Confining Li_(2)O_(2) in tortuous pores of mesoporous cathodes to facilitate low charge overpotentials for Li-O_(2) batteries

Achieving low charge overpotentials represents one of the most critical challenges for pursuing highperformance lithium-oxygen(Li-O_(2))batteries.Herein,we propose a strategy to realize low charge overpotentials by confining the growth of lithium peroxide(Li_(2)O_(2))inside mesoporous channels of cathodes(CMK-8).The CMK-8 cathode with tortuous pore structures can extend the diffusion distance of lithium superoxide(LiO_(2))in the mesoporous channels,facilitating the further reduction of LiO_(2) to lithium peroxide(Li_(2)O_(2))inside the pores and preventing them to be diffused out of the pores.Therefore,Li_(2)O_(2) is trapped in the mesoporous channels of CMK-8 cathodes,ensuring a good Li_(2)O_(2)/CMK-8 contact interface.The CMK-8 electrode exhibits a low charge overpotential of 0.43 V and a good cycle life for 72 cycles with a fixed capacity of 500 m Ah g^(-1) at 0.1 A g^(-1).This study proposes a strategy to achieve a low charge overpotential by confining Li_(2)O_(2) growth in the mesoporous channels of cathodes.

Industrial-current-density CO_(2)-to-formate conversion with low overpotentials enabled by disorder-engineered metal sites

CO_(2)electroreduction to formate is technically feasible and economically viable,but still suffers from low selectivity and high overpotential at industrial current densities.Here,lattice-distorted metallic nanosheets with disorder-engineered metal sites are designed for industrial-current-density CO_(2)-to-formate conversion at low overpotentials.As a prototype,richly lattice-distorted bismuth nanosheets are first constructed,where abundant disorder-engineered Bi sites could be observed by high-angle annular dark-field scanning transmission electron microscopy image.In-situ Fourier-transform infrared spectra reveal the CO_(2)•−*group is the key intermediate,while theoretical calculations suggest the electron-enriched Bi sites could effectively lower the CO_(2)activation energy barrier by stabilizing the CO_(2)•−*intermediate,further affirmed by the decreased formation energy from 0.49 to 0.39 eV.As a result,the richly lattice-distorted Bi nanosheets exhibit the ultrahigh current density of 800 mA·cm^(−2)with 91%Faradaic efficiencies for CO_(2)-to-formate electroreduction,and the formate selectivity can reach nearly 100%at the current density of 200 mA·cm^(−2)with a very low overpotential of ca.570 mV,outperforming most reported metal-based electrocatalysts.

Highly Reversible Zn Metal Anodes Enabled by Increased Nucleation Overpotential

Dendrite formation severely compromises further development of zinc ion batteries. Increasing the nucleation overpotential plays a crucial role in achieving uniform deposition of metal ions. However, this strategy has not yet attracted enough attention from researchers to our knowledge. Here, we propose that thermodynamic nucleation overpotential of Zn deposition can be boosted through complexing agent and select sodium L-tartrate(Na-L) as example. Theoretical and experimental characterization reveals L-tartrate anion can partially replace H_(2)O in the solvation sheath of Zn^(2+), increasing de-solvation energy. Concurrently, the Na^(+) could absorb on the surface of Zn anode preferentially to inhibit the deposition of Zn^(2+) aggregation. In consequence, the overpotential of Zn deposition could increase from 32.2 to 45.1 mV with the help of Na-L. The Zn-Zn cell could achieve a Zn utilization rate of 80% at areal capacity of 20 mAh cm^(-2). Zn-LiMn_(2)O_(4) full cell with Na-L additive delivers improved stability than that with blank electrolyte. This study also provides insight into the regulation of nucleation overpotential to achieve homogeneous Zn deposition.

