12.6μm-Thick Asymmetric Composite Electrolyte with Superior Interfacial Stability for Solid-State Lithium-Metal Batteries

Solid-state lithium metal batteries(SSLMBs)show great promise in terms of high-energy-density and high-safety performance.However,there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes,and to minimize the electrolyte thickness to achieve highenergy-density of SSLMBs.Herein,we develop an ultrathin(12.6μm)asymmetric composite solid-state electrolyte with ultralight areal density(1.69 mg cm^(−2))for SSLMBs.The electrolyte combining a garnet(LLZO)layer and a metal organic framework(MOF)layer,which are fabricated on both sides of the polyethylene(PE)separator separately by tape casting.The PE separator endows the electrolyte with flexibility and excellent mechanical properties.The LLZO layer on the cathode side ensures high chemical stability at high voltage.The MOF layer on the anode side achieves a stable electric field and uniform Li flux,thus promoting uniform Li^(+)deposition.Thanks to the well-designed structure,the Li symmetric battery exhibits an ultralong cycle life(5000 h),and high-voltage SSLMBs achieve stable cycle performance.The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg^(−1)/773.1 Wh L^(−1).This simple operation allows for large-scale preparation,and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs.

Grindability Evaluation of Ultrasonic Assisted Grinding of Silicon Nitride Ceramic Using Minimum Quantity Lubrication Based SiO_(2)Nanofluid

Minimum quantity Lubrication(MQL)is a sustainable lubrication system that is famous in many machining systems.It involve the spray of an infinitesimal amount of mist-like lubricants during machining processes.The MQL system is affirmed to exhibit an excellent machining performance,and it is highly economical.The nanofluids are understood to exhibit excellent lubricity and heat evacuation capability,compared to pure oil-based MQL system.Studies have shown that the surface quality and amount of energy expended in the grinding operations can be reduced considerably due to the positive effect of these nanofluids.This work presents an experimental study on the tribological performance of SiO_(2)nanofluid during grinding of Si_(3)N_(4)ceramic.The effect different grinding modes and lubrication systems during the grinding operation was also analyzed.Different concentrations of the SiO_(2)nanofluid was manufactured using canola,corn and sunflower oils.The quantitative evaluation of the grinding process was done based on the amount of grinding forces,specific grinding energy,frictional coefficient,and surface integrity.It was found that the canola oil exhibits optimal lubrication performance compared to corn oil,sunflower oil,and traditional lubrication systems.Additionally,the introduction of ultrasonic vibrations with the SiO_(2)nanofluid in MQL system was found to reduce the specific grinding energy,normal grinding forces,tangential grinding forces,and surface roughness by 65%,57%,65%,and 18%respectively.Finally,regression analysis was used to obtain an optimum parameter combinations.The observations from this work will aid the smooth transition towards ecofriendly and sustainable machining of engineering ceramics.

Advances in All-Solid-State Lithium-Sulfur Batteries for Commercialization

Solid-state batteries are commonly acknowledged as the forthcoming evolution in energy storage technologies.Recent development progress for these rechargeable batteries has notably accelerated their trajectory toward achieving commercial feasibility.In particular,all-solid-state lithium-sulfur batteries(ASSLSBs)that rely on lithium-sulfur reversible redox processes exhibit immense potential as an energy storage system,surpassing conventional lithium-ion batteries.This can be attributed predominantly to their exceptional energy density,extended operational lifespan,and heightened safety attributes.Despite these advantages,the adoption of ASSLSBs in the commercial sector has been sluggish.To expedite research and development in this particular area,this article provides a thorough review of the current state of ASSLSBs.We delve into an in-depth analysis of the rationale behind transitioning to ASSLSBs,explore the fundamental scientific principles involved,and provide a comprehensive evaluation of the main challenges faced by ASSLSBs.We suggest that future research in this field should prioritize plummeting the presence of inactive substances,adopting electrodes with optimum performance,minimizing interfacial resistance,and designing a scalable fabrication approach to facilitate the commercialization of ASSLSBs.

How Does Stacking Pressure Affect the Performance of Solid Electrolytes and All-Solid-State Lithium Metal Batteries?

