Cathodic Zn underpotential deposition:an evitable degradation mechanism in aqueous zinc-ion batteries

Aqueous zinc-ion batteries(AZIBs)are promising for large-scale energy storage,but their development is plagued by inadequate cycle life.Here,for the first time,we reveal an unusual phenomenon of cathodic underpotential deposition(UPD)of Zn,which is highly irreversible and considered the origin of the inferior cycling stability of AZIBs.Combining experimental and theoretical simulation approaches,we propose that the UPD process agrees with a two-dimensional nucleation and growth model,following a thermodynamically feasible mechanism.Furthermore,the universality of Zn UPD is identified in systems,including VO_(2)//Zn,TiO_(2)//Zn,and SnO_(2)//Zn.In practice,we propose and successfully implement removing cathodic Zn UPD and substantially mitigate the degradation of the battery by controlling the end-ofdischarge voltage.This work provides new insights into AZIBs degradation and brings the cathodic UPD behavior of rechargeable batteries into the limelight.

Underpotential Deposition Study and Determination of Bismuth on Gold Electrode by Using Voltammetry

The cyclic voltammetry (CV) and the semidifferential anodic stripping voltammetry (SdASV) were used for investigation of bismuth(III) underpotential deposition (UPD) on gold electrode. Based on the excellent electrochemical properties of Au/Bi UPD system, a new method for determining bismuth(III) was established. A solution of 0.1 mol/L HNO 3 was selected as the supporting electrolyte. Factors affecting the Bi(III) UPD and stripping steps were investigated and an optimized analytical procedure was developed. The calibration plots for Bi(III) concentration in the range 1.25×10 -8 -1.0×10 -7 mol/L were obtained. The detection limit, calculated as three times the standard deviation of the analytical signal of 8.3×10 -8 mol/L for a 90 s electrodeposition at 0.00 V (while the solution magnetically stirred at a speed of 300 rpm), was 7.5×10 -9 mol/ L. For 8 successive determinations of 1.25×10 -7 mol/L Bi(III), the obtained RSD (relative standard deviation) was 0.4%. The developed method was applied to bismuth determining in medicine and urine samples. The analytical results were compared with that of atomic emission spectrometry (AES) method.

Investigations of Thallium(Ⅰ) Underpotential Deposition on the Silver Rotating Disk Electrode and Its Analytical Application

The cyclic voltammetry(CV) and the square wave technique were used for the investigations of thallium(Ⅰ) underpotential deposition(UPD) on the silver electrode. A solution of 10 \{mmol/L\} HClO 4+10 mmol/L NaCl was selected as the supporting electrolyte. The calibration plots for Tl(Ⅰ) concentration in the range of 2×10 -9 -1×10 -7 mol/L were obtained. The detection limit was 5×10 -10 mol/L. For the solutions of 4 0×10 -9 mol/L thallium added before the urine sample pretreatment procedure, the average recovery was 105 6% with a relative standard deviation(RSD) of 15 5%.

Underpotential Deposition Preparation of Pt-loading AuNPs/Reduced Graphene Oxide and Its Catalytic Detection of Catechol

Ultralow Pt-loading Au nanoparticles have been fabricated on the surface of reduced graphene oxide （RGO） by using underpotential deposition （UPD） monolayer redox replacement process. The Pt/Au/RGO modified electrode exhibits an excellent electrocatalytic activity toward catechol and hydroquinone. Under the optimized condition, the separation of peak-to-peak between hydroquinone and catechol is 197 mV, which is wide enough to distinguish the isomers of benzenediol. Catechol is detected by the Pt/Au/RGO/GCE with a low detection limit in the presence of hydroquinone.

A strongly interactive adatom/substrate interface for dendrite-free and high-rate Li metal anodes

Lithium (Li) metal is considered as one of the most promising anode materials to build next-generation high-energy–density batteries. Nonetheless, dendritic Li deposition has dramatically hindered the practical applications of Li metal batteries (LMBs). Uniformizing Li deposition is a prerequisite to achieve safe and practical LMBs. Herein, an underpotential deposition (UPD) process is first proposed to alter the kinetic and uniformity of Li deposition morphology. Based on the strong interaction between the Li adatoms and manganese (Mn) based substrate, a competition between the UPD and bulk Li deposition is observed, on which the predominance of the UPD scenario tends to uniformize Li nucleation and deposition by the surface coverage of Li monolayers at potentials that are more positive than the Nernst potential of Li metal. Inspired by this process, an advanced hybrid Mn-graphene oxide structure is developed for Li protection, not only enabling dendrite-free Li anodes for high-capacity and -current density cycling, but also improving the interfacial kinetic of Li metal anodes at subzero temperatures, showing potential applicability in low temperature conditions.

