Influence of simulating deep-sea environmental factors on cathodic performance of seawater battery

A metal-dissolved oxygen seawater battery(SWB)uses metal and dissolved oxygen as the reactants,and it is ideal for use as a long-time low-power distributed power supply in deep sea,due to its advantages of open structure in service without electrolyte.However,several simulating deep-sea environmental factors,such as flow rate,dissolved oxygen concentration,and temperature of seawater may af fect the oxygen reduction reaction(ORR)rate and the stability of electrochemically modified polyacrylonitrile-based carbon fiber brush(MPAN-CFB)cathode,which was studied by steady-state polarization and galvanostatic discharge methods.In addition,the scales formed on MPAN-CFB surface were characterized by SEM and XRD.Results show that the ORR rate increased quickly with the increase of the seawater flow rate up to 3 cm/s,and then gradually stabilized.Moreover,the ORR rate was largely af fected by dissolved oxygen concentration,and the concentration of>3 mg/L was favorable.Compared with surface layer temperature of 15℃,the low temperature of deep sea(4℃)has a negligible ef fect on ORR rate.When the working current is too high,it will lead to the formation of CaCO_3 scales(aragonite)of at the cathodic surface,resulting in the decrease of ORR rate,and consequently the damage to the long-time stability of MPAN-CFB.

Spontaneous anchoring Cl intoα-Co(OH)_(2) as efficient and stable oxygen reduction electrocatalysts for seawater battery

Seawater battery is an advanced energy storage system that enables conversion of chemical energy to electricity by consuming metals,dissolved oxygen and seawater in anode,cathode and electrolyte,respectively.However,the oxygen reduction reaction(ORR)activity and stability of electrocatalysts can be easily deactivated due to the severe Cl~-permeation and corrosion in seawater electrolyte.Herein,we developed a structural buffer engineering strategy by spontaneously anchoring Cl~-intoα-Co(OH)_(2) as efficient and stable ORR electrocatalysts,in which the ultrathinα-Co(OH)_(2) nanosheets were synthesized using an ultrafast solution high-temperature shock(SHTS)strategy.The large lattice space(~0.8 nm)of layeredα-Co(OH)_(2) ensured the spontaneously penetration of Cl~-into the lattice structure and replaced part of OH~-to formα-Co(OH)_(2-x)Cl_x.The continuous leaching and compensating of saturated Cl inα-Co(OH)_(2-x)Cl_x could enhance the Cl~-corrosion resistance and modulate electronic structure of Co metallic sites,thus improving the ORR electrocatalytic activity and stability in seawater electrolyte.Theα-Co(OH)_(2-x)Cl_x seawater batteries display superior onset and half-wave potentials of 0.71 and 0.66 V,respectively,which are much better than the counterparts ofα-Co(OH)_(2) and ofβ-Co(OH)_(2) with no Cl~-penetrating and no buffer structure.Theα-Co(OH)_(2-x)Cl_x-based seawater batteries display stable open-circuit potential of 1.69 V and outstanding specific capacity of 1345 mAh·g^(-1).

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.

Electrochemical properties of magnesium alloy anodes discharged in seawater

Magnesium alloys can be developed as anode materials for seawater activated batteries. The electrochemical properties of AZ31, AP65 and Mg-3%Ga-2%Hg alloy anodes discharged in seawater were studied. The potentiodynamic polarization shows that the Mg-3%Ga-2%Hg alloy provides more negative corrosion potentials than AZ31 or AP65 alloy. The galvanostatic discharge results show that the Mg-3%Ga-2%Hg alloy exhibits good electrochemical properties as anodes in seawater. And the EIS studies reveal that the magnesium alloy anode/seawater interfacial process is determined by an activation controlled reaction. The Mg3Hg and Mg21Ga5Hg3 phases in Mg-3%Ga-2%Hg alloy improve its electrochemical properties better than the Mg17（Al,Zn）12 phase in AZ31 and Mg（Pb） solid solution phase in AP65 alloys.

Microstructures and electrochemical corrosion properties of Mg-Al-Pb and Mg-Al-Pb-Ce anode materials

Mg-Al-Pb alloy is a good candidate for the anode material of magnesium seawater battery. For improving the low current utilization efficiency of Mg-Al-Pb alloy, the influence of Ce on the microstructures and electrochemical corrosion properties in a 3.5% NaCl solution was investigated using scanning electron microscope and electrochemical measurements. The results indicate that Ce refines the grain structure of Mg-Al-Pb alloy. The formation of strip Al11Ce3 second phase promotes the uniform distribution of Mg17Al12 phase in Mg-Al-Pb-Ce alloy. The addition of cerium accelerates the discharge activity of Mg-Al-Pb alloy. Due to a large number of cathodic Al11Ce3 and MglyAla2 phases, Ce promotes the micro-galvanic corrosion and leads to larger corrosion current density and hydrogen evolution rate in Mg-Al-Pb-Ce alloy than those in Mg-Al-Pb alloy. However, Mg-Al-Pb alloy expresses smaller utilization efficiency than Mg-Al-Pb-Ce alloy because of grain detachment.

Influence of Al-Mn master alloys on microstructures and electrochemical properties of Mg-Al-Pb-Mn alloys

Mg-Al-Pb alloy is one of the newly developed materials for the seawater activated batteries. As-cast Mg-6Al-5Pb and Mg-6Al-5Pb-0.5Mn alloys with different additions of Al-15%Mn （mass fraction）, Al-30%Mn and Al-50%Mn master alloys were prepared by melting and casting. Their microstructures were observed by optical microscopy and scanning electron microscopy. The electrochemical properties, hydrogen evolution and mass loss of Mg-6Al-5Pb-0.5Mn alloys were studied. The results show that Mg-6Al-5Pb-0.5Mn alloy added with Al-50%Mn master alloy provides more negative corrosion average potential （-1.66 V）, smaller corrosion current density （7 μm/cm2） and lower free corrosion rate （0.51 mg·cm-2·h-1） than other alloys. This is probably attributed to the presence of Al11Mn4 phase, which facilitates the self-peeling of corrosion products and enlarges the electrochemical reaction area as well as enhances the electrochemical activity.

Effect of tin addition on microstructure and electrochemical properties of rolled AZ61-Sn magnesium anodic materials

Microstructure characterization, corrosion behavior, and electrochemical properties of magnesium anode materials containing 1-3 wt.% Sn in AZ61 alloy were studied by optical microscopy, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and energy-dispersive spec- troscopy （EDS）, constant current method, potential polarization, and drainage. The results showed that amount of Mg2Sn phase increased, and recrystallization ratio of Sn-contained Mg alloys during rolling process was improved with increasing of Sn content. This resulted in uniform and refined gains. The results also demonstrated that discharge potential was improved and hydrogen release rate was reduced with the addition of Sn. As the current density increased, the release hydrogen rate was rising, owing to negative variance effect of magnesium alloys. The current efficiency gets to 87% at 20 mA/cm2. The main components of the corrosion products are easy-to-peel-off MgO and Al2O3 that can lead to more negative and stable work potential and accelerate battery reaction continuously.

电子轴向拉伸提升贫氧环境海水电池性能

长寿命溶解氧海水电池是深远海观测能源网络的重要组成单元,但海水贫氧复杂环境对设计高性能氧还原催化剂提出了重要挑战.本文以酞菁铁为模型催化剂,通过理论计算与实验验证,提出了活性位点电子轴向拉伸可大幅提升催化剂在极端贫氧环境中的氧还原活性和稳定性.该研究为构建高性能海水电池提供了材料学解决方案,同时为极端环境下催化剂的变革性设计提供了新的思路.