All-solid-state lithium metal batteries(ASSLMBs)with solid electrolytes(SEs)have emerged as a promising alternative to liquid electrolyte-based Li-ion batteries due to their higher energy density and safety.However,since ASSLMBs lack the wetting properties of liquid electrolytes,they require stacking pressure to prevent contact loss between electrodes and SEs.Though previous studies showed that stacking pressure could impact certain performance aspects,a comprehensive investigation into the effects of stacking pressure has not been conducted.To address this gap,we utilized the Li_(6)PS_(5)Cl solid electrolyte as a reference and investigated the effects of stacking pressures on the performance of SEs and ASSLMBs.We also developed models to explain the underlying origin of these effects and predict battery performance,such as ionic conductivity and critical current density.Our results demonstrated that an appropriate stacking pressure is necessary to achieve optimal performance,and each step of applying pressure requires a specific pressure value.These findings can help explain discrepancies in the literature and provide guidance to establish standardized testing conditions and reporting benchmarks for ASSLMBs.Overall,this study contributes to the understanding of the impact of stacking pressure on the performance of ASSLMBs and highlights the importance of careful pressure optimization for optimal battery performance.

Atom substitution of the solid-state electrolyte Li_(10)GeP_(2)S_(12)for stabilized all-solid-state lithium metal batteries

Solid-state electrolyte Li_(10)GeP_(2)S_(12)(LGPS)has a high lithium ion conductivity of 12 mS cm^(-1)at room temperature,but its inferior chemical stability against lithium metal anode impedes its practical application.Among all solutions,Ge atom substitution of the solid-state electrolyte LGPS stands out as the most promising solution to this interface problem.A systematic screening framework for Ge atom substitution including ionic conductivity,thermodynamic stability,electronic and mechanical properties is utilized to solve it.For fast screening,an enhanced model Dop Net FC using chemical formulas for the dataset is adopted to predict ionic conductivity.Finally,Li_(10)SrP_(2)S_(12)(LSrPS)is screened out,which has high lithium ion conductivity(12.58 mS cm^(-1)).In addition,an enhanced migration of lithium ion across the LSr PS/Li interface is found.Meanwhile,compared to the LGPS/Li interface,LSrPS/Li interface exhibits a larger Schottky barrier(0.134 eV),smaller electron transfer region(3.103?),and enhanced ability to block additional electrons,all of which contribute to the stabilized interface.The applied theoretical atom substitution screening framework with the aid of machine learning can be extended to rapid determination of modified specific material schemes.

In-situ interfacial passivation and self-adaptability synergistically stabilizing all-solid-state lithium metal batteries

The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.

A dynamic database of solid-state electrolyte(DDSE)picturing all-solid-state batteries

All-solid-state batteries(ASSBs)are a class of safer and higher-energy-density materials compared to conventional devices,from which solid-state electrolytes(SSEs)are their essential components.To date,investigations to search for high ion-conducting solid-state electrolytes have attracted broad concern.However,obtaining SSEs with high ionic conductivity is challenging due to the complex structural information and the less-explored structure-performance relationship.To provide a solution to these challenges,developing a database containing typical SSEs from available experimental reports would be a new avenue to understand the structureperformance relationships and find out new design guidelines for reasonable SSEs.Herein,a dynamic experimental database containing>600 materials was developed in a wide range of temperatures(132.40–1261.60 K),including mono-and divalent cations(e.g.,Li^(+),Na^(+),K^(+),Ag^(+),Ca^(2+),Mg^(2+),and Zn^(2+))and various types of anions(e.g.,halide,hydride,sulfide,and oxide).Data-mining was conducted to explore the relationships among different variates(e.g.,transport ion,composition,activation energy,and conductivity).Overall,we expect that this database can provide essential guidelines for the design and development of high-performance SSEs in ASSB applications.This database is dynamically updated,which can be accessed via our open-source online system.

Design strategies and recent advancements of solid-state supercapacitor operating in wide temperature range

Solid-state supercapacitors(SSCs)are emerging as one of the promising energy storage devices due to their high safety,superior power density,and excellent cycling life.However,performance degradation and safety issues under extreme conditions are the main challenges for the practical application.With the expansion of human activities,such as space missions,polar exploration,and so on,the investigation of SSC with wide temperature tolerance,high energy density,power density,and sustainability is highly desired.In this review,the effects of temperature on SSC are systematically illustrated and clarified,including the properties of the electrolyte,ion diffusion,and reaction dynamics of the supercapacitor.Subsequently,we summarize the recent advances in wide-temperature-range SSCs from the aspect of electrolyte modification,electrode design,and interface adjustment between electrode and electrolyte,especially with critical concerns on ionic conductivity and cycling stability.In the end,a perspective is presented,expecting to promote the practical application of the SSC in harsh conditions.

