Plasma preparation of highly reactive Ag-Cu NPs anchored in N-PC as catalysts for Aluminum-air battery

Efficient,stable and economical catalysts play a crucial role in enhancing the kinetics of slow oxygen reduction reactions(ORR)in Aluminum-air batteries.Among the potential next-generation candidates,Ag catalysts are promising due to their high activity and low cost,but weaker oxygen adsorption has hindered industrialization.To address this bottleneck,Ag-alloying has emerged as a principal strategy.In this work,we successfully prepared Ag-Cu nanoparticles(NPs)with a rich eutectic phase and uniform dispersion structure using plasma evaporation.The increased solid solution of Ag and Cu led to changes in the electronic structure,resulting in an upward shift of the d-band center,which significantly improved oxygen adsorption.The combination of Ag and Cu in the NPs synergistically enhanced the adsorption of Ag and the desorption of Cu.Density functional theory(DFT)calculations revealed that Ag-Cu25 NPs exhibited the smallest limiting reaction barrier,leading to increased ORR activity.To further optimize the catalyst’s performance,we utilized N-doped porous nanocarbon(N-PC)with high electrical conductivity and abundant mesoporous channels as the support for the Ag-Cu NPs.The N-PC support provided optimal mass transfer carriers for the highly active Ag-Cu25 NPs.As a result,the Ag-Cu25/NPC catalyst displayed excellent ORR activity in alkaline media,with a half-wave potential(E_(1/2))of 0.82 V.Furthermore,the Al-air battery incorporating the Ag-Cu25/NPC catalyst exhibited outstanding electrochemical performance.It demonstrated high open-circuit voltages of 1.89 V and remarkable power densities of 193 m W cm^(-2).The battery also sustained a high current output and maintained a stable high voltage for 120 hours under mechanical charging,showcasing its significant potential for practical applications.

A comprehensive review on recent progress in aluminum-air batteries

The aluminum-air battery is considered to be an attractive candidate as a power source for electric vehicles(EVs) because of its high theoretical energy density(8100 Wh kg^(-1)), which is significantly greater than that of the state-of-the-art lithium-ion batteries(LIBs). However,some technical and scientific problems preventing the large-scale development of Al-air batteries have not yet to be resolved. In this review, we present the fundamentals, challenges and the recent advances in Al-air battery technology from aluminum anode, air cathode and electrocatalysts to electrolytes and inhibitors. Firstly, the alloying of aluminum with transition metal elements is reviewed and shown to reduce the selfcorrosion of Al and improve battery performance. Additionally for the cathode, extensive studies of electrocatalytic materials for oxygen reduction/evolution including Pt and Pt alloys, nonprecious metal catalysts, and carbonaceous materials at the air cathode are highlighted.Moreover, for the electrolyte, the application of aqueous and nonaqueous electrolytes in Al-air batteries are discussed. Meanwhile, the addition of inhibitors to the electrolyte to enhance electrochemical performance is also explored. Finally, the challenges and future research directions are proposed for the further development of Al-air batteries.

Rational design of vitamin C/defective carbon van der Waals heterostructure for enhanced activity,durability and storage stability toward oxygen reduction reaction

Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.

Mn-modified nitrogen-doped Pt-based electrocatalyst for efficient oxygen reduction in aluminum-air batteries

In this study,a Mn-modified Pt-based catalyst loaded on nitrogen-doped Ketjen black(Mn-Pt/NKB)is prepared using a simple ethylene glycol reduction method.The size of Pt nanoparticles(NPs)is effectively controlled by doping with Mn and N.With the smallest average particle size of 1.7 nm,Mn-Pt/NKB demonstrates half-wave potentials of 0.890 and 0.688 V in the alkaline and neutral electrolytes,respectively,which are superior to those of commercial platinum on activated carbon(Pt/C).When applied as an air cathode in aluminum-air battery,it exhibits ultra-high power densities of 190(alkaline)and 26.2 mW·cm^(−2)(neutral).Moreover,the voltage remains stable after 5 h of discharge.The practical application performance of the Mn-Pt/NKB catalyst in an aluminum-air battery is better than that of commercial Pt/C.Furthermore,the oxygen reduction reaction(ORR)mechanism on surfaces with different particle sizes is analyzed using density functional theory.Oxygen cracking is the major pathway on the surface of the small particles with lower energy consumption of 0.5 eV,while water molecule cleavage is the major pathway on the surface of the large particles with higher energy consumption of 0.97 eV.The lower energy consumption of the oxygen cracking pathway further confirms the ORR mechanism for higher activity on small-sized surfaces.This study provides a direction for the rational design of Pt-based catalysts for ORR and sheds light on the commercial development of aluminum-air batteries.