Fluorine-Doped High-Performance Li_6PS_5Cl Electrolyte by Lithium Fluoride Nanoparticles for All-Solid-State Lithium-Metal Batteries

All-solid-state lithium-metal batteries(ASSLMBs)are widely considered as the ultimately advanced lithium batteries owing to their improved energy density and enhanced safety features.Among various solid electrolytes,sulfide solid electrolyte(SSE)Li_(6)PS_(5)Cl has garnered significant attention.However,its application is limited by its poor cyclability and low critical current density(CCD).In this study,we introduce a novel approach to enhance the performance of Li_(6)PS_(5)Cl by doping it with fluorine,using lithium fluoride nanoparticles(LiFs)as the doping precursor.The F-doped electrolyte Li_(6)PS_(5)Cl-0.2LiF(nano)shows a doubled CCD,from 0.5 to 1.0 mA/cm~2 without compromising the ionic conductivity;in fact,conductivity is enhanced from 2.82 to 3.30 mS/cm,contrary to the typical performance decline seen in conventionally doped Li_(6)PS_(5)Cl electrolytes.In symmetric Li|SSE|Li cells,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is 4 times longer than that of Li_(6)PS_(5)Cl,achieving 1500 h vs.371 h under a charging/discharging current density of 0.2 mA/cm~2.In Li|SSE|LiNbO_3@NCM721 full cells,which are tested under a cycling rate of 0.1 C at 30℃,the lifetime of Li_(6)PS_(5)Cl-0.2LiF(nano)is four times that of Li_(6)PS_(5)Cl,reaching 100 cycles vs.26 cycles.Therefore,the doping of nano-LiF off ers a promising approach to developing high-performance Li_(6)PS_(5)Cl for ASSLMBs.

Stabilized cobalt-free lithium-rich cathode materials with an artificial lithium fluoride coating

Iron-substituted cobalt-free lithium-rich manganese-based materials,with advantages of high specific capacity,high safety,and low cost,have been considered as the potential cathodes for lithium ion batteries.However,challenges,such as poor cycle stability and fast voltage fade during cycling under high potential,hinder these materials from commercialization.Here,we developed a method to directly coat LiF on the particle surface of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2).A uniform and flat film was successfully formed with a thickness about 3 nm,which can effect-ively protect the cathode material from irreversible phase transition during the deintercalation of Li^(+).After surface coating with 0.5wt%LiF,the cycling stability of Li_(1.2)Ni_(0.15)Fe_(0.1)Mn_(0.55O2) cycled at high potential was significantly improved and the voltage fade was largely suppressed.

Synthesis of Barium Lithium Fluoride Nanocrystals Using Reverse Micelles as Microemulsion

Barium lithium fluoride nanocrystals were synthesized in cetyltrimethylammonium bromide (CTAB)/ 2-octanol/ water microemulsion systems. The impurity peaks in XRD patterns were not determined. The result of SEM confirmed that the average sizes and shape of the BaLiF3 nanocrystals. The formation of BaLiF3 and particles size were strongly affected by water content. With increasing water content and reaction times, the size of the particle increases. Meanwhile, the solvent was also found to play a key role in the synthesis of the BaLiF3 nanocrystals.

Thin buffer layer assist carbon-modifying separator for long-life lithium metal anodes

The guided Li dendrite growth by carbon-modifying separator is believed to be an effective strategy for enhancing life of lithium metal batteries(LMBs).However,the weak adhesions,as well as the large interface impedance between the smooth separator and the carbon functional layer(CFL) lead to an easily peeling of the CFL after repetitive cycles.Herein,we propose a promising solution by an inserting thin buffer layer(TBL) to strengthen the adhesion between CFL and separator as a double modifying layer(C-TBL) of the LMBs separator,which greatly improves the stability of the CFL and provides an effective Li metal anode protection.Owing to the sufficient ionic conductivity,chemical stability and strong adhesion to the separator of the TBL,it can avoid the failure of the CFL functionality with small interface impedance.Moreover,the CFL effectively reduces localized flux of Li+ through its abundant pores.The Li/Li cell with C-TBL separator displays the Li dendrite-free and stable cycling performance for at least 1500 h.When LiFePO_(4)(LFP) is employed as the cathode electrode,the assembled full cell with C-TBL separator shows the excellent rate performance and outstanding cycling capability.Our study builds a stable Li+conducting "bridge" between the functional layer and the separator in stabilizing Li metal anode,and provides a fresh idea of the artificial separator of LMBs.

