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.

Cooperation of metal-organic coordination complex separator and wide-temperature-range electrolyte enables safe and high-performance lithium batteries

With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion of commonly used polyolefin separators at high temperatures,as well as narrow usable temperature range and high flammability of conventionally commercialized liquid electrolytes.In this work,we report a multifunctional separator mainly consisting of Zn^(2+)-phytate coordination complex nanoparticles and bacterial cellulose nanofibers,named the BZP separator,which possesses high porosity,excellent thermotolerance,good flame retardancy,abilities of anion binding and Ni^(2+)capturing.Through cooperating with the fluoride-free wide-temperature-range electrolyte,Li//LiFePO_(4) cells not only deliver discharge capacities of 110.39 mA h g^(-1)and 113.25 mA h g^(-1)after 2200 cycles (2 C) and1600 cycles (5 C) at 25℃,with capacity retentions of 76.59%and 86.09%,respectively,but also exhibit excellent cycling performance at 80℃ and-40℃.Significantly,the Li//NCM811 cell with a loading of7.8 mg cm^(-2)delivers a discharge capacity of 146.64 mA h g^(-1)after 200 cycles at 0.5 C,with a capacity retention of 89.03%.In addition,pouch cells can work at 120℃ and have low flammability.

Reasonable design a high-entropy garnet-type solid electrolyte for all-solid-state lithium batteries

Traditional garnet solid electrolyte(Li_(7)La_(3)Zr_(2)O_(12))suffers from low room temperature ionic conductivity,poor air stability,high sintering temperature and energy consumption.Considering the development prospects of high-entropy materials with high structural disorder and strong component controllability in the field of electrochemical energy storage,herein,a novel high-entropy garnet-type oxide solid electrolyte,Li_(5.75)Ga_(0.25)La_(3)Zr_(0.5)Ti_(0.5)Sn_(0.5)Nb_(0.5)O_(12)(LGLZTSNO)was constructed by partially replacing the Li and Zr sites in Li_(7)La_(3)Zr_(2)O_(12)with Ga and Ti/Sn/Nb elements,respectively.The experimental and density functional theory(DFT)calculation results show that the high-entropy LGLZTSNO electrolyte has preferable room temperature ion conductivity,air stability,interface contact performance with lithium anode,and the ability to suppress lithium dendrites.Thanks to the improvement of electrolyte performance,the critical current density of Li/Ag@LGLZTSNO/Li symmetric cell was increased from 0.42 to 1.57 mA cm^(−2),and the interface area specific impedance(IASR)was reduced from 765.2 to 42.3Ωcm^(2).Meanwhile,the Li/Ag@LGLZTSNO/LFP full cell also exhibits excellent rate performance and cycling performance(148 mA h g^(−1)at 0.1 C and 124 mA h g^(−1)at 0.5 C,capacity retention up to 84.8%after 100 cycles at 0.1 C),showing the application prospects of high-entropy LGLZTSNO solid electrolyte in high-performance all solid state lithium batteries.

Key Issues for Modelling, Operation, Management and Diagnosis of Lithium Batteries: Current States and Prospects

1 Introduction.With the continuous growth of the global population,the energy demand continues to increase.However,due to the dominance of fossil fuels in global energy and fossil fuels are non-renewable,it has led to the global energy crisis[1].Besides,the use of fossil fuels will generate a mass of air pollutants(e.g.,carbon dioxide,sulfur dioxide,etc.),which will cause serious environmental pollution,climate change[2],etc.To resolve the aforementioned issues,countries around the world have implemented a variety of measures hoping to fundamentally adjust the global energy structure and achieve sustainable development.Thereinto,“Paris Agreement”reached in 2015 under the framework of“United Nations Framework Convention on Climate Change”aims to control the increase in the average temperature of the globe to within 2°C below preindustrial levels,and thereafter to peak global greenhouse gas emissions as soon as possible,continuously decreasing thereafter[3].United Kingdom plans to reduce the average exhaust emissions of“new cars”to approximately 50–70 g/km by 20230,which is roughly half of what it is now[4].In addition,China proposed a plan at“United Nations General Assembly”in 2020 to peak carbon dioxide emissions by 2030 and strive to achieve carbon neutrality by 2060.It is a fact that the whole world is committed to changing the current energy structure,protecting the Earth’s ecology,and achieving global sustainable development[5].

