A gelatin-based artificial SEI for lithium deposition regulation and polysulfide shuttle suppression in lithium-sulfur batteries

Lithium-sulfur(Li-S) battery is one of the best candidates for the next-generation energy storage system due to its high theoretical capacity(1675 mA h-1),low cost and environment friendliness.However,lithium(Li) dendrites formation and polysulfide shuttle effect are two major challenges that limit the commercialization of Li-S batteries.Here we design a facile bifunctional interlayer of gelatin-based fibers(GFs),aiming to protect the Li anode surface from the dendrites growth and also hinder the polysulfide shuttle effect.We reveal that the 3D structural network of GFs layer with abundant polar sites helps to homogenize Li-ion flux,leading to uniform Li-ion deposition.Meanwhile,the polar moieties also immobilize the lithium polysulfides and protect the Li metal from the side-reaction.As a result,the anodeprotected batteries have shown significantly enhanced performance.A high coulombic efficiency of 96% after 160 cycles has been achieved in the Li-Cu half cells.The Li-Li symmetric cells exhibit a prolonged lifespan for 800 h with voltage hysteresis(10 mV).With the as-prepared GFs layer,the Li-S battery shows approximately 14% higher capacity retention than the pristine battery at 0.5 C after 100 cycles.Our work presents that this gelatin-based bi-functional interlayer provides a viable strategy for the manufacturing of advanced Li-S batteries.

Enabling high-performance all-solid-state lithium batteries with high ionic conductive sulfide-based composite solid electrolyte and ex-situ artificial SEI film

All-solid-state lithium batteries(ASSLBs) employing sulfide electrolyte and lithium(Li) anode have received increasing attention due to the intrinsic safety and high energy density.However,the thick electrolyte layer and lithium dendrites formed at the electrolyte/Li anode interface hinder the realization of high-performance ASSLBs.Herein,a novel membrane consisting of Li_(6)PS_(5) Cl(LPSCl),poly(ethylene oxide)(PEO) and Li-salt(LiTFSI) was prepared as sulfide-based composite solid electrolyte(LPSCl-PEO3-LiTFSI)(LPSCl:PEO=97:3 wt/wt;EO:Li=8:1 mol/mol),which delivers high ionic conductivity(1.1 × 10^(-3) S cm^(-1)) and wide electrochemical window(4.9 V vs.Li^(+)/Li) at 25 ℃.In addition,an ex-situ artificial solid electrolyte interphase(SEI) film enriched with LiF and Li3 N was designed as a protective layer on Li anode(Li(SEI)) to suppress the growth of lithium dendrites.Benefiting from the synergy of sulfide-based composite solid electrolyte and ex-situ artificial SEI,cells of S-CNTs/LPSCI-PEO3-LiTFSI/Li(SEI) and Al_(2)O_(3)@LiNi_(0.5)Co_(0.3)Mn_(0.2)O_(2)/LPSCl-PEO3-LiTFSI/Li(SEI) are assembled and both exhibit high initial discharge capacity of 1221.1 mAh g^(-1)(135.8 mAh g^(-1)) and enhanced cycling stability with 81.6% capacity retention over 200 cycles at 0.05 C(89.2% over 100 cycles at 0.1 C).This work provides a new insight into the synergy of composite solid electrolyte and artificial SEI for achieving high-performance ASSLBs.

Dynamically lithium-compensated polymer artificial SEI to assist highly stable lithium-rich manganese-based anode-free lithium metal batteries

Owing to the unique structure,anode-free lithium metal batteries(AFLMBs)have higher energy density and lower production cost than traditional lithium metal batteries(LMBs)or lithium-ion batteries(LIBs),However,AFLMBs suffer from an inherently finite Li reservoir and exhibit poor cycle stability,low Coulombic efficiency(CE)and severe dendrite growth.In this work,polydiallyl lithium disulfide(PDS-Li)was successfully synthesized and coated on Cu current collector by electrochemical polymerization.The PDS-Li acts as an additional lithium resource to compensate for the irreversible loss of lithium during cycling.In addition,the special structure and lithiophilicity of PDS-Li contribute to lower nucleation overpotential and uniform lithium deposition.When coupled with Li-rich manganese-based(LRM)cathode of Li1.2Mn0.54Ni0.13Co0.13O2,the anode-free full cell exhibits significantly improved cycle stability over 100 cycles and capacity retention of 63.3%and 57%after 80 and 100 cycles,respectively.We believe that PDS-Li can be used to ensure stable cycling performance and high-energy-density in AFLMBs.

