. Herein, we develop a one-step annealing strategy to achieve a high covalent sulfur-carbon bridged hybrid(HCSC)utilizing phenylphosphinic acid as the carbon-source/catalyst and sodium sulfate as the sulfur-precursor/salt template, in which the sulfur mainly exists in the forms of C–S–C and C–S–S–C. Notably, most of the bridge bonds are electrochemically cleaved when the cycling voltage is lower than0.6 V versus Na/Na+, leading to the appearance of two visible redox peaks in the following cyclic voltammogram(CV) tests.The in-situ and ex-situ characterizations demonstrate that S^2- is formed in the reduction process and the carbon skeleton is concomitantly and irreversibly isomerized. Thus, the cleaved sulfur and isomerized carbon could jointly contribute to the sodium storage in 0.01–3.0 V. In a Na-S battery system, the activated HCSC in cut off voltage window of 0.6–2.8 V achieves a high reversible capacity(770 mA h g^-1 at 300 mA g^-1). This insight reveals the charge storage mechanism of sulfur-carbon bridged hybrid and provides an improved enlightenment on the interfacial chemistry of electrode materials.展开更多
Rechargeable lithium/sodium-sulfur batteries working at room temperature(RT-Li/S,RT-Na/S)appear to be a promising energy storage system in terms of high theoretical energy density,low cost,and abundant resources in na...Rechargeable lithium/sodium-sulfur batteries working at room temperature(RT-Li/S,RT-Na/S)appear to be a promising energy storage system in terms of high theoretical energy density,low cost,and abundant resources in nature.They are,thus,considered as highly attractive candidates for future application in energy storage devices.Nevertheless,the solubility of sulfur species,sluggish kinetics of lithium/sodium sulfide compounds,and high reactivity of metallic anodes render these cells unstable.As a consequence,metal-sulfur batteries present low reversible capacity and quick capacity loss,which hinder their practical application.Investigations to address these issues regarding S cathodes are critical to the increase of their performance and our fundamental understanding of RT-Li/S and RT-Na/S battery systems.Metal-sulfur interactions,recently,have attracted considerable attention,and there have been new insights on pathways to high‐performance RT-Li/Na sulfur batteries,due to the following factors:(1)deliberate construction of metal-sulfur interactions can enable a leap in capacity;(2)metal-sulfur interactions can confine S species,as well as sodium sulfide compounds,to stop shuttle effects;(3)traces of metal species can help to encapsulate a high loading mass of sulfur with high‐cost efficiency;and(4)metal components make electrodes more conductive.In this review,we highlight the latest progress in sulfide immobilization via constructing metal bonding between various metals and S cathodes.Also,we summarize the storage mechanisms of Li/Na as well as the metal-sulfur interaction mechanisms.Furthermore,the current challenges and future remedies in terms of intact confinement and optimization of the electrochemical performance of RT-Li/Na sulfur systems are discussed in this review.展开更多
The electrochemical mechanism of anode oxidation of HCHO in electroless copper plating solution with N, N, N′, N′-tetrakis(2-hydroxypropyl)ethylenediamine (THPED) was investigated by measuring cyclic voltammetry cur...The electrochemical mechanism of anode oxidation of HCHO in electroless copper plating solution with N, N, N′, N′-tetrakis(2-hydroxypropyl)ethylenediamine (THPED) was investigated by measuring cyclic voltammetry curves and anodic polarization curves. Three different oxidation peaks occur at the potentials of -0.62 V (Peak 1), -0.40 V (Peak 2) and -0.17 V (Peak 3) in the anode oxidation process of THPED-containing solution. The reaction at Peak 1, a main oxidation reaction, is the irreversible reaction of adsorbed HCHO with hydrogen evolution. The reaction at Peak 2, a secondary oxidation reaction, is the quasi-reversible reaction of adsorbed HCHO without hydrogen evolution. The reaction at Peak 3 is the irreversible oxidation of anode copper. The current density of Peak 1 increases gradually, that of Peak 2 remains constant and that of Peak 3 decreases with the increase of HCHO concentration. The current density of Peak 3 increases with the increase of THPED concentration and the complexation of THPED promotes the dissolution of anode copper.展开更多
基金support from the National Natural Science Foundation of China (52072257)the National Key Research and Development Program of China (2019YFE0118800).
