In situ high-quality LiF/Li_(3)N inorganic and phenyl-based organic solid electrolyte interphases for advanced lithium–oxygen batteries

Lithium metal shows a great advantage as the most promising anode for its unparalleled theoretical specific capacity and extremely low electrochemical potential.However,uncontrolled lithium dendrite growth and severe side reactions of the reactive intermediates and organic electrolytes still limit the broad application of lithium metal batteries.Herein,we propose 4-nitrobenzenesulfonyl fluoride(NBSF)as an electrolyte additive for forming a stable organic-inorganic hybrid solid electrolyte interphase(SEI)layer on the lithium surface.The abundance of lithium fluoride and lithium nitride can guarantee the SEI layer's toughness and high ionic conductivity,achieving dendrite-free lithium deposition.Meanwhile,the phenyl group of NBSF significantly contributes to both the chemical stability of the SEI layer and the good adaptation to volume changes of the lithium anode.The lithium-oxygen batteries with NBSF exhibit prolonged cycle lives and excellent cycling stability.This simple approach is hoped to improve the development of the organic-inorganic SEI layer to stabilize the lithium anodes for lithium-oxygen batteries.

Regulating solid electrolyte interphases on phosphorus/carbon anodes via localized high-concentration electrolytes for potassium-ion batteries

The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.

Towards high-performance lithium metal anodes via the modification of solid electrolyte interphases

Li metal has been regarded as one of the most promising anodes for high-energy-density storage systems due to its high theoretical capacity and lowest electrochemical potential.Unfortunately,an unstable and non-uniform solid electrolyte interphase(SEI)deriving from the spontaneous reaction between Li metal anode and electrolyte causes uneven Li deposition,resulting in the growth of Li dendrites and low Coulombic efficiency,which have greatly hindered the practical application of Li metal batteries.Thus,the construction of a stable SEI is an effective approach to suppress the growth of Li dendrites and enhance the electrochemical performances of Li metal anode.In this review,we firstly introduce the formation process of inferior SEI of Li metal anode and the corresponding challenges caused by the unstable SEI.Next,recent progresses to modify SEI layer through the regulation of electrolyte compositions and exsitu protective coating are summarized.Finally,the remained issues,challenges,and perspectives are also proposed on the basis of current research status and progress.

Analysis of lattices with non-linear interphases

Anti-plane deformation of square lattices containing interphases is analyzed. It is assumed that lattices are linear elastic but not necessarily isotropic, whereas interphases exhibit non-linear elastic behavior. It is demonstrated that such problems can be treated effectively using Green＇s functions, which allow to eliminate the degrees of freedom outside of the interphase. Illustrative numerical examples focus on the determination of applied stresses leading to lattice instability.

Protective electrode/electrolyte interphases for high energy lithium-ion batteries with p-toluenesulfonyl fluoride electrolyte additive

High energy density lithium-ion batteries using Ni-rich cathode(such as LiNi0.6Co0.2Mn0.2O2) suffer from severe capacity decay.P-toluenesulfonyl fluoride(pTSF) has been investigated as a novel film-forming electrolyte additive to enhance the cycling performances of graphite/LiNi0.6Co0.2Mn0.2O2 pouch cell.In comparison with the baseline electrolyte,a small dose of pTSF can significantly improve the cyclic stability of the cell.Theoretical calculations together with experimental results indicate that pTSF would be oxidized and reduced to construct protective interphase film on the surfaces of LiNi0.6Co0.2Mn0.2O2 cathode and graphite anode,respectively.These S-containing surface films derived from pTSF effectively mitigate the decomposition of electrolyte,reduce the interphasial impedance,as well as prevent the dissolution of transition metal ions from Ni-rich cathode upon cycling at high voltage.This finding is beneficial for the practical application of high energy density graphite/LiNi0.6Co0.2Mn0.2O2 cells.

Artificial interphases enable dendrite-free Li-metal anodes

Li-metal is an ideal anode that can provide rechargeable batteries with high energy density,but its application in large scale is restricted by its high activity that leads to the severe decomposition of electrolyte components(solvents and salts) and the growth of Li dendrites.These parasitic reactions are responsible for the cycle life deterioration and the safety accidents of rechargeable Li-metal batteries.Correspondingly,much effort has been made to regulate Li/electrolyte interface chemistry.In this review,we summarize some strategies that have been developed recently to stabilize Li/electrolyte interface by constructing protective interphases on Li-metal anodes.Firstly,the currently available understandings on the instability of Li/electrolyte interface are outlined.Then,artificial interphases recently constructed exsitu and in-situ are illustrated in detail.Finally,possible approaches to acquire more efficiently protective interphases are prospected.

