A comprehensive overview of the electrochemical mechanisms in emerging alkali metal-carbon dioxide batteries

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.

Electrochemical corrosion failure mechanism of M152 steel under a salt-spray environment

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.

Review and prospects on the low-voltage Na_(2)Ti_(3)O_(7) anode materials for sodium-ion batteries

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.

Corrosion inhibiting performance and mechanism of protic ionic liquids as green brass inhibitors in nitric acid

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.

Electrochemical behavior of tungsten in(NaCl–KCl–NaF–WO_3)molten salt

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.

Mechano-electrochemical perspectives on flexible lithium-ion batteries

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.

Interaction of Mechanical and Electrochemical Factors duringCorrosion Fatigue of Fe-26Cr-1Mo Stainless Steel in 1M H_2SO_4 Solution

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

Scalable synthesized high-performance TiO_(2)-Si-C hybrid anode for lithium batteries

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.

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.

Enhanced Reversible Zinc Ion Intercalation in Deficient Ammonium Vanadate for High-Performance Aqueous Zinc-Ion Battery

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.

Manipulating metal-sulfur interactions for achieving high-performance S cathodes for room temperature Li/Na-sulfur batteries

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.

DISSOLUTION KINETICS OF GOLD AND SILVER IN CYANIDATION

The dissolution kinetics of gold and silver cyanidation of Cu-Au sulfide concentrate has been investigated at ambient temperature in consideration of effects of various parameters,such as particle size of ores,hydrodyna.mics of the process and initial cyanide concentration as well as oxygen partial pressure.The experimental data are mathematically treated with an approach based on the shrinking core model.A phenomenological expression describing the rate and rate constants for cyanidation of the concentrate is developed from the treatment.The dissolution of gold and silver is explained by an electrochemical mechanism in which the rate determining step is,the diffusion of cyanide and dissolved molecular oxygen through a porous layer formed during the minerals dis-solutions.

Understanding the improved performance of sulfur-doped interconnected carbon microspheres for Na-ion storage

As one of the low-cost energy storage systems,Na-ion batteries(NIBs)have received tremendous attention.However,the performance of current anode materials still cannot meet the requirements of NIBs.In our work,we obtain sulfur-doped interconnected carbon microspheres(S-CSs)via a simple hydrothermal method and subsequent sulfurizing treatment.Our S-CSs exhibit an ultrahigh reversible capacity of 520 mAh g^(-1) at 100 mA g^(-1) after 50 cycles and an excellent rate capability of 257 mAh g^(-1),even at a high current density of 2 A g^(-1).The density functional theory calculations demonstrate that sulfur doping in carbon favors the adsorption of Na atom during the sodiation process,which is accountable for the performance enhancement.Furthermore,we also utilize operando Raman spectroscopy to analyze the electrochemical reaction of our S-CSs,which further highlights the sulfur doping in improving Na-ion storage performance.

Transition metal carbonate anodes for Li-ion battery: fundamentals,synthesis and modification

Even though transition metal carbonates(TMCs, TM = Fe, Mn, Co, Ni etc.), show high theoretical capacities, rich reserves and environmental friendliness as anodes for lithium-ion batteries(LIBs), they suffer from sluggish electronic/ionic conductivities and huge volume variation, which severely deteriorate the rate capacities and cycling performances. Understanding the intrinsic reaction mechanism and further developing ideal TMC-based anode with high specific capacity, excellent rate capabilities, and longterm cycling stability are critical for the practical application of TMCs. In this review, we firstly focus on the fundamental electrochemical energy-storage mechanisms of TMCs, in terms of conversionreaction process, pseudocapacitance-type charge storage, valence change for charge storage and catalytic conversion mechanisms. Based on the reaction mechanisms, various modification strategies to improve the electrochemical performance of TMCs are summarized, covering:(i) micro-nano structural engineering, in which the influence factors on the morphology are discussed, and multiple architectures are listed;(ii) elemental doping, in which the intrinsic mechanisms of metal/nonmetal elements doping on the electrochemical performance are deeply explored;(iii) multifunctional compositing strategies, in which the specific affections on structure, electronic conductivity and chemo-mechanical stability are summarized.Finally, the key challenges and opportunities to develop high-performance TMCs are discussed and some solutions are also proposed. This timely review sheds light on the path towards achieving cost-effective and safe LIBs with high energy density and long cycling life using TMCs-based anode materials.