文摘Alkali metal-carbon dioxide(Li/Na/K-CO_(2))batteries are emerging electrochemical energy storage technologies in the context of the energy crisis and the urgent demand for carbon neutrality.Alkali metal-CO_(2) batteries offer a new strategy for CO_(2) fixation and utilization,and thus has been receiving considerable attention in recent years.Considerable progress has been achieved since alkali metal-CO_(2) batteries were invented,especially in terms of development of new electrode materials,and yet,research is lacking on the underlying mechanisms of the systems.This is the first typical review focusing on the electrochemical mechanisms of metal-CO_(2) batteries that summarizes the current understanding of and provides insights into the thermodynamic reaction pathways,the kinetic characteristics,and the crucial factors determining the reaction mechanisms in alkali metal-CO_(2) batteries.The review starts with the fundamental concepts of alkali metal-CO_(2) batteries,followed by a comprehensive discussion of the working mechanisms on cathodes and anodes.Moreover,the operation mechanisms of state-of-the-art electrolytes,including liquid and(quasi-)solid-state electrolytes,are also described.Finally,we identify the unsolved problems in current alkali metal-CO_(2) batteries and propose potential topics for future research.
基金Project(50975058)supported by the National Science Foundation of China
文摘The optimization of electrolytes and the material removal mechanisms for Cu electrochemical mechanical planarization(ECMP)at different pH values including 5-methyl-1H-benzotriazole(TTA),hydroxyethylidenediphosphoric acid(HEDP),and tribasic ammonium citrate(TAC)were investigated by electrochemical techniques,X-ray photoelectron spectrometer(XPS)analysis,nano-scratch tests,AFM measurements,and polishing of Cu-coated blanket wafers.The experimental results show that the planarization efficiency and the surface quality after ECMP obtained in alkali-based solutions are superior to that in acidic-based solutions,especially at pH=8.The optimal electrolyte compositions(mass fraction)are 6% HEDP,0.3% TTA and 3% TAC at pH=8.The main factor affecting the thickness of the oxide layer formed during ECMP process is the applied potential.The soft layer formation is a major mechanism for electrochemical enhanced mechanical abrasion.The surface topography evolution before and after electrochemical polishing(ECP)illustrates the mechanism of mechanical abrasion accelerating electrochemical dissolution,that is,the residual stress caused by the mechanical wear enhances the electrochemical dissolution rate.This understanding is beneficial for optimization of ECMP processes.
基金financially supported by the Major State Basic Research Development Program of China (No. 2014CB643300)
文摘The corrosion failure mechanism of M152 was studied using the neutral salt-spray test to better understand the corrosion behavior of 1Cr12Ni3Mo2VN（M152）, provide a basis for the optimization of material selection, and prevent the occurrence of failure. Moreover, the mechanism was investigated using the mass loss method, polarization curves, electrochemical impedance spectroscopy（EIS）, stereology microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy（EDS）. The results show that M152 steel suffers severe corrosion, especially pitting corrosion, in a high-salt-spray environment. In the early stage of the experiment, the color of the corrosion products was mainly orange. The products then gradually evolved into a dense, brown substance, which coincided with a decrease of corrosion rate. Correspondingly, the EIS spectrum of M152 in the late test also exhibited three time constants and presented Warburg impedance at low frequencies.