Effective ethanol-to-CO_(2) electrocatalysis at iridium-bismuth oxide featuring the impressive negative shifting of the working potential

Since low overpotential for the anodic ethanol oxidation reaction(EOR)can favor the higher output voltage and power of direct ethanol fuel cells(DEFCs),it is critical to design new EOR catalysts with efficient ethanol-to-CO_(2)activity at low applied potentials.Thereby,carbon-supported Ir-Bi_(2)O_(3)(Ir-Bi_(2)O_(3)/C)catalysts with highly dispersive bismuth oxide on the iridium surface are designed and prepared,which can merit splitting the ethanol C–C bond and promoting the oxidation of C1 intermediates at the bifunctional interfaces.The as-obtained Ir-Bi2O3/C catalysts show superior EOR mass activity of up to ca.2250 m A mgIr-1.Moreover,they exhibit the record lowest onset oxidation potentials(0.17–0.22 V vs.RHE)and the peak potential(ca.0.58 V vs.RHE),being 130–300 m V lower than the previous landmark noble metallic catalysts.Furthermore,an apparent C1 pathway faraday efficiency(FEC1)of 28%±5.9%at 0.5 V vs.RHE can be obtained at Ir-Bi_(2)O_(3)/C.This work might provide new insights into the new anodic EOR catalysts for increasing the power of DEFCs.

Active straining engineering on self-assembled stacked Ni-based hybrid electrode for ultra-low overpotential

Generating sufficient strains on metal surfaces are highly challenging owing to that most metals can deform plastically to relax the strains on the surfaces.In this work,we developed a facile but highly efficient stacked deposition strategy to in situ activation and reconstruction of NiO/NiOOH on Ni matrix,following with the migration of Fe ions to NiOOH.The Fe sites on the Ni/NiO/NiOOH facilitate the formation of the stable*OH oxygenated intermediates,and the Ni matrix in the catalyst provides the catalyst excellent stability.The oxygen evolution reaction(OER)performance of the stacked NiFe-5 with compressive strain displays the strengthened binding to oxygenated intermediates and superior OER activity,the ultralow overpotentials of 162 versus reversible hydrogen electrode at 10 mA cm^(-2).On the other hand,the Ni-5 without the incorporation of Fe has shown an outstanding hydrogen evolution reaction(HER)activity,affording an overpotential of 47 mV at 10 mA cm^(-2).The NiFe-5‖Ni-5 enables the overall water splitting at a voltage of 1.508 V to achieve 20 mA cm^(-2) with remarkable durability.The stacked deposition strategy improves binding strength of Ni-based catalysts to oxygenated intermediates via generating compressive strain,causing high catalytic activities on OER and HER.

Microstructure and depositional mechanism of Ni-P coatings with nano-ceria particles by pulse electrodeposition

Nano-CeO2 （RE） particles were co-deposited into Ni-P binary composite coatings by applying pulse current （PC） under ultrasonic （U） field. Morphology, chemical content and crystal microstructure were characterized by environmental scanning electron microscopy （E-SEM） with energy dispersive X-ray analysis （EDXA）, XRD diffractometry and transmission electron microscopy （TEM）. Experimental results show that Ni-P coating reinforced with 15g/L nano-CeO2, in amorphous state and with compact structure, can be improved in the microhardness from HV0.2580 to HV0.2780 by annealing at 600 °C for 2 h. The highest content of codeposited Ce and deposition rate can reach 2.3% and 68 μm/h, respectively. Furthermore, the effect of RE adsorption and pulse overpotential on depositional mechanism was investigated. n-CeO2 particles or Ce4＋ ions with strong adsorption capacity acted as the catalytic nucleus to improve densification effectively. During annealing at 600 °C for 2 h, n-CeO2 particles will uniformly adsorb on crystal grain to preferentially pad and heal up gaps of cracking Ni boundaries, promoting dispersion strengthening with refiner-grained structure.

