Mo Doping and Electrochemical Activation Co-Induced Vanadium Composite as High-Rate and Long-Life Anode for Ca-Ion Batteries

Calcium-ion batteries have been considered attractive candidates for large-scale energy storage applications due to their natural abundance and low redox potential of Ca^(2+)/Ca.However,current calcium ion technology is still hampered by the lack of high-capacity and long-life electrode materials to accommodate the large Ca^(2+)(1.00Å).Herein,an amorphous vanadium structure induced by Mo doping and in-situ electrochemical activation is reported as a high-rate anode material for calcium ion batteries.The doping of Mo could destroy the lattice stability of VS4 material,enhancing the flexibility of the structure.The following electrochemical activation further converted the material into sulfide and oxides co-dominated composite(defined as MoVSO),which serves as an active material for the storage of Ca^(2+)during cycling.Consequently,this amorphous vanadium structure exhibits excellent rate capability,achieving discharge capacities of 306.7 and 149.2 mAh g^(-1)at 5 and 50 A g^(-1)and an ultra-long cycle life of 2000 cycles with 91.2%capacity retention.These values represent the highest level to date reported for calcium ion batteries.The mechanism studies show that the material undergoes a partial phase transition process to derive MoVSO.This work unveiled the calcium storage mechanism of vanadium sulfide in aqueous electrolytes and accelerated the development of high-performance aqueous calcium ion batteries.

Electrochemical Activation-Induced Structural Transformation in Ni(OH)_(2)/Ti_(3)C_(2)T_(x)/NF Systems with Enhanced Electrochemical Performance for Hybrid Supercapacitors

Exploring a novel strategy for large-scale production of battery-type Ni(OH)_(2)-based composites,with excellent capacitive performance,is still greatly challenging.Herein,we developed a facile and cost-effective strategy to in situ grow a layer of Ni(OH)_(2)/Ti_(3)C_(2)T_(x)composite on the nickel foam(NF)collector,where Ti_(3)C_(2)T_(x)is not only a conductive component,but also a catalyst that accelerates the oxidation of NF to Ni(OH)_(2).Detailed analysis reveals that the crystallinity,morphology,and electronic structure of the integrated electrode can be tuned via the electrochemical activation,which is beneficial for improving electrical conductivity and redox activity.As expected,the integrated electrode shows a specific capacity of 1.09 C cm^(-2)at 1 mA cm^(-2)after three custom activation cycles and maintains 92.4%of the initial capacity after 1500 cycles.Moreover,a hybrid supercapacitor composed of Ni(OH)_(2)/Ti_(3)C_(2)T_(x)/NF cathode and activated carbon anode provides an energy density of 0.1 mWh cm^(-2)at a power density of 0.97 mW cm^(-2),and excellent cycling stability with about 110%capacity retention rate after 5000 cycles.This work would afford an economical and convenient method to steer commercial Ni foam into advanced Ni(OH)_(2)-based composite materials as binder-free electrodes for hybrid supercapacitors.

Enhanced performance in the direct electrocatalytic synthesis of ammonia from N2 and H2O by an in-situ electrochemical activation of CNT-supported iron oxide nanoparticles