基金China Postdoctoral Science Foundation (2022M711686)Joint Project of Industry-University-Research of Jiangsu Province (BY20230490)。
文摘Aqueous proton batteries(APBs) offer a viable and attractive option in the field of affordable and sustainable energy solutions.Organic polymers are highly favored due to their environmentally friendly manufacturability and malleable molecular configurations,making them suitable materials for constructing APB electrodes.Nonetheless,their currently limited capacity for proton-associated redox reactions poses a challenge to the widespread usage.Herein,we have developed a highly redox-active organic polymer(PTA) tailored for APB applications.The inclusion of dual redox-active moieties in the extended nconjugated frameworks not only enhances the redox activity and refines the electronic properties,but also ensures the high structural integrity of the PTA polymer.When used as an electrode,the PTA polymer has a notable ability to store protons,with a large capacity of 213.99 mA h g^(-1) at 1 A g^(-1) and exceptional long-term stability,as evidenced by retaining 94.6% of its initial capacity after 20,000 cycles.In situ techniques alongside theoretical calculations have unveiled efficient redox processes occurring at C=N and C=O redox-active sites within the PTA electrode upon proton uptake/removal.Furthermore,a softpackage APB device has been assembled with impressive electrochemical behaviors and excellent operational lifespan,accentuating its significant promise for real-world deployment.
基金financially National Natural Science Foundation of China (22309165)Excellent Youth Foundation of Henan Province (242300421126)+6 种基金Talent Development Funding Project of Shanghai (2021030)Joint Fund of Science and Technology R&D Plan of Henan Province (232301420053)Postdoctoral Science Foundation of China (2023M743170)Key Research Projects of Higher Education Institutions of Henan Province (24A530010, and 23A530002)Key Laboratory of Adv. Mater. of Ministry of Education (Adv Mat2023-17)State Key Laboratory of Inorganic Synthesis & Preparative Chemistry Jilin University (2024-34)Frontier Exploration Projects of Longmen Laboratory of Henan (LMQYTSKT021)。
文摘Zn-based aqueous batteries(ZABs) are gaining widespread popularity due to their low cost and high safety profile. However, the application of ZABs faces significant challenges, such as dendrite growth and parasitic reactions of metallic Zn anodes. Therefore, achieving high-energy–density ZABs necessitates addressing the fundamental thermodynamics and kinetics of Zn anodes. Various strategies are available to mitigate these challenges, with electrolyte additive engineering emerging as one of the most efficient and promising approaches. Despite considerable research in this field, a comprehensive understanding of the intrinsic mechanisms behind the high performance of electrolyte additives remains limited. This review aims to provide a detailed introduction to functional electrolyte additives and thoroughly explore their underlying mechanisms. Additionally, it discusses potential directions and perspectives in additive engineering for ZABs, offering insights into future development and guidelines for achieving high-performance ZABs.
基金supported by the National Natural Science Foundation of China (52307239,52102300,52207234)the Natural Science Foundation of Hubei Province (2022CFB1003,2021CFA025)。
文摘Due to its low cost and natural abundance of sodium,Na-ion batteries(NIBs)are promising candidates for large-scale energy storage systems.The development of ultralow voltage anode materials is of great significance in improving the energy density of NIBs.Low-voltage anode materials,however,are severely lacking in NIBs.Of all the reported insertion oxides anodes,the Na_(2)Ti_(3)O_(7) has the lowest operating voltage(an average potential of 0.3 V vs.Na^(+)/Na)and is less likely to deposit sodium,which has excellent potential for achieving NIBs with high energy densities and high safety.Although significant progress has been made,achieving Na_(2)Ti_(3)O_(7) electrodes with excellent performance remains a severe challenge.This paper systematically summarizes and discusses the physicochemical properties and synthesis methods of Na_(2)Ti_(3)O_(7).Then,the sodium storage mechanisms,key issues and challenges,and the optimization strategies for the electrochemical performance of Na_(2)Ti_(3)O_(7) are classified and further elaborated.Finally,remaining challenges and future research directions on the Na_(2)Ti_(3)O_(7) anode are highlighted.This review offers insights into the design of high-energy and high-safety NIBs.
