Synthesizing an inorganic-rich solid electrolyte interphase by tailoring solvent chemistry in carbonate electrolyte for enabling high-voltage lithium metal batteries

High-voltage(>4.0 V)lithium metal battery(LBM)is considered to be one of the most promising candidates for next-generation high-energy batteries.However,the commercial carbonate electrolyte delivers a poor compatibility with Li metal anode,and its organic dominated solid electrolyte interphase(SEI)shows a low interfacial energy and a slow Li^(+)diffusion ability.In this work,an inorganic LiF-Li_(3)N rich SEI is designed to enable high-voltage LBM by introducing nano-cubic LiF and LiNO_(3)into1 M LiPF_(6)ethylene carbonate(EC)/dimethyl carbonate(DMC)(v:v=1:1)electrolyte.Specifically,the unique nano-cubic structure of as-synthetized LiF particles achieves its high concentration dissolution in carbonate electrolyte to enhance the interfacial energy of SEI.In addition,tetramethylene sulfolane(TMS)is used as a carrier solvent to dissolve LiNO_(3)in the carbonate electrolyte,thereby deriving a Li_(3)N-rich SEI.As a result,the as-designed electrolyte shows a high average Li plating/striping CE of 98.3%after 100 cycles at 0.5 m A cm^(-2)/0.5 mA h cm^(-2).Furthermore,it also enables the ultrathin Li(~50μm)‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM,4.4 mA h cm^(-2))full cell to deliver a high-capacity retention of 80.4%after 100 cycles with an outstanding average CE of 99.7%.Notably,the practical application prospect of the modified electrolyte is also estimated in LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)‖Li pouch cell with an energy density of 261.2 W h kg^(-1).This work sheds light on the internal mechanism of Li^(+)transport within the inorganic dominated SEI and provides a simple approach to stabilize the high-voltage LMBs.

Stable lithium metal anode enabled by a robust artificial fluorinated hybrid interphase

One of the key challenges for achieving stable lithium(Li) metal anode is the construction of the rational solid electrolyte interphase(SEI),but its realization still faces enormous challenges.In this work,a robust artificial fluorinated hybrid interphase consisting of lithium-bismuth(Li3Bi) alloy and lithium-fluoride(LiF) was designed to regulate Li deposition without Li dendrite growth.The obtained hybrid interphase showed the high Li+diffusion rate(3.5 × 10^(-4)S cm^(-1)),high electron resistivity(9.04 × 10^(4)Ω cm),and high mechanical strength(1348 MPa),thus enabling the uniform Li deposition at the Li/SEI interface.Specifically,Li3Bi alloy,as a superionic conductor,accelerated the Li+transport and stabilized the hybrid interphase.Meanwhile,LiF was identified as a superior electron-blocker to inhibit the electron tunneling from the Li anode into the SEI.As a result,the modified Li anode showed the stable Li plating/stripping behaviors over 1000 cycles even at 20 mA cm^(-2).Moreover,it also enabled the Li(50 μm)‖LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(4.4 mA h cm^(-2)) full cell to achieve an average Coulombic efficiency(CE) of 99.6%and a high-capacity retention of 79.2% after 100 cycles,whereas the bare Li anode only exhibited a low-capacity retention of 8.0%.This work sheds light on the internal mechanism of Li+transport within the hybrid interface and provides an effective approach to stabilize the interface of Li metal anode.

Bottom-up lithium growth guided by Ag concentration gradient in 3D PVDF framework towards stable lithium metal anode

Three-dimensional(3 D)frameworks have received much attention as an effective modification strategy for next-generation high-energy-density lithium metal batteries.However,the top-growth mode of lithium(Li)on the 3 D framework remains a tough challenge.To achieve a uniform bottom-up Li growth,a scheme involving Ag concentration gradient in 3 D PVDF framework(C-Ag/PVDF)is proposed.Ag nanoparticles with a concentration gradient induce an interface activity gradient in the 3 D framework,and this gradient feature is still maintained during the cycle.As a result,the C-Ag/PVDF framework delivers a long lifespan over 1800 h at a current density of 1 mA cm^(-2) with a capacity of 1 mAh cm^(-2),and shows an ultra-long life(>1300 h)even at a high current density of 4 mA cm^(-2) with a capacity of 4 mAh cm^(-2).The advantage of concentration gradient provides further insights into the optimal design of the 3 D framework for stable Li metal anode.

In situ formed FeS_(2)@CoS cathode for long cycling life lithium-ion battery

Pyrite FeS_(2)exhibits an ultrahigh energy density(1671 W·h·kg^(-1),for the reaction of FeS_(2)+4Li=Fe+2Li_(2)S)in secondary lithium-ion batteries,but its poor cycling stability,huge volume expansion,the shuttle effect of polysulfides,and slow kinetic properties limit its practical application.In this work,we synthesize a composite structure material CoS on FeS_(2)surface(FeSx@CoS,1<x≤2)by using a cobalt-containing MOF to improve its cycle stability.It is found that CoS inhibits the side reactions and adsorbs polysulfides.As a result,the modified FeS_(2)shows a higher discharge capacity of 577 mA·h·g^(-1)(919 W·h·kg^(-1))after 60 cycles than 484 mA·h·g^(-1)(778 W·h·kg^(-1))of bare pyrite FeS_(2).This efficient strategy provides a valuable step toward the realization of high cycling stability FeS_(2)cathode materials for secondary lithium-ion batteries and enriches the basic understanding of the influence of FeS_(2)interfacial stability on its electrochemical performances.

FeSO_(4) as a Novel Li-Ion Battery Cathode

FeSO_(4) has the characteristics of low cost and theoretical high energy density(799 W·h·kg^(-1) with a two-electron reaction),which can meet the demand for next-generation lithium-ion batteries.Herein,FeSO_(4) as a novel highperformance conversion-reaction type cathode is investigated.We use dopamine as a carbon coating source to increase its electronic conductivity.FeSO_(4)@C demonstrates a high reversible specific capacity(512 mA·h·g^(-1))and a superior cycling performance(482 mA·h·g^(-1) after 250 cycles).In addition,we further study its reaction mechanism.The FeSO_(4) is converted to Fe and Li2SO_(4) during lithium ion insertion and the Fe-Li_(2)SO_(4) grain boundaries further store additional lithium ions.Our findings are valuable in exploring other new conversion-type lithium ion battery cathodes.

Synthesis ofα-Li FeO_(2)/Graphene nanocomposite via layer by layer self-assembly strategy for lithium-ion batteries with excellent electrochemical performance

As a potential alternative cathode material,α-LiFeO2 suffers a realization handicap,mainly due to its poor electrical conductivity and low lithium ion diffusion rate.In this work,we have successfully synthesized α-LiFeO2/rGO nanocomposite through a layer by layer self-assembly modification process and annealing treatment.Due to the strong electrostatic attraction between opposite cha rged spices,α-LiFeO2 nanoparticles were homogeneously dispersed on the graphene sheet to form a typical interconnected conducting network which was bene ficial for electronic conductivity and ionic diffu sivity.In comparison to pristine α-LiFeO2,the α-LiFeO2/rGO displayed an excellent electrochemical perfo rmance with average discharge capacities of 238.9,187.2,178.4,121.8 and 99.5 mA hg^-1 at 0.1,0.2,0.5,1 and 2 C,respectively.Besides,the specific capacity retained 164.9 mA h g^-1 and 107.98 mA h g^-1 after 50 cycles at 0.5 C and 1 C,respectively.The remarkable progress in rate capability and cycling ability of this new nanocomposite developed a new approach to improve the electrochemical performance of α-LiFeO2.