The direct electrocatalytic synthesis of ammonia from N2 and H2O by using renewable energy sources and ambient pressure/temperature operations is a breakthrough technology,which can reduce by over 90%the greenhouse gas emissions of this chemical and energy storage process.We report here an in-situ electrochemical activation method to prepare Fe2O3-CNT(iron oxide on carbon nanotubes)electrocatalysts for the direct ammonia synthesis from N2 and H2O.The in-situ electrochemical activation leads to a large increase of the ammonia formation rate and Faradaic efficiency which reach the surprising high values of 41.6μg mgcat^−1 h^−1 and 17%,respectively,for an in-situ activation of 3 h,among the highest values reported so far for non-precious metal catalysts that use a continuous-flow polymer-electrolytemembrane cell and gas-phase operations for the ammonia synthesis hemicell.The electrocatalyst was stable at least 12 h at the working conditions.Tests by switching N2 to Ar evidence that ammonia was formed from the gas-phase nitrogen.The analysis of the changes of reactivity and of the electrocatalyst characteristics as a function of the time of activation indicates a linear relationship between the ammonia formation rate and a specific XPS(X-ray-photoelectron spectroscopy)oxygen signal related to O2−in iron-oxide species.This results together with characterization data by TEM and XRD suggest that the iron species active in the direct and selective synthesis of ammonia is a maghemite-type iron oxide,and this transformation from the initial hematite is responsible for the in-situ enhancement of 3-4 times of the TOF(turnover frequency)and NH3 Faradaic efficiency.This transformation is likely related to the stabilization of the maghemite species at CNT defect sites,although for longer times of preactivation a sintering occurs with a loss of performances.

Crystal plane induced in-situ electrochemical activation of manganese-based cathode enable long-term aqueous zinc-ion batteries

Rapid capacity decay and sluggish reaction kinetics are major barriers hindering the applications of manganese-based cathode materials for aqueous zinc-ion batteries.Herein,the effects of crystal plane on the in-situ transformation behavior and electrochemical performance of manganese-based cathode is discussed.A comprehensive discussion manifests that the exposed(100)crystal plane is beneficial to the phase transformation from tunnel-structured MnO_(2) to layer-structured ZnMn_(3)O_(7)·3H_(2)O,which plays a critical role for the high reactivity,high capacity,fast diffusion kinetics and long cycling stability.Additionally,a two-stage zinc storage mechanism can be demonstrated,involving continuous activation reaction and phase transition reaction.As expected,it exhibits a high capacity of 275 mAh g^(-1)at 100 mA g^(-1),a superior durability over 1000 cycles and good rate capability.This study may open new windows toward developing advanced cathodes for ZIBs,and facilitate the applications of ZIBs in large-scale energy storage system.

Determining the electrochemical activation mechanism of Prussian blue analog precatalysts for a high-efficiency oxygen evolution reaction

Prussian blue analogs(PBAs)are effective precatalysts for the oxygen evolution reaction(OER);however,the underlying mechanism of their electrochemical activation is still not well elucidated.In this study,we designed and constructed PBA-based precatalysts to determine the electrochemical activation mechanism and achieve high-efficiency OER.The PBAs undergo in situ electrochemical transformation to form the corre-sponding metal(oxy)hydroxides(M(O)OH)as the true OER catalyst.More importantly,the hexacyanoferrate ligands undergo repetitive interfacial coordination/etching with/from M(O)OH during the activation process.The distinct mechanism could achieve in situ Fe doping and enable defect incorporation.The defect-enriched Fe-NiOOH derived from a well-designed NiHCF/Ni(OH)2 precatalyst requires a low overpotential of 227 mV to reach a current density of 10 mA cm−2 and works stably at 130 mA cm−2 over 100 h.This study provides fundamental insights into the electrochemical activation mechanism for developing advanced precatalysts for OER.

In-situ electrochemical activation designed hybrid electrocatalysts for water electrolysis

Developing transition metal-based electrocatalysts with rich active sites for water electrolysis plays important roles in renewable energy fields. So far, some strategies including designing nanostructures, incorporating conductive support or foreign elements have been adopted to develop efficient electrocat- alysts. Herein, we summarize recent progresses and propose in-situ electrochemical activation as a new pretreating technique for enhanced catalytic performances. The activation techniques mainly comprise facile electrochemical processes such as anodic oxidation, cathodic reduction, etching, lithium-assisted tuning and counter electrode electro-dissolution. During these electrochemicaI treatments, the catalyst surfaces are modified from bulk phase, which can tune local electronic structures, create more active spe- cies. enlarge surface area and thus improve the catalytic performances. Meanwhile, this technique can couple the atomic, electronic structures with electrocatalysis mechanisms for water splitting. Compared to traditional chemical treatment, the in-situ electrochemical activation techniques have superior advantages such as facile operation, mild environment, variable control, high efficiency and flex- ibility. This review may provide guidance for improving water electrolysis efficiencies and hold promis- ing for application in many other energy-conversion fields such as supercapacitors, fuel cells and batteries.