金属电积中节能阳极的研究

本文研究了钛基IrO_2-PAN电极的制备,得到了一种有实际意义的新型节能阳极(锌电积条件下,η02=0.316V,在i=20,000A/m^2的加速寿命实验中τ=118.4hr)。该电极寿命较长,价格不算高,有工业生产可行性,可节约消耗在电解池部分的能量25%。还考察了不同制备条件对电极表面结构及电化学性能的影响,得出了最佳电极的大致表面结构。

Kinetics Study on O2 Adsorption and OHad Desorption at Pt（111）, Its Implication to Oxygen Reduction Reaction Kinetics

Kinetics of dissociative O2 adsorption, OHad desorption, and oxygen reduction reaction （ORR） at Pt（111） electrode in 0.1 mol/L HClO4 has been investigated. Reversible OHad adsorption/desorption occurs at potentials from 0.6 V to 1.0 V （vs. RHE） with the exchange current density of ca. 50 mA/cm^2 at 0.8 V, the fast kinetics of OHad desorption indicates that it should not be the rate determining step for ORR. In the kineticor kinetic-mass transport mix controlled potential region, ORR current at constant potential displays slight decrease with reaction time. ORR current in the positive-going potential scan is slightly larger than that in the subsequent negative-going scan with electrode rotation speed （〉800 r/min） and slow potential scan rate （〈100 mV/s）. The open circuit potential of Pt/0.1 mol/L HClO4 interface increases promptly from 0.9 V to 1.0 V after switch from O2 free- to O2-saturated solution. The increase of open circuit potential as well as ORR current decays under potential control due to the accumulation of OHad from dissociative adsorption of O2. It indicates that at Pt（111） the net rate for O2 decomposition to OHad is slightly faster than that for OHad removal, one cannot simply use the assumption of rate determining step to discuss ORR kinetics. Instead, the ORR kinetics is determined by both the kinetics for O2 decomposition to OHad as well as the thermo-equilibrium of OHad＋H^＋＋e→←H2O.

In situ growth of minimal Ir-incorporated CoxNi1-xO nanowire arrays on Ni foam with improved electrocatalytic activity for overall water splitting

Exploration of cost-effective electrocatalysts for boosting the overall water-splitting efficiency is vitally important for obtaining renewable fuels such as hydrogen.Here,earth-abundant CoxNi1-xO nanowire arrays were used as a structural framework to dilute Ir incorporation for fabricating electrocatalysts for water splitting.Minimal Ir-incorporated CoxNi1-xO nanowire arrays were synthesized through the facile hydrothermal method with subsequent calcination by using Ni foam(NF)as both the substrate and source of Ni.The electrocatalytic water-splitting performance was found to crucially depend on the Ir content of the parent CoxNi1-xO nanowire arrays.As a result,for a minimal Ir content,as low as 0.57 wt%,the obtained Ir-CoxNi1-xO/NF electrodes exhibited optimal catalytic activity in terms of a low overpotential of 260 mV for the oxygen evolution reaction and 53 mV for the hydrogen evolution reaction at 10 mA cm?2 in 1 mol L–1 KOH.When used as bifunctional electrodes in water splitting,the current density of 10 mA cm–2 was obtained at a low cell voltage of 1.55 V.Density functional theory calculations revealed that the Ir-doped CoxNi1-xO arrays exhibited enhanced electrical conductivity and low Gibbs free energy,which contributed to the improved electrocatalytic activity.The present study presents a new strategy for the development of transition metal oxide electrocatalysts with low levels of Ir incorporation for efficient water splitting.

N-heterocyclic carbene as a promising metal-free electrocatalyst with high efficiency for nitrogen reduction to ammonia

Electrocatalytic nitrogen reduction reaction(NRR)at ambient conditions holds great promise for sustainably synthesizing ammonia(NH3),while developing highly-efficient,long-term stable,and inexpensive catalysts to activate the inert N≡N bond is a key scientific issue.In this work,on the basis of the concept"N-heterocyclic carbenes(NHCs)",we propose a carbon decorated graphitic-carbon nitride(C/g-C3N4)as novel metal-free NRR electrocatalyst by means of density functional theory(DFT)computations.Our results reveal that the introduced C atom in g-C3N4 surface can be regarded as NHCs and catalytic sites for activating N≡N bond,and are stabilized by the g-C3N4 substrate due to sterically disfavored dimerization.Especially,this NHCs-based heterogeneous catalysis can efficiently reduce the activated N2 molecule to NH3 with a low overpotential of 0.05 V via an enzymatic mechanism.Our work is the first report of NHCs-based electrocatalyst for N2 fixation,thus opening an alternative avenue for advancing sustainable NH3 production.