In-situ construction of hybrid artificial SEI with fluorinated siloxane to enable dendrite-free Li metal anodes

Lithium(Li)metal anode holds great promise for high-energy-density rechargeable batteries.However,it suffers from the Li dendrites growth and uncontrollable side reactions with electrolyte due to the unstable solid electrolyte interphase(SEI)layer.Herein,we propose a facile strategy for the in-situ fabricate of organic-inorganic composite artificial SEI layers on Li surfaces,which consist of organic fluorinated siloxane and inorganic LiF-rich phases.The hybrid artificial SEI endows high mechanical strength(13.1 GPa)and Liþtransfer number(0.62).Such robust SEI protective layers can not only guide uniform nucleation and deposition of Li metal by facilitating uniform Li-ion distribution,but also prevent unfavourable side reactions.Accordingly,the protected metallic lithium anode(PMTFPS-Li)anode enables stable Li plating/stripping performance in symmetric cells for more than 300 h at 4 mA$h/cm^(2)under a high areal capacity of 4 mA/cm^(2).Moreover,the PMTFPS-Li/S cells could maintain more than 300 stable cycles at 0.5C and the PMTFPS-Li/LFP cells present excellent cycling performance(400 cycles at 1C)and enhanced rate capability(110.4 mA$h/g at 3 C).This work will inspire the design of artificial SEI on Li anodes for advanced Li metal batteries.

Artificial solid electrolyte interface layer based on sodium titanate hollow microspheres assembled by nanotubes to stabilize zinc metal electrodes

Recently,aqueous zinc-ion batteries with intrinsic safety,low cost,and environmental benignity have attracted tremendous research interest.However,zinc dendrites,harmful side reactions,and zinc metal corrosion stand in the way.Herein,we use lepidocrocite-type sodium titanate hollow microspheres assembled by nanotubes to constitute an artificial solid electrolyte interface layer on the zinc metal electrode.Thanks to the hierarchical structure with abundant open voids,negative-charged layered framework,low hydrophilicity,electrically insulting nature,and large ionic conductivity,the sodium titanate coating layer can effectively homogenize the electric field,promote the Zn^(2+)ion transfer,guide the Zn^(2+)ion flux,reduce the desolvation barrier,improve the exchange current density,and accommodate the plated zinc metal.Consequently,this coating layer can effectively suppress zinc dendrites and other unfavorable effects.With this coating layer,the Zn//Zn symmetric cell is able to provide an impressive cumulative zinc plating capacity of 1375 m Ah cm^(-2) at a current density of 5 m A cm^(-2).This coating layer also contributes to significantly improved electrochemical performances of Zn//MnO_(2) battery and zincion hybrid capacitor.This work offers new insights into the modifications of zinc metal electrodes.

A flexible artificial solid-electrolyte interlayer supported by compactness-tailored carbon nanotube network for dendrite-free lithium metal anode

A dendrite-free lithium metal anode requires a stable interface designed for efficient and reversible lithium plating and stripping. In this work, we have devised a mechanically flexible artificial Li_(3)N solid-electrolyte interlayer supported by a dual-layer compactness-tailored carbon nanotube fiber network. The more compact side of the network ensures a full coverage of Li_(3)N, which prevents the reaction between electrolyte and lithium. The other side, with sparsely distributed nanotube fibers, provides mechanical flexibility for the film, and induces three-dimensional lithium deposition along its structure without any dendrite formation. The resulting full cell with NCM811 cathode has a high capacity retention of 95.1% for 160 cycles compared with less than 80% for the control.

Lithiophilicity: The key to efficient lithium metal anodes for lithium batteries

Lithium metal anode of lithium batteries,including lithium-ion batteries,has been considered the anode for next-generation batteries with desired high energy densities due to its high theoretical specific capacity(3860 mA h g^(-1))and low standards electrode potential(-3.04 V vs.SHE).However,the highly reactive nature of metallic lithium and its direct contact with the electrolyte could lead to severe chemical reactions,leading to the continuous consumption of the electrolyte and a reduction in the cycle life and Coulombic efficiency.In addition,the solid electrolyte interface formed during battery cycling is mainly inorganic,which is too fragile to withstand the extreme volume change during the plating and stripping of lithium.The uneven flux of lithium ions could lead to excessive lithium deposition at local points,resulting in needle-like lithium dendrites,which could pierce the separator and cause short circuits,battery failure,and safety issues.In the last five years,tremendous efforts have been dedicated to addressing these issues,and the most successful improvements have been related to lithiophilicity optimizations.Thus,this paper comprehensively reviewed the lithiophilicity regulation in lithium metal anode modifications and highlighted the vital effect of lithiophilicity.The remaining challenges faced by the lithiophilicity optimization for lithium metal anodes are discussed with the proposed research directions for overcoming the technical challenges in this subject.