Activation of urchin-like Ni-doped W_(18)O_(49)/NF by electrochemical tuning for efficient water splitting

The electrochemical conversion is closely correlated with the electrocatalytic activities of the electrocatalyst.Herein,the urchin-like Ni-doped W_(18)O_(49)/NF with enriched active sites was prepared by solvothermal method followed by a low-temperature pyrolysis treatment was reported.Results demonstrate that the incorporation of Ni-doping triggers the lattice distortion of W_(18)O_(49) for the increasement of oxygen defects.Further,high-valent W^(6+)are partially reduced to low-valent W^(4+),wherein the electrons originate from the oxidation process of Ni^(2+)to Ni^(3+).The Ni^(3+)ions show an enhanced orbital overlap with the OER reaction intermediates.The generated W^(4+)ions contribute to release oxygen vacancies,eventually reorganizing Ni-doped W_(18)O_(49)/NF to unique electrochemical active species with a special amorphous-crystalline interface(AM/NiWO_x/NiOOH/NF).Simultaneously,the reconstruction results in an optimized valence band and conduction band.Eventually,the resultant AM/NiWO_x/NiOOH/NF with abundant active sites and improved oxidation/reduction capability exhibits more superior catalytic performance compared with the Ni-doped W_(18)O_(49)/NF counterpart.This study gives more insights in the electrochemical evolution of the tungsten-based oxide and provides effective strategies for optimizing the catalytic activity of materials with inherent hydrogen evolution reaction limitations.

Fast electrochemical activation of the broadband saturable absorption of tungsten oxide nanoporous film

The on-demand modulation of defects in materials for the effective modulation of optical nonlinearity is desirable,while it remains a great challenge.In this work,we demonstrate that electrochemical activation is a facile and convenient approach to modulating the broadband third-order nonlinear absorption of nanoporous tungsten oxide(WO3-x)thin film.The film does not exhibit optical nonlinearity at the initial state,while shows a distinct saturable absorption under an applied voltage of-2.5 V with the excitation of 515,800,and 1,030 nm laser.The nonlinear absorption coefficient(β_(eff))is-766.38±6.67 cm·GW^(-1) for 1,030 nm laser,-624.24±17.15 cm·GW-1 for 800 nm laser,and-120.70±11.49 cm·GW^(-1) for 515 nm laser,and the performance is competitive among inorganic saturable absorbers.The activation is accomplished in 2 min.The performance enhancement is ascribed to the formation of abundant in-gap defect states because of the reduction of the tungsten atoms,and a Pauli-blocking effect occurs during the excitation of in-gap defect states.The small feature size of WO_(3-x)(-12 nm)enables the effective and fast introduction and removal of the defects in porous film,and accordingly the fast and broadband modulation of optical nonlinearity.Our results suggest a controllable,effective,and convenient approach to tuning the nonlinear absorption of materials.

Influence of Ga and In on microstructure and electrochemical properties of Mg anodes

The influence of Ga and In on the electrochemical properties of Mg anode materials were investigated by the polarization and galvanostatic curve tests. The microstructure and the corroded surface of the Mg-In-Ga alloys were observed by scanning electron microscopy （SEM）. The corrosion product of the Mg-0.8%In （mass fraction） and Mg-0.8%Ga-0.3%In alloy were determined by X-ray diffraction. The results show that no second phase exists in the Mg-xIn （x=0-0.8%） allloys. Intergranular compounds containing Ga and In elements occur in the Mg-0.8%In-xGa （x=0-0.8%） alloys. The addition of In into Mg as well as the addition of 0.05%-0.5%Ga into Mg-In alloy promotes the corrosion resistance. The addition of Ga into Mg-In alloys also promotes the electrochemical activity. The Mg-0.8%In-0.8%Ga alloy has the most negative mean potential,-1.682 V, which is more negative than -1.406 V in AZ91D. The corrosion type of the Mg-In-Ga alloys is general corrosion and the corrosion product is Mg（OH）2.