ANALYTICAL SOLUTIONS FOR ELASTOSTATIC PROBLEMS OF PARTICLE-AND FIBER-REINFORCED COMPOSITES WITH INHOMOGENEOUS INTERPHASES

By transforming the governing equations for displacement components into Riccati equations, analytical solutions for displacements, strains and stresses for Representive Volume Elements (RVEs) of particle_ and fiber_reinforced composites containing inhomo geneous interphases were obtained. The analytical solutions derived here are new and general for power_law variations of the elastic moduli of the inhomogeneous interphases. Given a power exponent, analytical expressions for the bulk moduli of the composites with inho mogeneous interphases can be obtained. By changing the power exponent and the coefficients of the power terms, the solutions derived here can be applied to inhomogeneous interphases with many different property profiles. The results show that the modulus variation and the thickness of the inhomogeneous interphase have great effect on the bulk moduli of the composites. The particle will exhibit a sort of “size effect”, if there is an interphase.

Liquid-source plasma technology for construction of dual bromine-fluorine-enriched interphases on lithium metal anodes with enhanced performance

The electrochemical performance of Li metal anode is closely bound up with the interphase between Li and lithium-loaded skeleton as well as solid electrolyte interphase(SEI)on Li surface.Herein,for the first time,we propose a novel liquid-source CHBr_(2)F plasma technology to simultaneously construct dual bromine-fluorine-enriched interphases:NiBr_(2)-NiF_(2) interphase on sponge Ni(SN)skeleton and LiBr-LiF-enriched SEI on Li anode,respectively.Based on density functional theory(DFT)calculations and COMSOL multiphysics simulation results,SN skeleton with NiBr_(2)-NiF_(2)interphase can effectively decrease the local current density with good lithiophilicity.And the LiBr-LiF-enriched SEI on Li surface can function to block electron tunneling and hinder side electrochemical reduction of electrolyte components,thus suppressing the growth of dendrite and facilitating the homogeneous transportation of lithium ions.Consequently,the Li/SN electrodes with modified interphases show remarkable stability with a low overpotential of 22.6 mV over 1800 h at 1 mA cm^(-2)/1 mAh cm^(-2)and an exceptional average Coulombic efficiency of 99.6%.When coupled with LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cathode,the full cells deliver improved cycling stability with a capacity retention of 79.5%even after 350 cycles at 0.5 C.This study provides a facile and new plasma method for the construction of advanced Li anodes for energy storage.

Synergy of in-situ heterogeneous interphases tailored lithium deposition

The implementation of a robust artificial solid electrolyte interphase(ASEI)to replace the unstable natural SEI can regulate lithium deposition behaviors and avoid the safety hazards caused by dendrites permeation in lithium metal batteries.Despite of devoted efforts in tailoring components of ASEI,the intrinsic mechanism of interfacial synergy within the heterogeneous interphases has not been well elucidated yet.Herein,we show that the lithium plating/striping behaviors can be substantially enhanced(over 900 h with an overpotential of less than 20 mV at 1 mA·cm^(−2)in Li|Li symmetric cells and 146 cycles in anode-free cells)by regulating the heterogeneous interphases.This favorable ASEI composed of LiF and Li_(3)N components can be in-situ generated during cycling by large-scale fabricated fluorinated boron nitride coatings.Further,the synergy of each heterogeneous component within ASEI was explored theoretically and experimentally.Li_(3)N has high adsorption energy and low ion diffusion barrier,which facilitates the transport of lithium ions and avoids its local accumulation to evolve into dendrites.Both the substrate and LiF are interfacially stable with high electron tunneling barriers,preventing the electrolyte decomposition and parasitic reactions.Finally,the high stiffness of the boron nitride also ensures lithium dendrites are suppressed once they grow,providing a stable environment for long-term cycling of lithium metal batteries.