基金Project (51574294) supported by the National Natural Science Foundation of ChinaProject (2018zzts447) supported by the Fundamental Research Funds for the Central Universities of Central South University, China
文摘Cadmium was replaced by zinc in ammoniacal system using an electrically enhanced method under ultrasonic waves.Five main influencing factors were investigated by a single-factor experiment to determine the optimum parameters.Cyclic voltammetry and linear sweep voltammetry were applied to investigating the reaction mechanism of electrically enhanced cementation of cadmium on a zinc plate.The optimum parameters were a temperature of 35℃,a cathode-to-anode area ratio of 1:2,an anode current density of 15 A/m2,an ultrasonic frequency of 40 kHz a reaction time of 6 h and an ultrasonic power of 100 W.The extraction rate was 99.21%,and the production of byproduct“floating sponge cadmium”was inhibited.The analysis of the cyclic voltammetry and linear sweep voltammetry diagrams showed that ultrasonic waves can promote and accelerate the replacement reaction,decrease the voltage requirement of the electrically enhanced replacement reaction,and change the reaction steps.In addition,increasing the temperature and ultrasonic power can promote and accelerate electrically enhanced replacement reactions and decrease the electric potential requirement.
基金Project(50774094) supported by the National Natural Science Foundation of China
文摘The co-extraction behavior of galena-pyrolusite in a sodium chloride solution and the electrochemical mechanism of this process were investigated,and some factors affecting the leaching rate of Pb and Mn were optimized.The results show that all the factors such as the concentration of NaCl,HCl and pyrolusite ore,reaction time,temperature,adding times of HCl,affect the leaching rate of Pb.The main affecting factors are the concentration of NaCl,reaction time and temperature.The Tafel polarization curves and EIS plots of the galena and pyrolusite in the NaCl solution demonstrate that during the oxidation process of galena mineral electrode,film forms on the galena surface,which prevents galena from deeper oxidation.However,the film resistance can be greatly reduced in the presence of sodium chloride,thus promoting the reaction rate of galena.
基金The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China(grant no.21802047)and the Scientific Research Funds of Huaqiao University(grant no.600005-Z17Y0073),Xiamen,China.
文摘Four protic ionic liquids(ILs)were synthesized via a one-step method by using benzotriazole(BTA)and benzimidazole as cations,and benzenesulfonic acid and 2-naphthalenesulfonic acid(NSA)as anions.These ILs were used as green corrosion inhibitors for brass specimens in a nitric acid solution.The structure of the protic ILs was characterized by 1H-NMR,13C-NMR,and FT-IR spectroscopy.The effects of the IL structure,IL concentration,acid concentration,and corrosion time on the surface morphology of brass specimens and the inhibition efficiency(η%)of ILs were investigated by the weight loss method combined with SEM and EDS spectroscopy.Polarization curves and impedance spectroscopy were used to analyze the electrochemical corrosion inhibition mechanism of ILs.Results showed that IL synthesis was a proton transfer process,and the proton of the–SO3H group on NSA was deprived by BTA.IL[BTA][NSA],which had a high charge density and large conjugateπband,was the most effective inhibitor for brass corrosion.Theη%of[BTA][NSA]decreased with the increase in acid concentration and corrosion time,which showed an increment with the increase in[BTA][NSA]concentration.The higher theη%of[BTA][NSA]is,the smoother the surface of the brass specimens is,and the smaller the undistributed area of Cu element will be.Corrosion inhibiting mechanism from electrochemical analysis indicated that the addition of[BTA][NSA]increased the polarization resistance of the brass electrode significantly and suppressed both anodic and cathodic reactions.
基金supported by the National Natural Science Foundation of China (No. 51074060)
文摘Abstract The electrochemical reaction mechanism and electrocrystaUization process of tungsten in the NaCl- KCl-NaF-WO3 molten salt were investigated at 973 K （700℃） by means of cyclic voltammetry, chronopotentiometry, and chronoamperometry techniques. The results show that the electrochemical reaction process of tungsten in the NaCl-KCl-NaF-WO3 molten salt system is a quasireversible process mix-controlled by ion diffusion rate and electron transport rate. Tungsten ion in this system is reduced to W（0） in two steps. The electrocrystallization process of tungsten is found to be an instantaneous, hemispheroid three-dimensional nucleation process and the tungsten ion diffusion coefficient of 2.361 × 10^-4 cm2.s^-1 is obtained at experimental conditions.