Effects of Hg and Ga on microstructures and electrochemical corrosion behaviors of Mg anode alloys

The effects of Hg and Ga on the electrochemical corrosion behaviors of the Mg-2%Hg, Mg-2%Ga and Mg-2%Hg-2%Ga (mass fraction) alloys were investigated by measurements of polarization curves, galvanostatic tests and measurements of electrochemical impedance spectroscopy. Scanning electron microscopy, X-ray diffractometry and energy dispersive spectrometry were employed to characterize the microstructures and the corroded surface of the above alloys. The results demonstrate that the microstructure of the Mg-2%Ga alloy is solid solution and the Mg-2%Hg and Mg-2%Hg-2%Ga alloys have white second-phases at the grain boundaries. The Mg-2%Ga alloy has the worst electrochemical activity and the best corrosion resistance, showing a mean potential of -1.48 V and a corrosion current density of 0.15 mA/cm2. The Mg-2%Hg-2%Ga alloy has the best electrochemical activity and the worst corrosion resistance, showing a mean potential of -1.848 V and a corrosion current density of 2.136 mA/cm2. The activation mechanism of the Mg-Hg-Ga alloy is dissolution-deposition of the Hg and Ga atoms.

Perspectives in Electrochemical in situ Structural Reconstruction of Cathode Materials for Multivalent-ion Storage

Multivalent-ion(such as Zn^(2+),Mg^(2+),Al^(3+))batteries are considered as a prospective alternative for large-scale energy storage.However,the main problem of cathode materials for multivalent-ion batteries is the sluggish diffusion of multivalent ions.Many cathode materials will self-adjust under electrochemical conditions to achieve the optimal state for multivalent-ion storage.In this review,the significant role of electrochemical in situ structural reconstruction of cathode materials is suggested.The types,basic characteristics,and formation mechanisms of reconstructed phases have been systematically discussed and commented.The most important insight we pointed out is that the cathode materials with loose structures after in situ electrochemical activation are conducive to the reversible diffusion of multivalent ions.Moreover,several crucial issues of electrochemical activation and reconstruction were further analyzed and discussed.The challenges and future perspectives are presented in the final section.

Electrochemically reduced graphene oxide with enhanced electrocatalytic activity toward tetracycline detection

An electrochemically reduced graphene oxide sample, ERGO_0.8v, was prepared by electrochemical reduction of graphene oxide （GO） at -0.8 V, which shows unique electrocatalytic activity toward tetracycline （TTC） detection compared to the ERGO-12v （GO applied to a negative potential of-1.2 V）, GO, chemically reduced GO （CRGO）-modified glassy carbon electrode （GC） and bare GC electrodes. The redox peaks of TTC on an ERGO-0.8v-modifled glass carbon electrode （GC/ERGO-0.8v） were within 0-0.5 V in a pH 3.0 buffer solution with the oxidation peak current correlating well with TTC concentration over a wide range from 0.1 to 160 mg/L Physical characterizations with Fourier transform infrared （FT-IR）, Raman, and X-ray photoelectron spectroscopies （XPS） demonstrated that the oxygen-containing functional groups on GO diminished after the electrochemical reduction at -0.8 V, yet still existed in large amounts, and the defect density changed as new sp2 domains were formed. These changes demonstrated that this adjustment in the number of oxygen-containing groups might be the main factor affecting the electrocatalytic behavior of ERGO. Additionally, the defect density and sp2 domains also exert a profound influence on this behavior. A possible mechanism for the TTC redox reaction at the GC/ERGO-0.8v electrode is also presented. This work suggests that the electrochemical reduction is an effective method to establish new catalytic activities of GO by setting appropriate parameters.