SEI/dead Li-turning capacity loss for high-performance anode-free solid-state lithium batteries

Anode-free solid-state lithium metal batteries(AF-SSLBs)have the potential to deliver higher energy density and improved safety beyond lithium-metal batteries.However,the unclear mechanism for the fast capacity decay in AF-SSLBs,either determined by dead Li or solid electrolyte interface(SEI),limits the proposal of effective strategies to prolong cycling life.To clarify the underlying mechanism,herein,the evolution of SEI and dead Li is quantitatively analyzed by a solid-state nuclear magnetic resonance(ss-NMR)technology in a typical LiPF6-based polymer electrolyte.The results show that the initial capacity loss is attributed to the formation of SEI,while the dead Li dominates the following capacity loss and the growth rate is 0.141 mA h cm^(−2)cycle−1.To reduce the active Li loss,the combination of inorganic-rich SEI and self-healing electrostatic shield effect is proposed to improve the reversibility of Li deposition/dissolution behavior,which reduces the capacity loss rate for the initial SEI and following dead Li generation by 2.3 and 20.1 folds,respectively.As a result,the initial Coulombic efficiency(ICE)and stable CE increase by 15.1%and 15.3%in Li-Cu cells,which guides the rational design of high-performance AF-SSLBs.

A Review on Engineering Design for Enhancing Interfacial Contact in Solid-State Lithium–Sulfur Batteries

The utilization of solid-state electrolytes(SSEs)presents a promising solution to the issues of safety concern and shuttle effect in Li–S batteries,which has garnered significant interest recently.However,the high interfacial impedances existing between the SSEs and the electrodes(both lithium anodes and sulfur cathodes)hinder the charge transfer and intensify the uneven deposition of lithium,which ultimately result in insufficient capacity utilization and poor cycling stability.Hence,the reduction of interfacial resistance between SSEs and electrodes is of paramount importance in the pursuit of efficacious solid-state batteries.In this review,we focus on the experimental strategies employed to enhance the interfacial contact between SSEs and electrodes,and summarize recent progresses of their applications in solidstate Li–S batteries.Moreover,the challenges and perspectives of rational interfacial design in practical solid-state Li–S batteries are outlined as well.We expect that this review will provide new insights into the further technique development and practical applications of solid-state lithium batteries.

Interface-reinforced solid-state electrochromic Li-ion batteries enabled by in-situ liquid-solid transitional plastic glues

The electrochromic Li-ion batteries(ELIBs) combine the functions of electrochromism and energy storage,realizing the display of energy-storage levels by visual signals. However, the accompanying interfacial issues including physical contact and(electro)chemical stability should be taken into account when the conventional liquid/gel electrolytes are replaced with solid-state counterparts. Herein, the in-situ liquid-solid transitional succinonitrile(SCN) plastic glues are constructed between electrodes and poly(ethylene oxide)(PEO) polymer electrolytes, enabling an interface-reinforced solid-state ELIB.Specifically, the liquid SCN precursor can adequately wet electrode/PEO interfaces at high temperature,while it returns back to solid state at room temperature, leading to seamless interfacial contact and smooth ionic transfer without changing the solid state of the device. Moreover, the SCN interlayer suppresses the direct contact of PEO with electrodes containing high-valence metal ions, evoking the improved interfacial stability by inhibiting the oxidation of PEO. Therefore, the resultant solid-state ELIB with configuration of LiMn_(2)O_(4)/SCN-PEO-SCN/WO_(3) delivers an initial discharge capacity of 111 m A h g^(-1) along with a capacity retention of 88.3% after 200 cycles at 30 ℃. Meanwhile, the electrochromic function is integrated into the device by distinguishing its energy-storage levels through distinct color changes. This work proposes a promising solid-state ELIB with greatly reinforced interfacial compatibility by introducing in-situ solidified plastic glues.