基金supported by National Natural Science Foundation of China(No.52074036)Technology Innovation Program of Beijing Institute of Technology(No.2019CX01021)BIT Teli Young Fellow。
文摘With the advent of flexible/wearable electronic devices,flexible lithium-ion batteries(LIBs)have attracted significant attention as optimal power source candidates.Flexible LIBs with good flexibility,mechanical stability,and high energy density are still an enormous challenge.In recent years,many complex and diverse design methods for flexible LIBs have been reported.The design and evaluation of ideal flexible LIBs must take into consideration both mechanical and electrochemical factors.In this review,the recent progress and challenges of flexible LIBs are reviewed from a mechano-electrochemical perspective.The recent progress in flexible LIB design is addressed concerning flexible material and configuration design.The mechanical and electrochemical evaluations of flexible LIBs are also summarized.Furthermore,mechano-electrochemical perspectives for the future direction of flexible LIBs are also discussed.Finally,the relationship between mechanical loading and the electrode process is analyzed from a mechano-electrochemical perspective.The evaluation of flexible LIBs should be based on mechano-electrochemical processes.Reviews and perspectives are of great significance to the design and practicality of flexible LIBs,which is contributed to bridging the gap between laboratory exploration and practical applications.
文摘The cyclic plastic straining electrode technique has been used to investigate the transient electrochemical behaviour of Fe-26Cr1Mo stainless steel in 1M H2SO4 solution at a passive potential.The influence of plastic strain amplitude and plastic strain rate on the dissolution current response was analysed. The experimental results showed that the transient current was dependent on the competitive process of the surface film rupture and repassivation of the new surface. The high plastic strain amplitude and the high plastic strain rate caused a change of electrochemical activity of specimen surface. In the condition of low strain amplitude and strain rate, the characteristics of current response was mainly relative tp the process of new surface repassivation.The competition kinetics has been analysed through the comparison of plastic strain rate and repassivating rate
基金jointly supported by the Natural Science Foundations of China(22179020,12174057)the Fujian Natural Science Foundation for Distinguished Young Scholars(2020J06042)+1 种基金the Foreign Science and Technology Cooperation Project of Fuzhou Science and Technology Bureau(2021-Y-086)the Cultivation plan of outstanding young scientific research talents of Fujian Education Department(J1-1323)。
文摘At present,developing a simple strategy to effectively solve the shackles of volume expansion,poor conductivity and interface compatibility faced by Si-C anode in lithium batteries(LIBs)is the key to its commercialization.Here,low-cost nano-Si powders were prepared from Si-waste of solar-cells by sanding treatment,which can effectively reduce the commercialization cost for Si-C anode.Furthermore,micro-nano structured Gr@Si/C/TiO_(2) anode materials with graphite(Gr)as the inner core,TiO_(2)-doped and carbon-coated Si as the outer coating-layer,were synthesized at kilogram-scale per milling batch.Comprehensive characterization results indicate that TiO_(2)-doped carbon layer can improve the interface compatibility with the electrolyte,further promote the reduction of electrode polarization,and finally enhance the battery performance for the Gr@Si/C/TiO_(2) anodes.Accordingly,Gr@Si/C/TiO_(2) composites can output excellent LIB performance,especially with high initial coulombic efficiency(ICE)of 82.51%and large average reversible capacity of~810 mA h g^(-1) at 0.8 A g^(-1) after 1000 cycles.Moreover,Gr@Si/C/TiO_(2)‖NCM811 pouch full cells deliver impressive performance especially with high energy density of~489.3 W h kg^(-1) based on the total weight of active materials,suggesting its promising application in the high performance LIBs.
基金Great appreciation for the support of the funding of the Key R&D Program of Zhenjiang(GY201816)Student Innovation Project of Jiangsu University(22A030).
