Research progress of magnesium anodes and their applications in chemical power sources

Magnesium is a promising metal used as anodes for chemical power sources. This metal could theoretically provide negative discharge potential and exhibit large capacity during the discharge process. However, when the magnesium anode is adopted for practical applications, several issues, such as the discharge products adhered to the electrode surface, the self-discharge occurring on the anode material, and the detachment of metallic particles, adversely affect its inherently good discharge performance. In this work, the types of chemical power sources using magnesium as anodes were elaborated, and the approaches to enhance its anode performance were analyzed.

Discharge properties and electrochemical behaviors of AZ80-La-Gd magnesium anode for Mg-air battery

In this work,the discharge properties and electrochemical behaviors of as-cast AZ80-La-Gd anode for Mg-air battery have been investigated and compared with the AZ80 anode.The microstructure evolution,electrochemical behaviors and surface morphologies after discharge have been discussed to connect the discharge properties.The results indicate that the modified AZ80-La-Gd is an outstanding candidate for anode for Mg-air batter,which has high cell voltage,stable discharge curves,good specific capacity and energy,and good anodic efficiency.It exhibits the best anodic efficiency,specific capacity and energy of 76.45%,1703.6 mAh·g^(-1)and 2186.3 mWh·g^(-1),respectively,which are20.24%,18.92%and 25.71%higher than values for AZ80 anode.Such excellent discharge performance is attributed to the Al-RE particles.They refine the Mg_(17)Al_(12)phase and therefore improve the self-corrosion resistance and desorption ability of AZ80 anode.

Tailoring the microstructure of Mg-Al-Sn-RE alloy via friction stir processing and the impact on its electrochemical discharge behaviour as the anode for Mg-air battery

Constructing the magnesium alloy with fine grains,low density of dislocations,and weak crystal orientation is of crucial importance to enhance its comprehensive performance as the anode for Mg-air battery.However,this unique microstructure can hardly be achieved with conventional plastic deformation such as rolling or extrusion.Herein,we tailor the microstructure of Mg-Al-Sn-RE alloy by using the friction stir processing,which obviously refines the grains without increasing dislocation density or strengthening crystal orientation.The Mg-air battery with the processed Mg-Al-Sn-RE alloy as the anode exhibits higher discharge voltages and capacities than that employing the untreated anode.Furthermore,the impact of friction stir processing on the electrochemical discharge behaviour of Mg-Al-Sn-RE anode and the corresponding mechanism are also analysed according to microstructure characterization and electrochemical response.

Unlock the full potential of carbon cloth-based scaffolds towards magnesium metal storage via regulation on magnesiophilicity and surface geometric structure

The development of rechargeable magnesium(Mg) batteries is of practical significance to upgrade the electric energy storage devices due to exceptional capacity and abundant resources of Mg-metal anode.However,the reversible Mg electrochemistry suffers from unsatisfied rate capability and lifespan,mainly caused by non-uniform distribution of electrodeposits.In this work,a fresh design concept of threedimensional carbon cloths scaffolds is proposed to overcome the uncontrollable Mg growth via homogenizing electric field and improving magnesiophilicity.A microscopic smooth and nitrogen-containing defective carbonaceous layer is constructed through a facile pyrolysis of ZIF8 on carbon cloths.As revealed by finite element simulation and DFT calculation results,the smooth surface endows with uniform electric field distribution and simultaneously the nitrogen-doping species enable good magnesiophilicity of scaffolds.The fine and uniform Mg nucleus as well as the inner electrodeposit behavior are also disclosed.As a result,an exceptional cycle life of 500 cycles at 4.0 mA cm^(-2) and 4.0 mA h cm^(-2) is firstly realized to our best knowledge.Besides,the functional scaffolds can be cycled for over 2200 h at 2.0 mA cm^(-2) under a normalized capacity of 5.0 mA h cm^(-2),far exceeding previous results.This work offers an effective approach to enable the full potential of carbon cloths-based scaffolds towards metal storage for next generation battery applications.