Damage evolution and removal behaviors of GaN crystals involved in double-grits grinding

Elucidating the complex interactions between the work material and abrasives during grinding of gallium nitride(GaN)single crystals is an active and challenging research area.In this study,molecular dynamics simulations were performed on double-grits interacted grinding of GaN crystals;and the grinding force,coefficient of friction,stress distribution,plastic damage behaviors,and abrasive damage were systematically investigated.The results demonstrated that the interacted distance in both radial and transverse directions achieved better grinding quality than that in only one direction.The grinding force,grinding induced stress,subsurface damage depth,and abrasive wear increase as the transverse interacted distance increases.However,there was no clear correlation between the interaction distance and the number of atoms in the phase transition and dislocation length.Appropriate interacted distances between abrasives can decrease grinding force,coefficient of friction,grinding induced stress,subsurface damage depth,and abrasive wear during the grinding process.The results of grinding tests combined with cross-sectional transmission electron micrographs validated the simulated damage results,i.e.amorphous atoms,high-pressure phase transition,dislocations,stacking faults,and lattice distortions.The results of this study will deepen our understanding of damage accumulation and material removal resulting from coupling between abrasives during grinding and can be used to develop a feasible approach to the wheel design of ordered abrasives.

Towards Sustainable Grinding of Difficult-to-Cut Alloys-A Holistic Review and Trends

Grinding,a critical precision machining process for difficult-to-cut alloys,has undergone continual technological advancements to improve machining efficiency.However,the sustainability of this process is gaining heightened attention due to significant challenges associated with the substantial specific grinding energy and the extensive heat generated when working with difficult-to-cut alloys,renowned for their exceptional physical and mechanical properties.In response to these challenges,the widespread application of massive coolant in manufacturing industries to dissipate grinding heat has led to complex post-cleaning and disposal processes.This,in turn,has resulted in issues such as large energy consumption,a considerable carbon footprint,and concerns related to worker health and safety,which have become the main factors that restrict the development of grinding technology.This paper provides a holistic review of sustainability in grinding difficult-to-cut alloys,encompassing current trends and future directions.The examination extends to developing grinding technologies explicitly tailored for these alloys,comprehensively evaluating their sustainability performance.Additionally,the exploration delves into innovative sustainable technologies,such as heat pipe/oscillating heat pipe grinding wheels,minimum quantity lubrication,cryogenic cooling,and others.These groundbreaking technologies aim to reduce dependence on hazardous coolants,minimizing energy and resource consumption and carbon emissions associated with coolant-related or subsequent disposal processes.The essence of these technologies lies in their potential to revolutionize traditional grinding practices,presenting environmentally friendly alternatives.Finally,future development trends and research directions are put forward to pursue the current limitation of sustainable grinding for difficult-to-cut alloys.This paper can guide future research and development efforts toward more environmentally friendly grinding operations by understanding the current state of sustainable grinding and identifying emerging trends.

Effects of Different Grinding Methods on the Quality of Soybean Bean Milk

[Objectives] This study was conducted to improve the nutritional value of soybean milk, enrich the variety and taste of soybean milk, and find healthy food that is more conducive to people s nutritional needs. [Methods] Whole soybean milk was prepared by grinding with a grinding wheel at a low concentration (low-concentration grinding) and a stainless steel mill at a high concentration (high-concentration grinding). The sensory, physical and chemical characteristics and anti-nutritional factors of whole soybean milk produced by different grinding methods were studied. [Results] Compared with low-concentration grinding, the protein content in soybean milk prepared by high-concentration grinding increased by 24%, and the dietary fiber content increased by 74.7%. Before and after high-pressure homogenization, the particle size D(4, 3) of soybean milk prepared by low-concentration grinding was 212.1 and 93.59 μm, respectively, and the particle size D(4, 3) of soybean milk prepared by high-concentration grinding was 134.0 and 64.64 μm, respectively. The trypsin inhibitor activity and phytic acid content of soybean milk prepared by high-concentration grinding were significantly lower than those of soybean milk prepared by low-concentration grinding. [Conclusions] This study improves the diet structure of the broad masses of people, strengthens people s physique, and provides a new idea for the implementation and development of China s "Soybean Action Programme".