Graphite Anode for Potassium Ion Batteries: Current Status and Perspective

With the increased demand from the storage of renewable energy sources,some safe and inexpensive energy storage technologies instead of Li-ion batteries become urgently needed.Therefore,K-ion batteries(KIBs)have attracted much attention and evolved significant development because of the low price,safety,and similar property compared with Li-ion batteries.Due to the high reversibility,stability,and low potential plateau,graphite becomes a current research focus and is regarded as one of the most promising KIB’s anode materials.In this review,we mainly discuss the electrochemical reaction mechanism of graphite during potassiation-depotassiation process and analyze the effects of electrode/electrolyte interface on graphite for Kion storage.Besides,we summarize several kinds of methods to improve the performance of graphite for KIBs,including the design of graphite structure,selection of appropriate binder,solvent chemistry,and salt chemistry.Meanwhile,a concept of“relative energy density”is raised,which can be more accurate to evaluate the genuine electrochemical performance of graphite anode involving the specific capacity and potential.In addition,we also summarize the considerable challenges to current graphite anode in KIBs and we believe our work will offer alterative solutions to further explore high-performance graphite anode of K-ion storage.

Electrochemical oxidation of 1H,1H,2H,2H-perfluorooctane sulfonic acid(6:2 FTS) on DSA electrode:Operating parameters and mechanism

The 6：2 FTS was the substitute for perfluorooctane sulfonate（PFOS） in the chrome plating industry in Japan. Electrochemical oxidation of 6：2 FTS was investigated in this study. The degradabilities of PFOS and 6：2 FTS were tested on the Ti/SnO2–Sb2O5–Bi2O3anode. The effects of current density,potential,and supporting electrolyte on the degradation of 6：2 FTS were evaluated. Experimental results showed that 6：2 FTS was more easily degraded than PFOS on the Ti/SnO2–Sb2O5–Bi2O3anode. At a low current density of 1.42 mA/cm2,6：2 FTS was not degraded on Ti/SnO2–Sb2O5–Bi2O3,while the degradation ratio increased when the current density ranged from 4.25 to 6.80 mA/cm2. The degradation of 6：2 FTS at current density of 6.80 mA/cm2 followed pseudo first-order kinetics with the rate constant of 0.074 hr-1. The anodic potential played an important role in the degradation of 6：2 FTS,and the pseudo first-order rate constants increased with the potential. The surface of Ti/SnO2–Sb2O5–Bi2O3was contaminated after electrolysis at constant potential of 3 V,while the fouling phenomenon was not observed at 5 V. The fouled anode could be regenerated by incinerating at 600°C. The intermediates detected by ultra-performance liquid chromatography coupled with a triple-stage quadrupole mass spectrometer（UPLC–MS/MS） were shorter chain perfluorocarboxylic acids. The 6：2 FTS was first attacked by hydroxyl radical,and then formed perfluorinated carboxylates,which decarboxylated and removed CF2 units to yield shorter-chain perfluorocarboxylic acids.

Electrochemical reaction mechanism of porous Zn_(2)Ti_(3)O_(8)as a high-performance pseudocapacitive anode for Li-ion batteries

Zn_(2)Ti_(3)O_(8),as a new type of anode material for lithium-ion batteries,is attracting enormous attention because of its low cost and excellent safety.Though decent capacities have been reported,the electrochemical reaction mechanism of Zn_(2)Ti_(3)O_(8)has rarely been studied.In this work,a porous Zn_(2)Ti_(3)O_(8)anode with considerably high capacity(421 mAh/g at 100 mA/g and 209 mAh/g at 5000 mA/g after 1500 cycles)was reported,which is even higher than ever reported titanium-based anodes materials including Li_(4)Ti_(5)O_(12),TiO_(2)and Li_(2)ZnTi_(3)O_(8).Here,for the first time,the accurate theoretical capacity of Zn_(2)Ti_(3)O_(8)was confirmed to be 266.4 mAh/g.It was also found that both intercalation reaction and pseudocapacitance contribute to the actual capacity of Zn_(2)Ti_(3)O_(8),making it possibly higher than the theoretical value.Most importantly,the porous structure of Zn_(2)Ti_(3)O_(8)not only promotes the intercalation reaction,but also induces high pseudocapacitance capacity(225.4 mAh/g),which boosts the reversible capacity.Therefore,it is the outstanding pseudocapacitance capacity of porous Zn_(2)Ti_(3)O_(8)that accounts for high actual capacity exceeding the theoretical one.This work elucidates the superiorities of porous structure and provides an example in designing high-performance electrodes for lithium-ion batteries.