Rationally designing electrolyte additives for highly improving cyclability of LiNi_(0.5)Mn_(1.5)O_(4)/Graphite cells

High voltage is necessary for high energy lithium-ion batteries but difficult to achieve because of the highly deteriorated cyclability of the batteries.A novel strategy is developed to extend cyclability of a high voltage lithium-ion battery,LiNi_(0.5)Mn_(1.5)O_(4)/Graphite(LNMO/Graphite)cell,which emphasizes a rational design of an electrolyte additive that can effectively construct protective interphases on anode and cathode and highly eliminate the effect of hydrogen fluoride(HF).5-Trifluoromethylpyridine-trime thyl lithium borate(LTFMP-TMB),is synthesized,featuring with multi-functionalities.Its anion TFMPTMB-tends to be enriched on cathode and can be preferentially oxidized yielding TMB and radical TFMP-.Both TMB and radical TFMP can combine HF and thus eliminate the detrimental effect of HF on cathode,while the TMB dragged on cathode thus takes a preferential oxidation and constructs a protective cathode interphase.On the other hand,LTFMP-TMB is preferentially reduced on anode and constructs a protective anode interphase.Consequently,a small amount of LTFMP-TMB(0.2%)in 1.0 M LiPF6in EC/DEC/EMC(3/2/5,wt%)results in a highly improved cyclability of LNMO/Graphite cell,with the capacity retention enhanced from 52%to 80%after 150 cycles at 0.5 C between 3.5 and 4.8 V.The as-developed strategy provides a model of designing electrolyte additives for improving cyclability of high voltage batteries.

Long‐life lithium batteries enabled by a pseudo‐oversaturated electrolyte

The specific energy of Li metal batteries(LMBs)can be improved by using high‐voltage cathode materials;however,achieving long‐term stable cycling performance in the corresponding system is particularly challenging for the liquid electrolyte.Herein,a novel pseudo‐oversaturated electrolyte(POSE)is prepared by introducing 1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropyl ether(TTE)to adjust the coordination structure between diglyme(G2)and lithium bis(trifluoromethanesulfonyl)imide(LiTFSI).Surprisingly,although TTE shows little solubility to LiTFSI,the molar ratio between LiTFSI and G2 in the POSE can be increased to 1:1,which is much higher than that of the saturation state,1:2.8.Simulation and experimental results prove that TTE promotes closer contact of the G2 molecular with Li^(+)in the POSE.Moreover,it also participates in the formation of electrolyte/electrode interphases.The electrolyte shows outstanding compatibility with both the Li metal anode and typical high‐voltage cathodes.Li||Li symmetric cells show a long life of more than 2000 h at 1 mA cm^(−2),1 mAh cm^(−2).In the meantime,Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)cell with the POSE shows a high reversible capacity of 134.8 mAh g^(−1 )after 900 cycles at 4.5 V,1 C rate.The concept of POSE can provide new insight into the Li^(+)solvation structure and in the design of advanced electrolytes for LMBs.

Unique double-layer solid electrolyte interphase formed with fluorinated ether-based electrolytes for high-voltage lithium metal batteries

Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.

Lignin-derived hard carbon anode with a robust solid electrolyte interphase for boosted sodium storage performance

Hard carbon is regarded as a promising anode candidate for sodium-ion batteries due to its low cost,relatively low working voltage,and satisfactory specific capacity.However,it still remains a challenge to obtain a high-performance hard carbon anode from cost-effective carbon sources.In addition,the solid electrolyte interphase(SEI)is subjected to continuous rupture during battery cycling,leading to fast capacity decay.Herein,a lignin-based hard carbon with robust SEI is developed to address these issues,effectively killing two birds with one stone.An innovative gas-phase removal-assisted aqueous washing strategy is developed to remove excessive sodium in the precursor to upcycle industrial lignin into high-value hard carbon,which demonstrated an ultrahigh sodium storage capacity of 359 mAh g^(-1).It is found that the residual sodium components from lignin on hard carbon act as active sites that controllably regulate the composition and morphology of SEI and guide homogeneous SEI growth by a near-shore aggregation mechanism to form thin,dense,and organic-rich SEI.Benefiting from these merits,the as-developed SEI shows fast Na+transfer at the interphases and enhanced structural stability,thus preventing SEI rupture and reformation,and ultimately leading to a comprehensive improvement in sodium storage performance.

