Designing Conformal Electrode-electrolyte Interface by Semi-solid NaK Anode for Sodium Metal Batteries

Solid-state Na metal batteries(SSNBs),known for its low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of NaK alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the intimate contact of electrode-electrolyte interface.Additionally,the filling of SiO_(2)nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 h.The full cell coupled with Na_(3)V_(3)(PO_(4))_(2)cathodes had an initial discharge capacity of 106.8 mAh·g^(-1)with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1)even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.

Unraveling the incompatibility mechanism of ethylene carbonate-based electrolytes in sodium metal anodes

Ethylene carbonate(EC)is widely used in lithium-ion batteries due to its optimal overall performance with satisfactory conductivity,relatively stable solid electrolyte interphase(SEI),and wide electrochemical window.EC is also the most widely used electrolyte solvent in sodium ion batteries.However,compared to lithium metal,sodium metal(Na)shows higher activity and reacts violently with EC-based electrolyte(NaPF_(6)as solute),which leads to the failure of sodium metal batteries(SMBs).Herein,we reveal the electrochemical instability mechanism of EC on sodium metal battery,and find that the com-bination of EC and NaPF_(6) is electrically reduced in sodium metal anode during charging,resulting in the reduction of the first coulombic efficiency,and the continuous consumption of electrolyte leads to the cell failure.To address the above issues,an additive modified linear carbonate-based electrolyte is provided as a substitute for EC based electrolytes.Specifically,ethyl methyl carbonate(EMC)and dimethyl carbon-ate(DMC)as solvents and fluoroethylene carbonate(FEC)as SEI-forming additive have been identified as the optimal solvent for NaFP_(6)based electrolyte and used in Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7))/Na batteries.The batter-ies exhibit excellent capacity retention rate of about 80%over 1000 cycles at a cut-off voltage of 4.3 V.

Dendrite‐free lithium and sodium metal anodes with deep plating/stripping properties for lithium and sodium batteries

Although lithium(Li)and sodium(Na)metals can be selected as the promising anode materials for next‐generation rechargeable batteries of high energy density,their practical applications are greatly restricted by the uncontrollable dendrite growth.Herein,a platinum(Pt)–copper(Cu)alloycoated Cu foam(Pt–Cu foam)is prepared and then used as the substrate for Li and Na metal anodes.Owing to the ultrarough morphology with a threedimensional porous structure and the quite large surface area as well as lithiophilicity and sodiophilicity,both Li and Na dendrite growths are significantly suppressed on the substrate.Moreover,during Li plating,the lithiated Pt atoms can dissolve into Li phase,leaving a lot of microsized holes on the substrate.During Na plating,although the sodiated Pt atoms cannot dissolve into Na phase,the sodiation of Pt atoms elevates many microsized blocks above the current collector.Either the holes or the voids on the surface of Pt–Cu foam what can be extra place for deposited alkali metal,what effectively relaxes the internal stress caused by the volume exchange during Li and Na plating/stripping.Therefore,the symmetric batteries of Li@Pt–Cu foam and Na@Pt–Cu foam have both achieved long‐term cycling stability even at ultrahigh areal capacity at 20 mAh cm−2.

Rooting Zn into metallic Na bulk for energetic metal anode

Metallic Na with high theoretical capacity and low redox potential is an attractive anode material for highenergy rechargeable metal batteries.The poor wettability of Na on current collectors and the weak interaction between Na atoms lead to uneven plating/stripping of Na and dendrite formation.Here,we report an encouraging strategy to tackle these issues by rooting Zn into metallic Na bulk through a molten infusion process.The introduction of Zn not only tunes molten Na into highly sodiophilic Na(Zn)but also guides the uniform nucleation of Na through a much stronger interaction.As a result,smooth Na plating and stripping with a low energy barrier and homogeneous current distribution are simultaneously accomplished.Stable galvanostatic cycling over 3000 h in symmetric Na(Zn)cells and low voltage hysteresis below 15 mV at a rate of 5 mA cm^(-2) have been recorded.When coupled with a Na_(3)V_(2)(PO_(4))_(2)O_(2)F cathode,the Na(Zn)-Na_(3)V_(2)(PO_(4))_(2)O_(2)F full cell demonstrates an energetic performance,highlighting the strategy of rooting Zn into alkali metal bulk for rechargeable metal batteries.