Hydrated ammonium manganese phosphates by electrochemically induced manganese-defect as cathode material for aqueous zinc ion batteries

Aqueous zinc ion batteries(AZIBs) with the merits of low cost, low toxicity, high safety, environmental benignity as well as multi-valence properties as the large-scale energy storage devices demonstrate tremendous application prospect. However, the explorations for the most competitive manganese-based cathode materials of AZIBs have been mainly limited to some known manganese oxides. Herein, we report a new type of cathode material NH_(4)MnPO_(4)·H_(2)O(abbreviated as AMPH) for rechargeable AZIBs synthesized through a simple hydrothermal method. An in-situ electrochemical strategy inducing Mn-defect has been used to unlock the electrochemical activity of AMPH through the initial charge process, which can convert poor electrochemical characteristic of AMPH towards Zn^(2+)and NH_(4)+into great electrochemically active cathode for AZIBs. It still delivers a reversible discharge capacity up to 90.0 m Ah/g at 0.5 A/g even after 1000thcycles, which indicates a considerable capacity and an impressive cycle stability. Furthermore, this cathode reveals an(de)insertion mechanism of Zn^(2+)and NH_(4)+without structural collapse during the charge/discharge process. The work not only supplements a new member for the family of manganese-based compound for AZIBs, but also provides a potential direction for developing novel cathode material for AZIBs by introducing defect chemistry.

Electrochemical Corrosion Behavior and Mechanical Response of Selective Laser Melted Porous Metallic Biomaterials

The porous metallic biomaterials have attracted significant attention for implants because their lower young's modulus matches the human bones, which can eliminate the stress shielding effect and facilitate the growth of bone tissue cells. The porous metallic biomaterials fabricated by selective laser melting (SLM) have broad prospects, but the surface of the SLM-built porous structure has been severely adhered with unmelted powders, which affects the forming accuracy and surface quality. The porous metallic biomaterials face the corrosion problem of complex body fluid environments during service, so their corrosion resistance in the human body is extremely important. The surface quality will affect the corrosion resistance of the porous metallic biomaterials. Therefore, it is necessary to study the effect of post-treatment on the corrosion resistance of SLMed samples. In this work, the mechanical response and the electrochemical corrosion behavior in simulated body fluid of diamond and pentamode metamaterials Ti-6Al-4V alloy fabricated by SLM before and after sandblasting were studied. After sandblasting, the mechanical properties of the two porous metallic biomaterials were slightly improved, and the self-corrosion potential and pitting potential were more negative;meanwhile, the self-corrosion current density and passive current density increased, indicating that its corrosion performance decreased, and the passive film stability of sandblasted samples got worse.

Enhanced cycling stability and rate performance of Co-doped and La_(2)O_(3)-coated LiNi_(0.9)Mn_(0.1)O_(2) toward power battery

Ultra-high nickel layered oxide cathode material with high energy density is the most promising material to improve the electrochemical performance of lithium-ion batteries(LIBs).However,the poor structural stability and severe surface/interface side reactions of the material lead to poor rate performance and cyclic stability,which limits its application in practice.In this paper,the dual-modification strategy of Co doping and La_(2)O_(3) coating is used to meet the above challenges.Co doping can effectively widen layer spacing and reduce Li^(+)/Ni^(2+) mixing,and La_(2)O_(3) coating can effectively eliminate the residual alkali on the surface of active material,inhibit the thickening of cathode electrolyte interphase(CEI)film and reduce surface/interface side reactions.Therefore,the modified material(NM90-CL)with excellent electrochemical properties is achieved through the synergistic enhancement of Co doping and La_(2)O_(3) coating.Its capacity retention rate can reach 77.9%after 200 cycles at 1.0℃ and 75.7%after 200 cycles at 5.0℃.Its reversible capacity can up to 153.5 mAh·g^(–1) at 10.0℃.This dual-modification strategy will provide theoretical guidance and technical support for the synthesis of other high-performance electrode materials.