Electrolyte Design for Low‑Temperature Li‑Metal Batteries:Challenges and Prospects

Electrolyte design holds the greatest opportunity for the development of batteries that are capable of sub-zero temperature operation.To get the most energy storage out of the battery at low temperatures,improvements in electrolyte chemistry need to be coupled with optimized electrode materials and tailored electrolyte/electrode interphases.Herein,this review critically outlines electrolytes’limiting factors,including reduced ionic conductivity,large de-solvation energy,sluggish charge transfer,and slow Li-ion transportation across the electrolyte/electrode interphases,which affect the low-temperature performance of Li-metal batteries.Detailed theoretical derivations that explain the explicit influence of temperature on battery performance are presented to deepen understanding.Emerging improvement strategies from the aspects of electrolyte design and electrolyte/electrode interphase engineering are summarized and rigorously compared.Perspectives on future research are proposed to guide the ongoing exploration for better low-temperature Li-metal batteries.

Enabling an Inorganic-Rich Interface via Cationic Surfactant for High-Performance Lithium Metal Batteries

An anion-rich electric double layer(EDL)region is favorable for fabricating an inorganic-rich solid-electrolyte interphase(SEI)towards stable lithium metal anode in ester electrolyte.Herein,cetyltrimethylammonium bromide(CTAB),a cationic surfactant,is adopted to draw more anions into EDL by ionic interactions that shield the repelling force on anions during lithium plating.In situ electrochemical surface-enhanced Raman spectroscopy results combined with molecular dynamics simulations validate the enrichment of NO_(3)^(−)/FSI−anions in the EDL region due to the positively charged CTA^(+).In-depth analysis of SEI structure by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry results confirmed the formation of the inorganic-rich SEI,which helps improve the kinetics of Li^(+)transfer,lower the charge transfer activation energy,and homogenize Li deposition.As a result,the Li||Li symmetric cell in the designed electrolyte displays a prolongated cycling time from 500 to 1300 h compared to that in the blank electrolyte at 0.5 mA cm^(-2) with a capacity of 1 mAh cm^(-2).Moreover,Li||LiFePO_(4) and Li||LiCoO_(2) with a high cathode mass loading of>10 mg cm^(-2) can be stably cycled over 180 cycles.

Mechanical and electromagnetic wave absorption properties of Cf-Si3N4 ceramics with PyC/SiC interphases

Aiming to obtain microwave absorbing materials with excellent mechanical and microwave absorption properties, carbon fiber reinforced Si3N4 ceramics(Cf-Si3N4) with pyrolytic carbon(PyC)/SiC interphases were fabricated by gel casting. The influences of carbon fibers content on mechanical and microwave absorption properties of as-prepared Si3N4 based ceramics were investigated. Results show that chemical compatibility between carbon fibers and Si3N4 matrix in high temperature environment can be significantly improved after introduction of Py C/SiC interphases. As carbon fibers content increases from 0 to 4 wt%, flexural strength of Si3N4 based ceramics decreases slightly while fracture toughness obviously increases. Moreover, both the real and imaginary parts of complex permittivity increase with the rising of carbon fibers content within the frequency range of 8.2–12.4 GHz. Investigation of microwave absorption shows that the microwave attenuation ability of Cf-Si3N4 ceramics with Py C/SiC interphases is remarkably enhanced compared with pure Si3N4 ceramics. Effective absorption bandwidth(<-10 d B) of10.17–12.4 GHz and the minimum reflection less of-19.6 d B are obtained for Si3N4 ceramics with 4 wt%carbon fibers in 2.0 mm thickness. Cf-Si3N4 ceramics with Py C/SiC interphases are promising candidates for microwave absorbing materials with favorable mechanical property.

All-fluorinated electrolyte for non-flammable batteries with ultra-high specific capacity at 4.7 V

Li metal batteries(LMBs)with LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)cathodes could release a specific energy of>500 Wh kg^(-1) by increasing the charge voltage.However,high-nickel cathodes working at high voltages accelerate degradations in bulk and at interfaces,thus significantly degrading the cycling lifespan and decreasing the specific capacity.Here,we rationally design an all-fluorinated electrolyte with addictive tri(2,2,2-trifluoroethyl)borate(TFEB),based on 3,3,3-fluoroethylmethylcarbonate(FEMC)and fluoroethylene carbonate(FEC),which enables stable cycling of high nickel cathode(LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2),NMC811)under a cut-off voltage of 4.7 V in Li metal batteries.The electrolyte not only shows the fire-extinguishing properties,but also inhibits the transition metal dissolution,the gas production,side reactions on the cathode side.Therefore,the NMC811||Li cell demonstrates excellent performance by using limited Li and high-loading cathode,delivering a specific capacity>220 mA h g^(-1),an average Coulombic efficiency>99.6%and capacity retention>99.7%over 100 cycles.