Influence of zinc on electrochemical discharge activity of Mg-6%Al-5%Pb anode

Mg-6%Al-5%Pb(mass fraction) anodes with different contents of zinc were prepared by melting and casting.The electrochemical discharge behavior of these anodes in 3.5% NaCl solutions was investigated by galvanostatic test and electrochemical impedance spectroscopy(EIS).The microstructures and the corroded surfaces of these anodes were studied by scanning electron microscopy(SEM) and emission spectrum analysis(ESA).The phase structures and the corrosion products of the anodes were analyzed by X-ray diffraction(XRD).The results show that zinc promotes the grain refinement of Mg-6%Al-5%Pb anode and makes the average discharge potential of Mg-6%Al-5%Pb anode more negative during galvanostatic test.Mg-6%Al-5%Pb anode with the addition of 1%(mass fraction) zinc has the best electrochemical performance.The activation mechanism of zinc to Mg-6%Al-5%Pb anode is as follows:The hydrolyzation of dissolved Zn2+ ions reduces the pH value of the solution near the surface of the anode and accelerates the dissolution of Mg(OH)2 film;The precipitated Zn(OH)2 with similar structure as Mg(OH)2 combines with Mg(OH)2 film easily and makes it break down.

Controllably partial removal of thiolate ligands from unsupported Au_(25) nanoclusters by rapid thermal treatments for electrochemical CO_(2)reduction

Colloidal synthesis of metal nanoclusters will inevitably lead to the blockage of catalytically active sites by organic ligands.Here,taking[Au_(25)(PET)_(18)]-(PET=2-phenylethanethiol)nanocluster as a model catalyst,this work reports a feasible procedure to achieve the controllably partial removal of thiolate ligands from unsupported[Au_(25)(PET)_(18)]-nanoclusters with the preservation of the core structure.This procedure shortens the processing duration by rapid heating and cooling on the basis of traditional annealing treatment,avoiding the reconfiguration or agglomeration of Au_(25)nanoclusters,where the degree of dethiolation can be regulated by the control of duration.This work finds that a moderate degree of dethiolation can expose the Au active sites while maintaining the suppression of the competing hydrogen evolution reaction.Consequently,the activity and selectivity towards CO formation in electrochemical CO_(2)reduction reaction of Au_(25)nanoclusters can be promoted.This work provides a new approach for the removal of thiolate ligands from atomically precise gold nanoclusters.

High Fe^(LS)(C)electrochemical activity of an iron hexacyanoferrate cathode boosts superior sodium ion storage

Sodium iron hexacyanoferrate(FeHCF)is one of the most promising cathode materials for sodium-ion batteries(SIBs)due to its low cost theoretical capacity.However,the low electrochemical activity of Fe^(LS)(C)in FeHCF drags down its practical capacity and potential plateau.Herein,FeHCF with high Fe^(LS)(C)electrochemical activity(C-FeHCF)is synthesized via a facile citric acid-assisted solvothermal method.As the cathode of SIBs,C-FeHCF shows superior cycling stability(ca.87.3%capacity retention for 1000 cycles at 10 C)and outstanding rate performance(ca.68.5%capacity retention at 50 C).Importantly,the contribution of Fe^(LS)(C)to the whole capacity was quantitatively analyzed via combining dQ/dV and discharge curve for the first time,and the index reaches 44.53%for C-FeHCF,close to the theoretical value.In-situ X-ray diffraction proves the structure stability of C-FeHCF during charge-discharge process,ensuring its superior cycling performance.Furthermore,the application feasibility of the C-FeHCF cathode in quasi-solid SIBs is also evaluated.The quasi-solid SIBs with the C-FeHCF cathode exhibit excellent electrochemical performance,delivering an initial discharge capacity of 106.5 mAh g^(−1) at 5 C and high capacity retention of 89.8%over 1200 cycles.This work opens new insights into the design and development of advanced cathode materials for SIBs and the beyond.

