Facile construction of a water-defendable Li anode protection enables rechargeable Li-O_(2) battery operating in humid atmosphere

The rechargeable Li-O_(2) battery endowed with high theoretical specific energy density has sparked intense research interest as a promising energy storage system. However, the intrinsic high activity of Li anode,especially to moisture, usually leads to inferior electrochemical performance of Li-O_(2) battery in humid environments, hindering its widespread application. To settle the trouble of poor moisture tolerance, fabricating a water-proof layer on the Li-metal anode could be an effective tactic. Herein, a facile strategy for constructing an ibuprofen-based protective layer on the Li anode has been proposed to realize highly rechargeable Li-O_(2) battery in humid atmosphere. Due to the in-situ reaction between ibuprofen reagent and metallic Li, the protective layer with a thickness of ~30 μm has been uniformly deposited on the surface of Li anode. Particularly, the protective layer, consisting of a large amount of hydrophobic alkyl group and benzene ring, can significantly resist water ingress and enhance the electrochemical stability of Li anode. As a result, the Li-O_(2) battery based on the protected Li anode achieves a long cycle life of 210 h(21 cycles at 1000 m Ah/g, 200 m A/g) in highly moist atmosphere with relative humidity(RH) of68%. This convenient and efficient strategy offers novel design concept of water-resistant metal anode,and paves the way to the promising future prospect for the high-energy Li-O_(2) battery implementing in the ambient atmosphere.

Revealing the importance of suppressing formation of lithium hydride and hydrogen in Li anode protection

The reviving of the“Holy Grail”lithium metal batteries(LMBs)is greatly hindered by severe parasitic reactions between Li anode and electrolytes.Herein,first,we comprehensively summarize the failure mechanisms and protection principles of the Li anode.Wherein,despite being in dispute,the formation of lithium hydride(LiH)is demonstrated to be one of the most critical factors for Li anode pulverization.Secondly,we trace the research history of LiH at electrodes of lithium batteries.In LMBs,LiH formation is suggested to be greatly associated with the generation of H_(2)from Li/electrolyte intrinsic parasitic reactions,and these intrinsic reactions are still not fully understood.Finally,density functional theory calculations reveal that H_(2)adsorption ability of representative Li anode protective species(such as LiF,Li_(3)N,BN,Li_(2)O,and graphene)is much higher than that of Li and LiH.Therefore,as an important supplement of well-known lithiophilicity theory/high interfacial energy theory and three key principles(mechanical stability,uniform ion transport,and chemical passivation),we propose that constructing an artificial solid electrolyte interphase layer enriched of components with much higher H_(2)adsorption ability than Li will serve as an effective principle for Li anode protection.In summary,suppressing formation of LiH and H_(2)will be very important for cycle life enhancement of practical LMBs.

Hybrid electrolyte with robust garnet-ceramic electrolyte for lithium anode protection in lithium-oxygen batteries

Rechargeable lithium-oxygen （Li-O2） batteries have received intensive research interest due to its ultrahigh energy density, while its cycle stability is still hindered by the high reactivity of the Li anode with oxygen and moisture. To alleviate the corrosion of the metallic lithium anodes for achieving a stable Li-O2 battery, and as a proof-of-concept experiment, a distinctive hybrid electrolyte system with an organic/ceramic/organic electrolyte （OCOE） architecture is designed. Importantl~ the cycle number of Li-O2 batteries with OCOE is significantly improved compared with batteries with an organic electrolyte （OE）. This might be attributed to the effective suppression of the lithium anode corrosion caused by the OE degradation and the crossover of oxygen from the cathode. We consider that our facile, low-cost, and highly effective lithium protection strategy presents a new avenue to address the daunting corrosion problem of lithium metal anodes in Li-O2 batteries. In addition, the proposed strategy can be easily extended to other metal-O2 battery systems, such as Na-O2 batteries.

MXene derivative Ta_(4)C_(3)-Ta_(2)O_(5) heterostructure as bi-functional barrier for Li-S batteries

The shuttle effect of polysulfides during the charging and discharging of lithium-sulfur(Li-S)batteries and the growth of Li dendrites are crucial obstacles to hinder the commercialization of Li-S batteries.Heterostructure engineering is an effective strategy to accelerate catalytic conversion and suppress the dissolution of polysulfides.Herein,we report a Ta_(4)C_(3)-Ta_(2)O_(5) heterostructure composite as a bi-functional modified separator that not only achieves effective protection for lithium metal but also accelerates the polysulfides redox kinetics process.This heterostructure possesses efficient chemical anchoring and abundant active sites to immobilize polysulfides by synergistic effect,which endows a stable long cycling performance for Li-S batteries.This corresponds to an initial high capacity of 801.9 mAh g^(–1) at 1 C with a decay rate of 0.086%for 500 cycles.Due to its high Young’s modulus(up to 384 GPa),Ta_(4)C_(3) contributes to forming a protective layer on the Li metal surface to inhibit the growth of Li dendrites.Accordingly,the symmetrical cell has a stable overpotential for 700 cycles at 20 mA cm^(–2)/20 mAh cm^(–2).So,this“one stone two birds”design affords a novel perspective for high-energy Li-S battery storage system design and Li metal protection.

Ultrathin Al2O3-coated reduced graphene oxide membrane for stable lithium metal anode

Lithium （Li） metal has been considered as the most attractive anode materials for Li-ion batteries （LIBs） due to its high theoretic specific capacity. The formation of unstable solid electrolyte interphase （SEI） and dendritic Li on the metal anode, however, hindered its practical application. Herein, to address the issues, a Li-free electrode with ultrathin Al2O3 coated on reduced graphene oxide （rGO） membrane that covers a Cu foil current collector was developed. The composite electrode exhibits excellent interfacial protection of lithium metal deposited between Cu foil and rGO electrochemically. Firstly, it affords good Li^＋ permeability from the electrolyte. Secondly, the ultrathin Al2O3 has sufficient mechanical strength to inhibit the penetration of Li dendrite. Li metal was observed uniformly deposited between rGO membrane and Cu collector, and stable cycle performance of Li plating/stripping with Coulombic efficiency of ~ 91.75% at the lOOth cycle is achieved in organic carbonate electrolyte without any additives.

Interface issues of lithium metal anode for high-energy batteries: Challenges, strategies, and perspectives

Lithium(Li)metal is considered as one of the most promising anode materials for next-generation high-energy-density storage systems.However,the practical application of Li metal anode is hindered by interfacial instability and air instability due to the highly reactivity of Li metal.Unstable interface in Li metal batteries(LMBs)directly dictates Li dendrite growth,“dead Li”and low Coulombic efficiency,resulting in inferior electrochemical performance of LMBs and even safety issues.In addition,its sensitivity to ambient air leads to the severe corrosion of Li metal anode,high requirements of production and storage,and increased manufacturing cost.Plenty of efforts in recent years have overcome many bottlenecks in these fields and hastened the practical applications of high-energy-density LMBs.In this review,we focus on emerging methods of these two aspects to fulfill a stable and low cost electrode.In this perspective,design artificial solid electrolyte interphase(SEI)layers,construct three-dimensional conductive current collectors,optimize electrolytes,employ solid-state electrolytes,and modify separators are summarized to be propitious to ameliorate interfacial stability.Meanwhile,ex situ/in situ formed protective layers are highlighted in favor of heightening air stability.Finally,several possible directions for the future research on advanced Li metal anode are addressed.