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.

Re-evaluating the nano-sized inorganic protective layer on Cu current collector for anode free lithium metal batteries

Anode free lithium metal batteries(AF-LMBs)have conspicuous advantages both in energy density and the compatibility of battery manufacturing process.However,the limited cycle life of AF-LMBs is a crucial factor hindering its practical application.Fluorinated or nitride artificial inorganic solid electrolyte interphase(SEI)has been found as an effective method to prolong the lifespan of AF-LMBs.Herein,by investigating the impact of nano-sized inorganic gradient layers(LiF or Li3N)on initial Li deposition behavior,we notice that the Li^(+) diffusion barrier and the deposition morphology are highly depended on the thickness of inorganic layers.Thicker protective layers cause larger overpotential as well as more aggregated Li^(+) distribution.This study reveals that the ideal SEI should be synthesized thin and uniformly enough and uncontrollable artificial SEI can cause damage to the lifespan of AF-LMBs.

Improving the electrochemical performance of LiMn_2O_4/graphite batteries using LiF additive during fabrication

LiMn2O4/graphite batteries using LiF additive were fabricated and their electrochemical performance including discharge, cycling and storage performances were tested and compared with LiF-free LiMnEO4/graphite batteries. The LiMnEO4/graphite battery with LiF added shows better capacity （107.5 mAh/g）, cycling performance （capacity retention ratio of 93% after 100 cycles）, and capacity recovery ratio （98.1%） than the LiF-free battery. The improvement in electrochemical performance of the LiF-added LiMnEO4/graphite battery was due to the fact that LiF can restrain the dissolution of Mn from the spinel LiMn2O4 cathode into the electrolyte, leading to a smaller resistance and polariza- tion.

Carbon coating of air-sensitive insulating transition metal fluorides:An example study on α-Li3FeF6 high-performance cathode for lithium ion batteries

Li_(3)FeF_(6)has been the focus of research of fluorine-based cathode materials for lithium-ion batteries.Because of the low electronic conductivity of Li3 FeF6,the decrease of particle size,by an energyconsuming long-time ball milling process with carbon,is necessary to achieve a high electrochemical performance.The most successful method to enhance electrochemical activity,carbon coating,seemed to be impracticable,so far,for sensitive fluorides like Li3 FeF6.In this work,carbon coating on Li3 FeF6 particles has been successfully achieved for the first time,while avoiding both extended hydrolysis and Fe(Ⅲ)-Fe(Ⅱ)reduction.The heat treatment and atmosphere,yielding the maximal transformation of organic carbon to both graphitised and disordered carbon,has been determined.Carbon coating,with a thickness of approximately 2.5 nm,has been achieved by controlled thermal decomposition of glucose,under air,at 300℃.Raman and X-ray photoelectron spectroscopy(XPS)experiments have proved the existence of carbon and Fe2O3 on the surface of Li3FeF6 nanoparticles.XPS spectroscopy indicates the presence of organic residues from glucose decomposition.Attempts to further reduce the orga nic carbon content results in a decrease of the amorphous carbon coating layer.Optimised carbon-coated Li3 FeF6 nanoparticles deliver 122 mA h g^(-1)(85%of theoretical capacity)significantly higher than that of a noncoated sample(58 mA h g^(-1)).Even more,a significant beneficial effect of carbon coating on both capacity retention and coulombic efficiency is observed.