文摘Supercapacitors are electrochemical energy storage devices with great potential applications.Mean-while,the oxygen evolution reaction(OER)determines the efficiency of some electrochemical energy conversions.This study aims at constructing,exploring,and optimizing Ramsdellite-MnO_(2)@NiCoAl-LDH@CC(R-MNCA@CC)composites.The effect of microstructure and Al role on the performance is investigated when R-MNCA@CC was used as supercapacitor electrode material and OER catalyst.Coral-like R-MNCA@CC in-situ growth composites were synthesized by a two-step hydrothermal method.R-MNCA@CC-2(molar ratio of Ni:Co:Al is 1:1:1)performs the best with the largest specific capacitance,1,742 F/g at 1 A/g,increased by 797%and 1,489%compared to that of NiCoAl-LDH and Ramsdellite-MnO_(2).The capacitance retention rate of the R-MNCA@CC-2//AC@CC supercapacitor is 80.1%after 5,000 cycles at 0.8 A/g.The overpotential for driving an OER to reach 10 m/cm^(2)is only 276 mV,which is lower than that of commercial IrO_(2)(300 mV).Noteworthy,we propose a view that is“competing to trigger redox re-action”of electrochemical active sites in LDH during electrochemical processes derived from a discrepancy between theory and experimental results.
基金financially supported by the National Natural Science Foundation of China (Nos. 21820102002, 21931012, 22111530178, 51932001, 51872024, and 51972305)the Cooperation Fund of the Dalian National Laboratory for Clean Energy(DNL), Chinese Academy of Science (CAS) (No. DNL202020)+1 种基金the National Key Research and Development Program of China (No. 2018YFA0703503)the Scientific Instrument Developing Project of the Chinese Academy of Sciences (No. YZ201623)
文摘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.
基金This work was supported by the National Science Foundation(CBET-1803256)National Natural Science Foundation of China(Grant No.51772267)+3 种基金the National Key R&D Program of China(Grant No.2016YFB0401501)the Key R&D Program of Zhejiang Province(Grant No.2020C01004)The author acknowledges the financial support from China Scholarship Council(No.201906320198)2019 Zhejiang University Academic Award for Outstanding Doctoral Candidates.
文摘Ammonium vanadate with bronze structure(NH_(4)V_(4)O_(10))is a promising cathode material for zinc-ion batteries due to its high specific capacity and low cost.However,the extraction of NH^(+)_(4) at a high voltage during charge/discharge processes leads to irreversible reaction and structure degradation.In this work,partial NH^(+)_(4) ions were pre-removed from NH_(4)V_(4)O_(10) through heat treatment;NH_(4)V_(4)O_(10) nanosheets were directly grown on carbon cloth through hydrothermal method.Defi-cient NH_(4)V_(4)O_(10)(denoted as NVO),with enlarged interlayer spacing,facilitated fast zinc ions transport and high storage capacity and ensured the highly reversible electrochemical reaction and the good stability of layered structure.The NVO nanosheets delivered a high specific capac-ity of 457 mAh g^(−1) at a current density of 100 mA g^(−1) and a capacity retention of 81%over 1000 cycles at 2 A g^(−1).The initial Coulombic efficiency of NVO could reach up to 97%compared to 85%of NH_(4)V_(4)O_(10) and maintain almost 100%during cycling,indicating the high reaction reversibility in NVO electrode.
基金financial supports from the National Key Research and Development Program of China(No.2018YFC1900403)。
文摘A new hydrometallurgical process based on the methanesulfonic acid system was proposed to extract the bismuth efficiently from by-products of lead smelting.The bismuth extraction process included electrorefining,oxidation leaching,and electrodeposition.The optimum conditions of the bismuth extraction process were determined by a single-factor test.The bismuth plate with a purity of 99.8%was obtained under the optimum conditions.Cyclic voltammetry and linear sweep voltammetry were applied to investigating the cathode reaction mechanism of electrorefining.The results show that lead deposition,bismuth deposition,and hydrogen evolution occur at the cathode,and the reactions of metals deposition are irreversible and diffusion-controlled.In addition,decreasing the temperature and acidity can improve the purity of the cathodic product(lead powder)in the electrorefining process.