Effects of Al and Sn on electrochemical properties of Mg-6%Al-1%Sn (mass fraction) magnesium alloy as anode in 3.5%NaCl solution

Mg-6%Al-1%Sn(mass fraction) alloy is a newly developed anode material for seawater activated batteries. The electrochemical properties of Mg-1%Sn, Mg-6%Al and Mg-6%Al-1%Sn alloys are measured by galvanostatic and potentiodynamic tests. Scanning electron microscopy(SEM) with energy dispersive spectrometry(EDS) is used to characterize the microstructures of the experimental alloys. The results show that the Mg-6%Al-1%Sn alloy obtains more negative discharge potential(-1.38 V(vs SCE)) in hot-rolled condition. This is attributed to the fine dynamically recrystallized grains during the hot rolling process. After the experimental alloys are annealed at 473 K for 1 h, the discharge potentials of Mg-6%Al-1%Sn alloy are more negative than those of Mg-6%Al alloy under different current densities. After annealing at 673 K, the discharge potentials of Mg-6%Al-1%Sn alloy become more positive than those of Mg-6%Al alloy. Such phenomenon is due to the coarse grains and the second phase Mg2 Sn. The discharge potentials of Mg-1%Sn shift positively obviously in the discharge process compared with Mg-6%Al-1%Sn alloy. This is due to the corrosion products pasting on the discharge surface, which leads to anode polarization.

Discharge behavior and electrochemical properties of Mg-Al-Sn alloy anode for seawater activated battery

Mg-Al-Sn alloy is one of the new developed anode materials for seawater activated batteries. The potentiodynamic polarization, galvanostatic discharge and electrochemical impedance spectroscopy of Mg-6%Al-1%Sn and Mg-6%Al-5%Sn(mass fraction) alloys in seawater were studied and compared with the commercial AZ31 and AP65 alloys. The results show that the Mg-6%Al-1%Sn alloy obtains the most negative discharge potential of average-1.611V with a electric current density of 100 mA/cm2. EIS studies reveal that the Mg-Al-Sn alloy/seawater interfacial electrochemical process is determined by an activation controlled reaction. The assembled prototype batteries with Mg-6%Al-1%Sn alloy as anodes and Ag Cl as cathodes exhibit a satisfactory integrated discharge properties.

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.

Recent advances based on Mg anodes and their interfacial modulation in Mg batteries

Magnesium(Mg)batteries(MBs),as post-lithium-ion batteries,have received great attention in recent years due to their advantages of high energy density,low cost,and safety insurance.However,the formation of passivation layers on the surface of Mg metal anode and the poor compatibility between Mg metal and conventional electrolytes during charge-discharge cycles seriously affect the performance of MBs.The great possibility of generating Mg dendrites has also caused controversy among researchers.Moreover,the regulation of Mg deposition and the enhancement of battery cycle stability is largely limited by interfacial stability between Mg metal anode and electrolyte.In this review,recent advances in interfacial science and engineering of MBs are summarized and discussed.Special attention is given to interfacial chemistry including passivation layer formation,incompatibilities,ion transport,and dendrite growth.Strategies for building stable electrode/interfaces,such as anode designing and electrolyte modification,construction of artificial solid electrolyte interphase(SEI)layers,and development of solid-state electrolytes to improve interfacial contacts and inhibit Mg dendrite and passivation layer formation,are reviewed.Innovative approaches,representative examples,and challenges in developing high-performance anodes are described in detail.Based on the review of these strategies,reference is provided for future research to improve the performance of MBs,especially in terms of interface and anode design.

Corrosion protection of magnesium alloys anode by cerium-based anodization coating in magnesium-ait battery