Analysis of electrochemical performance of lithium carbon fluorides primary batteries after storage

Lithium carbon fluorides(Li/CFx)primary batteries are of highly interests due to their high specific energy and power densities.The shelf life is one of the major concerns when they are used as backup power,emergency power and storage power in landers,manned spacecraft or military applications.In this work,real-time storage tests are carried out for both energy-type and power-type Li/CFx pouch batteries at 25℃.Accelerated storage tests are performed at elevated temperature of 55℃.The electrochemical tests are conducted throughout the aging period of 0-365 days for various batteries to study the effects of temperature on both type of batteries.The observed electrochemical behaviors are explained with the evidences from multiple characterizations for post-tested samples.

Charge regulation by ferromagnetic metal/LiF spin-polarized interface for high-performance Li metal anodes

The interfacial characteristics of the Li metal anode(LMA)play a crucial role in its overall performance.Despite various materials being applied to modify the interface,a comprehensive understanding of their specific mechanisms remains to be investigated.Herein,we have prepared carbon cloth(CC)frameworks with their surfaces modified using ferromagnetic metal/LiF heterogeneous films(T^(M)-LiF-CC)as the substrate for LMA,which exhibit superior electrochemical performance.Utilizing ferromagnetic Co as a representative example,our study demonstrates that the enhanced performance of Co-LiF-CC,compared to bare CC,is attributed to the spinpolarized interface contributed by the Co/LiF heterostructure.Co and LiF play individual roles in redistributing electrons and Li^(+)to promote homogeneous Li deposition.Co nanoparticles play a crucial role in generating strong surface capacitance by storing electrons in spin-split bands,while LiF,with low surface diffusion barriers,ensures fast transportation of Li^(+).The Co-LiF-CC@Li electrodes deliver long lives of 7400 and 3600 h at 1 and 2 mA·cm^(-2)in symmetric cells,respectively;moreover,they enable full batteries with high and durable capacities,particularly when the N/P ratios are low(3.3 or even 1.7).

Two-dimensional lithiophilic YF_(δ) enabled lithium dendrite removal for quasi-solid-state lithium batteries

Lithium metal batteries are regarded as promising alternatives to lithium ion batteries due to their high specific capacity.However,lithium dendrite growth during cycling causes safety problem and rapid capacity loss.Here,we report a composite Li anode composed(LYF)of metallic Li and trace amounts(1 e2 wt%)of two-dimensional YF_(δ).The lithiophilic nature of YF_(δ) enables its homogeneous dispersion in metallic lithium.The LYF electrode exhibits lower resistance,higher chemical and mechanical stability,and longer cycle life compared to bare Li electrode due to uniform Li stripping and plating with YF_(δ) incorporation,which was confirmed by in-situ optical microscope observation.X-ray photoelectron spectroscopy reveals that LiF can in-situ form on the LYF electrode with reactions between Li and YF_(δ) during cycling.The spontaneous reactions are clarified by density functional theory calculations.A quasisolid-state cell with LYF anode,LiFePO_(4) cathode and cathode-supported solid electrolyte layer has been constructed with a soft interface constructed between Li anode and solid electrolyte by in-situ thermal polymerization.The cell shows a high initial discharge capacity of 147 mAh g1 at 0.5℃ at 60℃ and sustains a stable cycling over 50 cycles with the in-situ formed LiF-rich layer and soft interface.

Simultaneous upconversion luminescence and color centers generated by femtosecond laser irradiation of LiF crystals

We report the upconversion luminescence of lithium fluoride single crystals excited by an infrared femtosecond laser at room temperature. The luminescence spectra demonstrate that upconversion luminescence originates from the color center of F3^＋. The dependence of fluorescence intensity on pump power reveals that a two-photon excitation process dominates the conversion of infrared radiation into visible emission. Simultaneous absorption of two infrared photons is suggested to produce the F3^＋ center population, which leads to the characteristic visible emission. The results are on the reveal and evaluation of the simultaneous two-photon absorption on the green upconversion process.