A systematical study on the electrodeposition process of metallic lithium

In this study,commercial copper(Cu)foil and Cu foam are used as the working electrodes to systematically investigate the electrochemical deposition and dissolution processes of metallic lithium(Li)on these electrodes;Li metal deposited on the Cu foil electrode is porous and loose.The surface solid electrolyte interface(SEI)film after dissolution from Li dendrites maintains a dendritic porous structure,resulting in a large volume effect of the electrode during the cycle.The Cu foam electrode provides preferential nucleation and deposition sites near the side surface of the separator;the difference in Li affinity results in a heterogeneous deposition and dendrite growth of metallic Li.

Environment friendly hydrothermal synthesis of carbon–Co3O4 nanorods composite as an efficient catalyst for oxygen evolution reaction

The design of cost-effective, highly active catalysts for hydrogen energy production is a vital element in the societal pursuit of sustainable energy. Water electrolysis is one of the most convenient processes to produce high purity hydrogen. Cobalt-based catalysts are well-known electrocatalysts for oxygen evolution reaction（OER）. In this article, all these merits indicate that the present cobalt nanocomposite is a promising electrocatalyst for OER. C–CoO-nanorods catalyst with nanorod structure was synthesized by hydrothermal treatment of CoCl·6HO/dextrose/urea mixture at 180 °C for 18 h and then calcined at400 °C for 3.5 h. The role of dextrose percentage in solution to achieve the uniform coating of carbon on the surface of CoO-nanorods has been demonstrated. The prepared materials were characterized by X-ray diffraction（XRD）, X-ray photoelectron spectrum（XPS）, field emission scanning electron microscopy（FE-SEM）, high-resolution transmission electron microscopy（HR-TEM）, and Brunauer–Emmett–Teller instrument（BET）. Due to its unique morphology, the C–CoO-nanorods catalyst exhibited better activity than CoO-microplates catalyst for OER in 1 M KOH aqueous solution. The results showed a highly efficient, scalable, and low-cost method for developing highly active and stable OER electrocatalysts in alkaline solution.

A theoretical study of electrocatalytic ammonia synthesis on single metal atom/MXene

Electrocatalytic ammonia synthesis under mild conditions is an attractive and challenging process in the earth’s nitrogen cycle,which requires efficient and stable catalysts to reduce the overpotential.The N2 activation and reduction overpotential of different Ti3C2O2-supported transition metal(TM)(Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Mo,Ru,Rh,Pd,Ag,Cd,and Au)single-atom catalysts have been analyzed in terms of the Gibbs free energies calculated using the density functional theory(DFT).The end-on N2 adsorption was more energetically favorable,and the negative free energies represented good N2 activation performance,especially in the presence Fe/Ti3C2O2(﹣0.75 eV).The overpotentials of Fe/Ti3C2O2,Co/Ti3C2O2,Ru/Ti3C2O2,and Rh/Ti3C2O2 were 0.92,0.89,1.16,and 0.84 eV,respectively.The potential required for ammonia synthesis was different for different TMs and ranged from 0.68 to 2.33 eV.Two possible potential-limiting steps may be involved in the process:(i)hydrogenation of N2 to*NNH and(ii)hydrogenation of*NH2 to ammonia.These catalysts can change the reaction pathway and avoid the traditional N–N bond-breaking barrier.It also simplifies the understanding of the relationship between the Gibbs free energy and overpotential,which is a significant factor in the rational designing and large-scale screening of catalysts for the electrocatalytic ammonia synthesis.