CeN_(3)O_(9)·6H_(2)O(0.5,1.0,1.5,and 2.0 g/L)was added into an 8.0%NaCl electrolyte solution to investigate this electrolyte for use in a Mg-air battery.The effects of the amount of CeN_(3)O_(9)-6H_(2)O on the corrosion resistance of an AZ31 Mg alloy anode and battery performance were investigated using microstructure,electrochemical(dynamic potential polarization method and electrochemical impedance spectroscopy),and battery measurements.The re sults show that the addition of CeN_(3)O_(9)·6H_(2)O to the electrolyte leads to the formation of a Ce(OH)_(3)protective film on the surface of the AZ31 Mg alloy that improves the corrosion resistance of the Mg alloy.An increase in the concentration of CeN_(3)O_(9)·6H_(2)O results in a denser Ce(OH)_(3)protective film and decreases corrosion rate of the AZ31 Mg alloy.When the concentration of CeN_(3)O_(9)·6H_(2)O is 1.0 g/L,the corrosion rate of the Mg alloy is the lowest with a corrosion inhibition rate of70.4%.However,the corrosion rate increases due to the dissolution of the Ce(OH)_(3)protective film when the concentration of CeN_(3)O_(9)-6H_(2)O is greater than 1.0 g/L.Immersing the Mg alloy in the electrolyte solution containing CeN_(3)O_(9)-6H_(2)O for 50 h leads to the formation of the Ce(HO)_(3)protective film on its surface,which was confirmed by scanning electron microscopy of the AZ31 alloy.The Mg^(2+)charge transfer resistance increases by 69.5Ωfrom the equivalent circuit diagram,which improves the corrosion resistance of the Mg alloy.The discharge performance of CeN_(3)O_(9)·6H_(2)O improves according to a discharge test,and the discharge time increases by 40 min.

Effect of organic carbon sources on the anodic corrosion of magnesium AZ31B by sulfate-reducing prokaryote

Corrosion caused by sulfate-reducing prokaryotes(SRP)is an important cause of magnesium alloy anode failure in oil pipeline.In this study,the effects of Desulfovibrio sp.HQM3 on the corrosion behavior of AZ31B magnesium alloy anode in organic carbon sources with different contents in simulated tidal flat environment were analyzed using weight loss test,surface analysis and electrochemical analysis technologies.The results showed that the weight loss rate of coupons in low carbon sources contents(0%,1%,10%)was higher than that in 100%carbon sources.Electrochemical analyses showed that the corrosion current density(J_(corr))under low carbon sources contents was larger,while the charge transfer resistance(R_(ct))was lower,leading to a higher corrosion rate compared to those under 100%carbon sources content.Observations from scanning electron microscopy(SEM)and confocal laser scanning microscopy(CLSM)revealed more severe pitting corrosion on the alloy surface in the absence of carbon sources.In addition,a large number of nanowires were observed between bacteria on the alloy surface using SEM.Combined with thermodynamic calculations,it was demonstrated that the corrosion of coupons by Desulfovibrio sp.HQM3 in the absence of carbon sources was achieved through extracellular electron transfer.

Corrosion behavior of Mg-Al-Pb and Mg-Al-Pb-Zn-Mn alloys in 3.5% NaCl solution

Mg-6%Al-5%Pb and Mg-6%Al-5%Pb-0.55%Zn-0.22%Mn(mass fraction) alloys were prepared by induction melting with the protection of argon.The corrosion behaviors of these alloys were studied by electrochemical measurements and immersion tests.The results show that at the corrosion onset of Mg-Al-Pb anode there is an incubation period that can be shortened with 0.55%Zn and 0.22%Mn additions in the magnesium matrix.The corrosion rate of Mg-Al-Pb anode is mainly determined by the incubation period.Short incubation period always leads to high corrosion rate while long incubation period leads to low corrosion rate.The corrosion rates based on the corrosion current density by the electrochemical measurements do not agree with the measurements evaluated from the evolved hydrogen volume.

Investigation on corrosion of yttrium-doped magnesium-based sacrificial anode in ground grid protection

In the simulated DC and AC discharge circuit in ground grid protection of substation,corrosion and potential of magnesium anode with yttrium addition were studied by potential measurement and scanning electron microscopy.The results showed that potential of anode increased with increasing current density in DC simulation,potential increase of anode with 0.1% yttrium addition was the smallest,and the affordable current density of the anode reached 1.85 A/cm2,which was two times that of the anode without yttrium addition.In AC simulation,addition of yttrium had less effect on its potential.Grains of magnesium alloy sacrificial anode without yttrium addition were the equiaxed grains of magnesium grains coated with β-Mg17Al12,while the anode with yttrium was α-Mg phase with dispersed β phase.The corroded magnesium anode with 0.1% yttrium addition showed the most uniform and the smallest pit on its surface.