基金supported by the National Key Research and Development Program of China(2017YFB0102003 and2018YFB0104204)the National Natural Science Foundation of China(51622406,21673298 and 21473258)+2 种基金Young Elite Scientists Sponsorship Program By CAST(2017QNRC001)the Project of Innovation Driven Plan in Central South University(2017CX004 and 2018CX005)the Program for Innovative Team(in Science and Technology)in the University of Henan Province of China(17IRTSTHN003)
文摘The excellent energy storage performance of covalent sulfur-carbon material has gradually attracted great interest. However, in the electrochemical sodium storage process, the bond evolution mechanism remains an elusive topic. Herein, we develop a one-step annealing strategy to achieve a high covalent sulfur-carbon bridged hybrid(HCSC)utilizing phenylphosphinic acid as the carbon-source/catalyst and sodium sulfate as the sulfur-precursor/salt template, in which the sulfur mainly exists in the forms of C–S–C and C–S–S–C. Notably, most of the bridge bonds are electrochemically cleaved when the cycling voltage is lower than0.6 V versus Na/Na+, leading to the appearance of two visible redox peaks in the following cyclic voltammogram(CV) tests.The in-situ and ex-situ characterizations demonstrate that S^2- is formed in the reduction process and the carbon skeleton is concomitantly and irreversibly isomerized. Thus, the cleaved sulfur and isomerized carbon could jointly contribute to the sodium storage in 0.01–3.0 V. In a Na-S battery system, the activated HCSC in cut off voltage window of 0.6–2.8 V achieves a high reversible capacity(770 mA h g^-1 at 300 mA g^-1). This insight reveals the charge storage mechanism of sulfur-carbon bridged hybrid and provides an improved enlightenment on the interfacial chemistry of electrode materials.
基金This study was financially supported by the National Natural Science Foundation of China(No.51971124).
文摘Rechargeable lithium/sodium-sulfur batteries working at room temperature(RT-Li/S,RT-Na/S)appear to be a promising energy storage system in terms of high theoretical energy density,low cost,and abundant resources in nature.They are,thus,considered as highly attractive candidates for future application in energy storage devices.Nevertheless,the solubility of sulfur species,sluggish kinetics of lithium/sodium sulfide compounds,and high reactivity of metallic anodes render these cells unstable.As a consequence,metal-sulfur batteries present low reversible capacity and quick capacity loss,which hinder their practical application.Investigations to address these issues regarding S cathodes are critical to the increase of their performance and our fundamental understanding of RT-Li/S and RT-Na/S battery systems.Metal-sulfur interactions,recently,have attracted considerable attention,and there have been new insights on pathways to high‐performance RT-Li/Na sulfur batteries,due to the following factors:(1)deliberate construction of metal-sulfur interactions can enable a leap in capacity;(2)metal-sulfur interactions can confine S species,as well as sodium sulfide compounds,to stop shuttle effects;(3)traces of metal species can help to encapsulate a high loading mass of sulfur with high‐cost efficiency;and(4)metal components make electrodes more conductive.In this review,we highlight the latest progress in sulfide immobilization via constructing metal bonding between various metals and S cathodes.Also,we summarize the storage mechanisms of Li/Na as well as the metal-sulfur interaction mechanisms.Furthermore,the current challenges and future remedies in terms of intact confinement and optimization of the electrochemical performance of RT-Li/Na sulfur systems are discussed in this review.
基金Project(200501045) supported by Innovation Fund of Guangdong Province of China
文摘The electrochemical mechanism of anode oxidation of HCHO in electroless copper plating solution with N, N, N′, N′-tetrakis(2-hydroxypropyl)ethylenediamine (THPED) was investigated by measuring cyclic voltammetry curves and anodic polarization curves. Three different oxidation peaks occur at the potentials of -0.62 V (Peak 1), -0.40 V (Peak 2) and -0.17 V (Peak 3) in the anode oxidation process of THPED-containing solution. The reaction at Peak 1, a main oxidation reaction, is the irreversible reaction of adsorbed HCHO with hydrogen evolution. The reaction at Peak 2, a secondary oxidation reaction, is the quasi-reversible reaction of adsorbed HCHO without hydrogen evolution. The reaction at Peak 3 is the irreversible oxidation of anode copper. The current density of Peak 1 increases gradually, that of Peak 2 remains constant and that of Peak 3 decreases with the increase of HCHO concentration. The current density of Peak 3 increases with the increase of THPED concentration and the complexation of THPED promotes the dissolution of anode copper.