Developing artificial solid-state interphase for Li metal electrodes:recent advances and perspective

The failure of Li metal anodes can be attributed to their unstable electrode/electrolyte interface,especially the continuous formation of solid electrolyte interphase(SEI)and dendrite growth.To address this challenge,scholars proposed the construction of artificial SEI(ASEI)as a promising strategy.The ASEI mainly homoge-nizes the distribution of Li+,mitigates dendrite growth,facilitates Li+diffusion,and protects the Li metal anode from electrolyte erosion.This review comprehensively summarizes the recent progress in the construction of ASEI layers in terms of their chemical composition.Fundamental understanding of the mechanisms,design principles,and functions of the main components are analyzed.We also propose future research directions to facilitate the in-depth study of ASEI and its practical applications in Li metal batteries.This review offers perspectives that will greatly contribute to the design of practical Li metal electrodes.

Solid Electrolyte Interface in Zn-Based Battery Systems

Due to its high theoretical capacity(820 mAh g^(−1)),low standard electrode potential(−0.76 V vs.SHE),excellent stability in aqueous solutions,low cost,environmental friendliness and intrinsically high safety,zinc(Zn)-based batteries have attracted much attention in developing new energy storage devices.In Zn battery system,the battery performance is significantly affected by the solid electrolyte interface(SEI),which is controlled by electrode and electrolyte,and attracts dendrite growth,electrochemical stability window range,metallic Zn anode corrosion and passivation,and electrolyte mutations.Therefore,the design of SEI is decisive for the overall performance of Zn battery systems.This paper summarizes the formation mechanism,the types and characteristics,and the characterization techniques associated with SEI.Meanwhile,we analyze the influence of SEI on battery performance,and put forward the design strategies of SEI.Finally,the future research of SEI in Zn battery system is prospected to seize the nature of SEI,improve the battery performance and promote the large-scale application.

二维sp^(2)碳连接共价有机框架作为无枝晶锂金属电池的人工SEI膜

锂金属负极(LMA)具有前所未有的理论比容量和超低的氧化还原电位,因此锂金属电池(LMBs)得到了广泛的研究.然而,不可控的锂枝晶生长和易碎的固体电解质界面相(SEI)严重阻碍了LMBs的实际商业应用.本文制备了二维sp^(2)碳连接的共价有机框架sp^(2)c-COF,并在LMA表面构建了人工SEI膜,以抑制锂枝晶的形成,并调节界面稳定性.sp^(2)c-COF被设计成沿x和y方向全π共轭的高导电性的结构,从而起到降低界面阻抗、促进Li^(+)通量均匀分布的作用.因此,sp^(2)c-COF改性的对称电池Li^(+)迁移数高达0.85,并且在5mA cm^(-2)电流密度下具有较长的循环寿命(4000 h)和极低的过电位(10 mV).此外还利用原位光学显微镜研究了锂沉积行为,结果表明sp^(2)c-COF能显著提高LMA的界面稳定性.该策略对抑制锂枝晶的形成具有重要的应用价值,可促进COF人工SEI膜的发展.

In-situ constructed polymer/alloy composite with high ionic conductivity as an artificial solid electrolyte interphase to stabilize lithium metal anode

Lithium(Li)metal is regarded as the best anode material for lithium metal batteries(LMBs)due to its high theoretical specific capacity and low redox potential.However,the notorious dendrites growth and extreme instability of the solid electrolyte interphase(SEI)layers have severely retarded the commercialization process of LMBs.Herein,a double-layered polymer/alloy composite artificial SEI composed of a robust poly(1,3-dioxolane)(PDOL)protective layer,Sn and LiCl nanoparticles,denoted as PDOL@Sn-LiCl,is fabricated by the combination of in-situ substitution and polymerization processes on the surface of Li metal anode.The lithiophilic Sn-LiCl multiphase can supply plenty of Li-ion transport channels,contributing to the homogeneous nucleation and dense accumulation of Li metal.The mechanically tough PDOL layer can maintain the stability and compact structure of the inorganic layer in the long-term cycling,and suppress the volume fluctuation and dendrites formation of the Li metal anode.As a result,the symmetrical cell under the double-layered artificial SEI protection shows excellent cycling stability of 300 h at 5.0 mA·cm^(−2)for 1 mAh·cm^(−2).Notably,the Li||LiFePO_(4)full cell also exhibits enhanced capacity retention of 150.1 mAh·g^(−1)after 600 cycles at 1.0 C.Additionally,the protected Li foil can effectively resist the air and water corrosion,signifying the safe operation of Li metal in practical applications.This present finding proposed a different tactic to achieve safe and dendrite-free Li metal anodes with excellent cycling stability.