Electrochemical formation process and phase control of Mg-Li-Ce alloys in molten chlorides

An electrochemical approach for the preparation of Mg-Li-Ce alloys by co-reduction of Mg, Li and Ce on a molybdenum electrode in KCl-LiCl-MgCl2-CeCl3 melts at 873 K was investigated. Cyclic voltammograms （CVs） and square wave voltammograms indicated that the underpotential deposition （UPD） of cerium on pre-deposited magnesium led to the formation of Mg-Ce alloys at electrode potentials around –1.87 V. The order of electrode reactions was as follows： discharge of Mg（II） to Mg-metal, UPD of Ce on the surface of pre-deposited Mg with formation of Mg-Ce alloys, discharge of Ce（III） to Ce-metal and after that the discharge of Li＋ with the deposition of Mg-Li-Ce alloys, which was investigated by CVs, chronoamperometry, chronopotentiometry and open circuit chronopotentiometry. X-ray diffraction （XRD） illuminated that Mg-Li-Ce alloys with different phases were obtained via galvanostatic electrolysis by different current densities. The microstructures of Mg-Li-Ce alloys were characterized by optical microscopy （OM） and scanning electron microscopy （SEM）, respectively. The analysis of energy dispersive spectrometry （EDS） showed that Ce existed at grain boundaries to restrain the grain growth. The compositions and the average grain sizes of Mg-Li-Ce alloys could be obtained controllably corresponding with the phase structures of the XRD patterns.

Electrochemical quartz crystal microbalance study on Au-supported Pt adlayers for electrocatalytic oxidation of methanol in alkaline solution

Underpotential deposition(UPD) of Cu on an Au electrode followed by redox replacement reaction(RRR) of CuUPD with a Pt source(H2PtCl6 or K2PtCl4) yielded Au-supported Pt adlayers(for short,Pt(CuUPD-Pt4+)n/Au for H2PtCl6,or Pt(CuUPD-Pt2+)n/Au for K2PtCl4,where n denotes the number of UPD-redox replacement cycles).The electrochemical quartz crystal microbalance(EQCM) technique was used for the first time to quantitatively study the fabricated electrodes and estimate their mass-normalized specific electrocatalytic activity(SECA) for methanol oxidation in alkaline solution.In comparison with Pt(CuUPD-Pt2+)n/Au,Pt(CuUPD-Pt4+)n/Au exhibited a higher electrocatalytic activity,and the maximum SECA was obtained to be as high as 35.7 mA ?g?1 at Pt(CuUPD-Pt4+)3/Au.The layer-by-layer architecture of Pt atoms on Au is briefly discussed based on the EQCM-revealed redox replacement efficiency,and the calculated distribution percentages of bare Au sites agree with the experimental results deduced from the charge under the AuOx-reduction peaks.The EQCM is highly recommended as an efficient technique to quantitatively examine various electrode-supported catalyst adlayers,and the highly efficient catalyst adlayers of noble metals are promising in electrocatalysis relevant to biological,energy and environmental sciences and technologies.

Au nanowires with high aspect ratio and atomic shell of Pt-Ru alloy for enhanced methanol oxidation reaction

The methanol oxidation reaction(MOR)is the limiting half-reaction in direct methanol fuel cell(DMFC).Although Pt is the most active single-metal electrocatalyst for MOR,it is hampered by high cost and CO poisoning.Constructing a Pt or Ru monolayer on a second metal substrate by means of galvanic replacement of underpotentially deposited(UPD)Cu monolayer has been shown as an efficient catalyst design strategy for the electrocatalysis of MOR because of the presumed 100%utilization of atoms and resistance to CO poisoning.Herein,we prepared one-dimensional surface-alloyed electrocatalyst from predominantly(111)faceted Au nanowires with high aspect ratio as the substrate of under-potential deposition.The electrocatalyst comprises a core of the Au nanowire and a shell of catalytically active Pt coated by Ru.Coverage-dependent electro-catalytic activity and stability is demonstrated on the Pt/Ru submonolayers on Au wires for MOR.Among all these catalysts,Au@Pt_(ML)@Ru_(ML)exhibits the best electrocatalytic activity and poisoning tolerance to CO.This presents a viable method for the rational catalyst design for achieving high noble-metal utilization efficiency and high catalytic performance.