Biomass-derived activated carbon materials with plentiful heteroatoms for high-performance electrochemical capacitor electrodes

Activated carbons for electrochemical capacitor electrodes are prepared from soyabean using chemical activation with KOH. The pore size is easily controllable by changing the mass ratio between KOH and carbonized product. The as-prepared materials possess a large specific surface area, unique structure, well- developed hierarchical porosity and plentiful heteroatoms（mainly O and N）. Thus resulted in its high specific capacitance,good rate capacity and cycling stability. Moreover, attributing to worldwide availability, renewable nature and low-cost, activated carbon prepared from soyabean has a good potential in energy conversion and storage devices.

SYNTHESIS OF POLYCATECHOL WITH ELECTROCHEMICAL ACTIVITY AND ITS PROPERTIES

The electrochemical polymerization of catechol on platinum has been carried out using repeated potential cycling between -0.2 and 1.1 V (versus SCE). The electrolytic solution consisted of 0.2 mol dm(-3) catechol, 0.5 mol dm(-3) NaCl and 0.1 mol dm(-3) Na2HPO4 with pH 8.72. Catechol can not be polymerized at pH greater than or equal to 10.12. Polycatechol has an electrochemical lactivity at pH less than or equal to 4. The anodic and cathodic peak potentials of polycatechol shift towards more negative values as the pH of the solution increases from 1 to 4. The electrochemical activity of polycatechol hardly changes in this pH region, but it decreases slowly with time. This is caused by oxygen in air, which leads to an irreversible oxidation of polycatechol. This property is favorable for protecting metals from corrosion. Raman and FTIR spectra of polycatechol and catechol are quite different. AFM images of polycatechol films provide evidence that the image of the oxidized state of polycatechol is markedly different from that of the reduced one. This difference is caused by doping and dedoping of polycatechol.

Synthesis and Electrochemical Characterization of Azomethine Containing N-Ethylcarbazole Group

Conjugated aromatic azomethines containing a carbazole group were synthesized. Their structures have been confirmed by IR, MS and UV spectrometries. When iodine was used as the dope to the conjugated compounds, the electrical conductivities （EC） of the doped conjugated compounds were increased by several orders of magnitude. The thermal stability of these two compounds investigated by TGA shows a good result, which guarantees the correct result of EC when the compounds are heated. As can be seen from the CV characterization of the electrochemical properties of these two compounds, the azomethine diamine and p-aminophenyl-9-ethylcarbazolyl azomethine possess electrochemical activity, which arises from the heteroatom of molecules.

Heterointerface Engineering-Induced Oxygen Defects for the Manganese Dissolution Inhibition in Aqueous Zinc Ion Batteries

Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy.

Bulk nanoporous platinum for electrochemical actuation

Bulk nanoporous platinum(np-Pt)samples with a remarkably fine ligament size down to 2 nm and good mechanical robustness were fabricated for the first time by electrochemically dealloying Pt15Cu85 master alloy in 1 mol L−1 H_(2)SO_(4)at 60℃.The as-prepared np-Pt shows an electrochemically active specific surface area as high as 25 m^(2)/g due to the ultrafine nanostructure.The active surface area remains almost invariable even after 15%macroscopic compressive strain.Furthermore,np-Pt shows considerably high thermal stability due to the low surface diffusivity of Pt.Np-Pt is a promising surface-or interface-controlled functional material,particularly when excellent electrochemical and mechanical performance are necessary due to its high surface-to-volume ratio and mechanical robustness.This work demonstrated the potential application of np-Pt as an electrochemical actuation material.In-situ dilatometry experiments revealed that the surface adsorp-tion-desorption of OH species on np-Pt causes significant strain variations.The proposed np-Pt electrochem-ical actuator shows an operating voltage down to 1.0 V,a large reversible strain amplitude of 0.37%,and a strain energy density of 1.64 MJ/m^(3).