Constructing a fluorinated interface layer enriched with Ge nanoparticles and Li-Ge alloy for stable lithium metal anodes

Lithium metal batteries(LMBs)based on metallic Li exhibit high energy density to be competent for advanced energy storage applications.However,the unstable solid electrolyte interphase(SEI)layer due to continuous decomposition of electrolytes,and the attendant problem of Li dendrite growth frustrate their commercialization process.Herein,a hybrid SEI comprising abundant LiF,lithiophilic Li-Ge alloy,and Ge nanoparticles is constructed via a simple brush coating method.This fluorinated interface layer with embedded Ge-containing components isolates the Li anode from the corrosive electrolyte and facilitates homogenous Li nucleation as well as uniform growth.Consequently,the modified Li anode exhibits remarkable stability without notorious Li dendrites,delivering stable cycling lives of more than 1000 h for symmetric Li||Li cells and over 600 cycles for Li||Cu cells at 1 mA·cm^(−2).Moreover,the reinforced Li anodes endow multiple full-cell architectures with dramatically improved cyclability under different test conditions.This work provides rational guidance to design an artificial hybrid SEI layer and would stimulate more ideas to solve the dendrite issue and promote the further development of advanced LMBs.

Artificial Solid Electrolyte Interphase Acting as “ Armor” to Protect the Anode Materials for High-performance Lithium-ion Battery

The electrochemical performances of lithium-ion batteries(LIBs)are closely related to the interphase between the electrode materials and electrolytes.However,the development of lithium-ion batteries is hampered by the formation of uncontrollable solid electrolyte interphase(SEI)and subsequent potential safety issues associated with dendritic formation and cell short-circuits during cycling.Fabricating artificial SEI layer can be one promising approach to solve the above issues.This review summarizes the principles and methods of fabricating artificial SEI for three types of main anodes:deposition-type(e.g.,Li),intercalation-type(e.g.,graphite)and alloy-type(e.g.,Si,Al).The review elucidates recent progress and discusses possible methods for constructing stable artificial SEIs composed of salts,polymers,oxides,and nanomaterials that simultaneously passivate anode against side reactions with electrolytes and regulate Li^+ions transport at interfaces.Moreover,the reaction mechanism of artificial SEIs was briefly analyzed,and the research prospect was also discussed.

Ultralong-life lithium metal batteries enabled by decorating robust hybrid interphases on 3D layered framworks

Stable solid-electrolyte interphase(SEI)is crucial for advanced development of lithium metal batteries.However,the continuous collapse and reconstruction of SEI will deplete fresh Li and electrolytes upon cycling,leading to irreversible capacity loss.Herein,we addressed this issue by pre-formation of artificial robust hybrid interphase on a 3D layered graphene/lithium metal framework,in which is constructed by LiF associated with Li2TiF 6generated by the in-situ reaction between the surfacial lithium and titanium fluoride contained electrolytes.The as-obtained interphase can maintain the structure integrality and avoid continuous consumption of the fresh Li and electrolytes.As a consequence,the Li symmetric cells achieve high-efficiency Li deposition and stable cycling over 3600 h.When paired with LiFePO_(4)cathodes,the coin cells exhibit long lifespan(>800 cycles)with almost 88.3%retention of the initial capacity.

AgTFSI Pretreated Li Anode in LiI-Mediated Li-O_(2)Battery:Enabling Lithiophilic Solid Electrolyte Interphase Generation to Suppress the Redox Shuttling

Although lithium iodide(LiI)as a redox mediator(RM)can decrease the overpotential in Li-O_(2)batteries,the stability of the Li anode is still one critical issue due to the redox shuttling.Here,we firstly present a novel approach for generating Ag and LiTFSI enriched Li anode(designated as ALE@Li anode)via a spontaneous substitution between pure Li and bis(trifluoromethanesulfonyl)imide silver,in a LiI-participated Li-O_(2)cell.It can induce the generation of a lithiophilic solid electrolyte interphase(SEI)enriched with Ag,F,and N species(e.g.,Ag_(2)O,Li-Ag alloy,LiF,and Li_(3)N)during cell operation,which contributes to promoting the electrochemical performance through the shuttling inhibition.Compared to a cell with a bare Li anode,the one with as-prepared ALE@Li anode shows an enhanced cyclability,a considerable rate capability,and a good reversibility.In addition,a synchrotron X-ray computed tomography technique is employed to investigate the inhibition mechanism for shuttling effect by monitoring the morphological evolution on the cell interfaces.Therefore,this work highlights the deliberate design in the modified Li anode in an easy-to-operate and cost-effective way as well as providing guidance for the construction of artificial SEI layers to suppress the redox shuttling of RMs in Li-O_(2)batteries.