Electrochemical properties of powder-pressed Pb-Ag-PbO_(2) anodes

Pb?Ag?PbO2 composite anodes with different mass fractions(1%,2%,3%,4%and 5%)ofβ-PbO2 were prepared by powder-pressed(PP)method.The galvanostatic polarization curves,Tafel curves and anodic polarization curves were tested in sulfuric acid solution.The morphologies and phase compositions of the anodic layers formed after galvanostatic polarization were investigated by using scanning electron microscope(SEM)and X-ray diffractometer(XRD),respectively.The results showed thatβ-PbO2 can improve the electrocatalytic activity of anodic oxide.The anode containing 3%β-PbO2 had the lowest overpotential of oxygen evolution reaction(OER)and the best corrosion resistance.The morphologies of the anode surfaces were gradually transformed from regular crystals to amorphous ones as the content ofβ-PbO2 increased in anodes.

Mathematical analysis of SOFC based on co-ionic conducting electrolyte

In co-ionic conducting solid oxide fuel cell （SOFC）, both oxygen ion （O2） and proton （H＋） can transport through the electrolyte, generating steam in both the an-ode and cathode. Thus the mass transport phenomenon in the electrodes is quite different from that in conventional SOFC with oxygen ion conducting electrolyte （O-SOFC） or with proton conducting electrolyte （H-SOFC）. The generation of steam in both electrodes also affects the concentration over-potential loss and further the SOFC performance. However, no detailed modeling study on SOFCs with co-ionic electrolyte has been reported yet. In this paper, a new mathematical model for SOFC based on co-ionic electrolyte was developed to predict its actual performance considering three major kinds of overpotentials. Ohm＇s law and the Butler-Volmer formula were used to model the ion conduction and electrochemical reactions, respectively. The dusty gas model （DGM） was employed to simulate the mass transport processes in the porous electrodes. Parametric simulations were performed to investigate the effects of proton transfer number （tH） and current density （jtotal） on the cell performance. It is interesting to find that the co-ionic conducting SOFC could perform better than O-SOFC and H-SOFC by choosing an appropriate proton transfer number. In addition, the co-ionic SOFC shows smaller difference between the anode and cathode concentration overpotentials than O-SOFC and H-SOFC at certain t H values. The results could help material selection for enhancing SOFC performance.

Revealing the illumination effect on the discharge products in high-performance Li-O_(2) batteries with heterostructured photocatalysts

Aprotic lithium–oxygen batteries(LOBs)have been recognized as novel energy storage devices for their outstanding specific energy density,while the large discharge/charge overpotential is a tough barrier to be overcome.Here,hetero-structured MoS_(2)/ZnIn_(2)S_(4) nanosheets have been prepared to capture visible light and the generated charge carriers are utilized for promoting both the oxygen reduction reaction and the oxygen evolution reaction.With the light illumination in the discharge process,the abundant photo-inspired electrons serve as the reaction sites to promote the reduction of O_(2) into LiO_(2) which is finally deposited as Li_(2)O_(2).On the contrary,the generated holes in the valence band can contribute to the low oxidization potential of Li_(2)O_(2) during the charge process.It delivers a low charge potential of 3.29 V,with an excellent resulting energy efficiency of 96.7%,much superior to that of 69.2%in the dark condition.It is noted that the involvement of photoelectrons has influenced the growth of Li_(2)O_(2) films on the MoS_(2)/ZnIn_(2)S_(4) nanosheets through the surface-adsorption pathway.The insights from the theoretical calculation confirm that the photoelectrons favor the absorption of LiO_(2) and the formation of the Li_(2)O_(2) film through the surface route.Therefore,this paper provides a deeper understanding of the mechanism of photoinspired charge carriers in LOBs and will enable further exploration of photo-involved energy storage systems.