Improving fatigue properties of normal direction ultrasonic vibration assisted face grinding Inconel 718 by regulating machined surface integrity

Fatigue properties are crucial for critical aero-engine components in extreme serviceenvironments,which are significantly affected by surface integrity(SI)indexes(especially surface topography,residual stressσ_(res),and microhardness)after machining processes.Normal-direction ultrasonic vibration-assisted face grinding(ND-UVAFG)has advantages in improving the machinability of Inconel 718,but there is a competitive relationship between higher compressiveσ_(res)and higher surface roughness R_(a)in affecting fatigue strength.The lack of a quantitative relationship between multiple SI indexes and fatigue strength makes theindeterminacy of a regulatory strategy for improving fatigue properties.In this work,a model of fatigue strength(σ_f)_(sur)considering multiple SI indexes was developed.Then,high-cycle fatigue tests were carried out on Inconel 718 samples with different SI characteristics,and the influence of ND-UVAFG process parameters on SI was analyzed.Based on SI indexes data,the(σ_f)_(sur)distribution in the grinding surface layer for ND-UVAFG Inconel 718 samples was determined using the developed model,and then the fatigue crack initiation(FCI)sites were furtherpredicted.The predicted FCI sites corresponded well with the experimental results,therebyverifying this model.A strategy for improving the fatigue life was proposed in this work,which was to transfer the fatigue source from the machined surface to the bulk material by controlling the SI indexes.Finally,a critical condition of SI indexes that FCI sites appeared on the surface or in bulk material was given by fitting the predicted results.According to the critical condition,an SI field where FCI sites appeared in the bulk material could be obtained.In this field,thefatigue life of Inconel 718 samples could be improved by approximately 140%.

Lithiophilic Li-Si alloy-solid electrolyte interface enabled by high-concentration dual salt-reinforced quasi-solid-state electrolyte

Solid polymer electrolytes(SPEs)are urgently required to achieve practical solid-state lithium metal batteries(LMBs)and lithium-ion batteries(LIBs),Herein,we proposed a mechanism for modulating interfacial conduction and anode interfaces in high-concentration SPEs by LiDFBOP.Optimized electrolyte exhibits superior ionic conductivity and remarkable interface compatibility with salt-rich clusters:(1)polymer-plastic crystal electrolyte(P-PCE,TPU-SN matrix)dissociates ion pairs to facilitate Li+transport in the electrolyte and regulates Li^(+)diffusion in the SEI.The crosslinking structure of the matrix compensates for the loss of mechanical strength at high-salt concentrations;(2)dual-anion TFSI^(-)_(n)-DFBOP^(-)_(m)in the Li^(+)solvation sheath facilitates facile Li^(+)desolvation and formation of salt-rich clusters and is conducive to the formation of Li conductive segments of TPU-SN matrix;(3)theoretical calculations indicate that the decomposition products of LiDFBOP form SEI with lower binding energy with LiF in the SN system,thereby enhancing the interfacial electrochemical redox kinetics of SPE and creating a solid interface SEI layer rich in LiF.As a result,the optimized electrolyte exhibits an excellent ionic conductivity of9.31×10^(-4)S cm^(-1)at 30℃and a broadened electrochemical stability up to 4.73 V.The designed electrolyte effectively prevents the formation of Li dendrites in Li symmetric cells for over 6500 h at0.1 mA cm^(-2).The specific Li-Si alloy-solid state half-cell capacity shows 711.6 mAh g^(-1)after 60 cycles at 0.3 A g^(-1).Excellent rate performance and cycling stability are achieved for these solid-state batteries with Li-Si alloy anodes and NCM 811 cathodes.NCM 811‖Prelithiated silicon-based anode solid-state cell delivers a discharge capacity of 195.55 mAh g^(-1)and a capacity retention of 97.8%after 120 cycles.NCM 811‖Li solid-state cell also delivers capacity retention of 84.2%after 450 cycles.

A gel polymer electrolyte based on IL@NH_(2)-MIL-53(Al)for high-performance all-solid-state lithium metal batteries

Solid polymer composite electrolytes possess the benefits of superior compatibility with electrodes and good thermal characteristics for more secure energy storage equipment.Herein,a new gel polymer electrolyte(GPE)containing NH_(2)-MIL-53(Al),[PP_(13)][TFSI],LiTFSI,and PVDF-HFP was prepared using a simple method of solution casting.The effects of encapsulating different ratios of ionic liquid([PP_(13)][TFSI])into the micropores of functionalized metal-organic frameworks(NH_(2)-MIL-53(Al))on the electrochemical properties were compared.XRD,SEM,nitrogen adsorption-desorption isotherms,and electrochemical measurements were conducted.This GPE demonstrates a superior ionic conductivity of 8.08×10^(-4)S·cm^(-1)at 60℃and can sustain a discharge specific capacity of 156.6 mA·h·g^(-1)at 0.2 C for over 100 cycles.This work might offer a potential approach to alleviate the solid-solid contact with the solid-state electrolyte and electrodes and broaden a new window for the creation of all-solid-state batteries.