Rational design of F,N-rich artificial interphase via chemical prelithiation initiation strategy enabling high coulombic efficiency and stable micro-sized SiO anodes

Silicon monoxide(SiO)is regarded as a potential candidate for anode materials of lithium-ion batteries(LIBs).Unfortunately,the application of SiO is limited by poor initial Coulombic efficiency(ICE)and unsteady solid electrolyte interface(SEI),which induce low energy,short cycling life,and poor rate properties.To address these drawbacks of SiO,we achieve in-situ construction of robust and fast-ion conducting F,N-rich SEI layer on prelithiated micro-sized SiO(P-μSiO)via the simple and continuous treatment ofμSiO in mild lithium 4,4′-dimethylbiphenyl solution and nonflammable hexafluorocyclotriphosphazene solution.Chemical prelithiation eliminates irreversible capacity through pre-forming inactive lithium silicates.Meanwhile,the symbiotic F,N-rich SEI with good mechanical stability and fast Li^(+)permeability is conductive to relieve volume expansion ofμSiO and boost the Li+diffusion kinetics.Consequently,the P-μSiO realizes an impressive electrochemical performance with an elevated ICE of 99.57%and a capacity retention of 90.67%after 350 cycles.Additionally,the full cell with P-μSiO anode and commercial LiFePO_(4) cathode displays an ICE of 92.03%and a high reversible capacity of 144.97 mA h g^(-1).This work offers a general construction strategy of robust and ionically conductive SEI for advanced LIBs.

An efficient recycling strategy to eliminate the residual“impurities”while heal the damaged structure of spent graphite anodes

The recycling of graphite from spent lithium-ion batteries(LIBs)is overlooked due to its relatively low added value and the lack of efficient recovering methods.To reuse the spent graphite anodes,we need to eliminate their useless components(mainly the degraded solid electrolyte interphase,SEI)and reconstruct their damaged structure.Herein,a facile and efficient strategy is proposed to recycle the spent graphite on the basis of the careful investigation of the composition of the cycled graphite anodes and the rational design of the regeneration processes.The regenerated graphite,which is revitalized by calcination treatment and acid leaching,delivers superb rate performance and a high specific capacity of 370 mAh g^(-1)(~99% of its theoretical capacity)after 100 cycles at 0.1 C,superior to the commercial graphite anodes.The improved electrochemical performance could be attributed to unchoked Li^(+) transport channels and enhanced charge transfer reaction due to the effective destruction of the degraded SEI and the full recovery of the damaged structure of the spent graphite.This work clarifies that the electrochemical performance of the regenerated graphite could be deteriorated by even a trace amount of the residual“impurity”and provides a facile method for the efficient regeneration of graphite anodes.

Lamellar sulfonated acid polymer-initiated in situ construction of robust LiF-rich SEI enabling superior charge transport for ultrastable and fast charging silicon anodes

The extreme volume expansion of the silicon(Si) anodes during repeated cycles seriously induces undesirable interfacial side reactions,forming an unstable solid electrolyte interphase(SEI) that degrades the electrode integrity and cycle stability in lithium-ion batteries,limiting their practical applications.Despite considerable efforts to stabilize the SEI through surface modification,challenges persist in the development of high-performance Si anodes that effectively regulate intrinsic SEI properties and simultaneously facilitate electron/ion transport.Here,a highly conductive and organic electrolyte-compatible lamellar p-toluenesulfonic acid-doped polyaniline(pTAP) layer is proposed for constructing a robust artificial SEI on Si nanoparticles to achieve fast charging,lo ng-term cycle lifespan and high areal capacity.The spatially uniform pTAP layer,formed through a facile direct-encapsulation approach assisted by enriched hydrogen bonding,contributes to the effective formation of in situ SEI with an even distribution of the LiF-rich phase in its interlamination spaces.Furthermore,the integrated artificial SEI facilitates isotropic ion/electron transport,increased robustness,and effectively dissipates stress from volume changes.Consequently,a notably high rate performance of 570 mA h g^(-1),even at a substantially high current density of 10 A g^(-1),is achieved with excellent cyclic stability by showing a superior capacity over 1430 mA h g^(-1) at 1 A g^(-1) after 250 cycles and a high areal capacity of ca.2 mA h cm^(-2) at 0.5 C in a full cell system.This study demonstrates that the rational design of conductive polymers with SEI modulation for surface protection has great potential for use in high-energy-density Si anodes.