Integrated Ni-P-S nanosheets array as superior electrocatalysts for hydrogen generation

Searching for efficient and robust non-noble electrocatalysts for hydrogen generation is extremely desirable for future green energy systems.Here, we present the synthesis of integrated Ni-P-S nanosheets array including Ni_2P and NiS on nickel foam by a simple simultaneous phosphorization and sulfurization strategy. The resultant sample with optimal composition exhibits superior electrocatalytic performance for hydrogen evolution reaction(HER) in a wide pH range. In alkaline media, it can generate current densities of 10, 20 and 100 mA cm^(-2) at low overpotentials of only-101.9,-142.0 and-207.8 mV with robust durability. It still exhibits high electrocatalytic activities even in acid or neutral media. Such superior electrocatalytic performances can be mainly attributed to the synergistic enhancement of the hybrid Ni-P-S nanosheets array with integration microstructure. The kind of catalyst gives a new insight on achieving efficient and robust hydrogen generation.

Influence of process parameters on electrochemical and physical properties of sputtered iron-doped nickel oxide thin films

The iron-doped nickel oxide films used as oxygen evolution catalysts in the photoelectrochemical production of hydrogen from solar energy were deposited by means of RF reactive magnetron sputtering from a Ni-Fe alloy target in oxygen and argon atmosphere.The effects of processing parameters on the film properties,such as overpotential,composition,surface morphology and preferred orientation,were investigated.The electrochemical experiment,structural and compositional measurements indicate that the relative lower substrate temperature,higher RF power,higher working pressure and oxygen content are necessary to gain lower overpotential.The lowest overpotential of 251 mV is obtained at a current density of 80 mA/cm2.The existence of iron,which acts as activity site,and Ni3+ ion is responsible for lowering overpotential.By analyzing SEM and XRD data,it is also noticed that an improvement in crystallinity,appropriate grain size and less crystalline phase contribute to an increased electrocatalytic activity in oxygen evolution reaction.These results mentioned above indicate that iron-doped nickel oxide is promising as an oxygen catalyst.

Ag nanoparticles anchored on MIL-100/nickel foam nanosheets as an electrocatalyst for efficient oxygen evolution reaction performance

Metal-organic frameworks(MOFs)exhibit excellent application potential in the field of electrocatalysis.In this study,we first prepare MIL-100 nanosheets on nickel foam(MIL-100/NF)and then successfully anchor Ag nanoparticles(NPs)on the nanosheets(Ag@MIL-100/NF)for oxygen evolution reaction(OER)catalysis.This strategy dramatically improves the conductivity of MIL-100 and the Ag NPs are uniformly dispersed on the nanosheets.The Ag@MIL-100/NF catalyst has excellent electrocatalytic performance and long-term corrosion resistance,with a low overpotential of 207 mV and a long-term stability of at least 100 h at a current density of 50 mA·cm^(-2).The experimental results demonstrate that this high OER catalytic performance is due to the improved charge transfer after loading Ag NPs,the combination of nanosheets and highly dispersed Ag NPs that expose more active sites and the adjusted chemical valence states of Fe and Ni in MIL-100.This work provides a surface decoration approach for the preparation of excellent catalysts directly used in the OER.

Uniform zinc deposition on O,N-dual functionalized carbon cloth current collector

The society’s urgent demand for environmentally friendly, safe and low-cost energy storage devices has promoted the research of aqueous zinc-ion batteries. However, the uneven deposition of Zn ions on anodes will lead to the growth of the dendrite and reduce the Coulombic efficiency as well as the lifespan of the devices. Herein, we construct an O,N-dual functionalized carbon cloth current collector via a simple hydrothermal strategy, in which the oxygen-containing functional groups and the N heteroatoms can regulate the transmission and deposition of Zn ions, respectively. The proposed synergistic strategy ensures the uniform distribution of Zn ions on the surface of the Zn anode and inhibits the formation of dendrites. The symmetric cell based on the O,N-dual doped carbon cloth presents superior cycling stability(318 h) with a low voltage hysteresis(11.2 mV) at an areal capacity of 1 m Ah cm^(-2)(20% depth of diacharge). Meanwhile, the appreciably low overpotential(16 m V) and high Columbic efficiency(98.2%)also demonstrate that the O,N-dual functionalized carbon cloth can be worked as a promising host for Zn ions deposition.