Structural analysis of silk using solid-state NMR

Silkworms and spiders are capable of generating fibers that are both highly durable and elastic in a short span of time,using a silk solution stored within their bodies at room temperature and normal atmospheric pressure.The dragline silk fiber,which is essentially a spider's lifeline,surpasses the strength of a steel wire of equivalent thickness.Regrettably,humans have yet to replicate this process to produce fibers with similar high strength and elasticity in an eco-friendly manner.Therefore,it is of utmost importance to thoroughly comprehend the extraordinary structure and fibrillation mechanism of silk,and leverage this understanding in the manufacturing of high-strength,high-elasticity fibers.This review will delve into the recent progress in comprehending the structure of silks derived from silkworms and spiders,emphasizing the distinctive attributes of solidstate NMR.

High-performance grinding of ceramic matrix composites

Ceramic matrix composites(CMCs)are highly promising materials for the next generation of aero-engines.However,machining of CMCs suffers from low efficiency and poor surfacefinish,which presents an obstacle to their wider application.To overcome these problems,this study investigates high-efficiency deep grinding of CMCs,focusing on the effects of grinding depth.The results show that both the sur-face roughness and the depth of subsurface damage(SSD)are insensitive to grinding depth.The material removal rate can be increased sixfold by increasing the grinding depth,while the surface roughness and SSD depth increase by only about 10%.Moreover,it is found that the behavior of material removal is strongly dependent on grinding depth.As the grinding depth is increased,fibers are removed in smaller sizes,with thefiber length in chips being reduced by about 34%.However,too large a grinding depth will result in blockage by chip powder,which leads to a dramatic increase in the ratio of tangential to normal grinding forces.This study demonstrates that increasing the depth of cut is an effective approach to improve the machining efficiency of CMCs,while maintaining a good surfacefin-ish.It provides the basis for the further development of high-performance grinding methods for CMCs,which should facilitate their wider application.

Li-Ion Transport Mechanisms in Selenide-Based Solid-State Electrolytes in Lithium-Metal Batteries:A Study of Li_(8)SeN_(2),Li_(7)PSe_(6),and Li_(6)PSe_(5)X(X=Cl,Br,I)

To achieve high-energy-density and safe lithium-metal batteries(LMBs),solid-state electrolytes(SSEs)that exhibit fast Li-ion conductivity and good stability against lithium metal are of great importance.This study presents a systematic exploration of selenide-based materials as potential SSE candidates.Initially,Li_(8)SeN_(2)and Li_(7)PSe_(6)were selected from 25 ternary selenides based on their ability to form stable interfaces with lithium metal.Subsequently,their favorable electronic insulation and mechanical properties were verified.Furthermore,extensive theoretical investigations were conducted to elucidate the fundamental mechanisms underlying Li-ion migration in Li_(8)SeN_(2),Li_(7)PSe_(6),and derived Li_(6)PSe_(5)X(X=Cl,Br,I).Notably,the highly favorable Li-ion conduction mechanism of vacancy diffusion was identified in Li6PSe5Cl and Li_(7)PSe_(6),which exhibited remarkably low activation energies of 0.21 and 0.23 eV,and conductivity values of 3.85×10^(-2)and 2.47×10^(-2)S cm^(-1)at 300 K,respectively.In contrast,Li-ion migration in Li_(8)SeN_(2)was found to occur via a substitution mechanism with a significant diffusion energy barrier,resulting in a high activation energy and low Li-ion conductivity of 0.54 eV and 3.6×10^(-6)S cm^(-1),respectively.Throughout this study,it was found that the ab initio molecular dynamics and nudged elastic band methods are complementary in revealing the Li-ion conduction mechanisms.Utilizing both methods proved to be efficient,as relying on only one of them would be insufficient.The discoveries made and methodology presented in this work lay a solid foundation and provide valuable insights for future research on SSEs for LMBs.