Two-Dimensional Graphitic Carbon-Nitride(g-C_(3)N_(4))-Coated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) Cathodes for High-Energy-Density and Long-Life Lithium Batteries

High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.

Inherent thermal-responsive strategies for safe lithium batteries

Safe batteries are the basis for next-generation application scenarios such as portable energy storage devices and electric vehicles,which are crucial to achieving carbon neutralization.Electrolytes,separators,and electrodes as main components of lithium batteries strongly affect the occurrence of safety accidents.Responsive materials,which can respond to external stimuli or environmental change,have triggered extensive attentions recently,holding great promise in facilitating safe and smart batteries.This review thoroughly discusses recent advances regarding the construction of high-safety lithium batteries based on internal thermal-responsive strategies,together with the corresponding changes in electrochemical performance under external stimulus.Furthermore,the existing challenges and outlook for the design of safe batteries are presented,creating valuable insights and proposing directions for the practical implementation of safe lithium batteries.

Functionally gradient materials for sustainable and high-energy rechargeable lithium batteries:Design principles,progress,and perspectives

Rechargeable lithium batteries with high-capacity cathodes/anodes promise high energy densities for nextgeneration electrochemical energy storage.However,the associated limitations at various scales greatly hinder their practical applications.Functional gradient material(FGM)design endows the electrode materials with property gradient,thus providing great opportunities to address the kinetics and stability obstacles.To date,still no review or perspective has covered recent advancements in gradient design at multiple scales for boosting lithium battery performances.To fill this void,this work provides a timely and comprehensive overview of this exciting and sustainable research field.We begin by overviewing the fundamental features of FGM and the rationales of gradient design for improved electrochemical performance.Then,we comprehensively review FGM design for rechargeable lithium batteries at various scales,including natural or artificial solid electrolyte interphase(SEI)at the nanoscale,micrometer-scale electrode particles,and macroscale electrode films.The link between gradient structure design and improved electrochemical performance is particularly highlighted.The most recent research into constructing novel functional gradients,such as valence and temperature gradients,has also been explored.Finally,we discussed the current constraints and future scope of FGM in rechargeable lithium batteries,aiming to inspire the development of novel FGM for next-generation high-performance lithium batteries.

Boron Nitride-Integrated Lithium Batteries:Exploring Innovations in Longevity and Performance

The current global warming,coupled with the growing demand for energy in our daily lives,necessitates the development of more efficient and reliable energy storage devices.Lithium batteries(LBs)are at the forefront of emerging power sources addressing these challenges.Recent studies have shown that integrating hexagonal boron nitride(h-BN)nanomaterials into LBs enhances the safety,longevity,and electrochemical performance of all LB components,including electrodes,electrolytes,and separators,thereby suggesting their potential value in advancing eco-friendly energy solutions.This review provides an overview of the most recent applications of h-BN nanomaterials in LBs.It begins with an informative introduction to h-BN nanomaterials and their relevant properties in the context of LB applications.Subsequently,it addresses the challenges posed by h-BN and discusses existing strategies to overcome these limitations,offering valuable insights into the potential of BN nanomaterials.The review then proceeds to outline the functions of h-BN in LB components,emphasizing the molecular-level mechanisms responsible for performance improvements.Finally,the review concludes by presenting the current challenges and prospects of integrating h-BN nanomaterials into battery research.

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.

Template synthesis of MnO_2/CNT nanocomposite and its application in rechargeable lithium batteries

Nanostructured MnO2/CNT composite was synthesized by a soft template approach in the presence of Pluronic P123 surfactant. The product was characterized by X-ray diffraction, thermogravimetric and differential thermal analyses, Fourier transformed infrared spectroscopy and high-resolution transmission electron microscopy. The results show that the sample consists of poor crystalline α-MnO2 nanorods with a diameter of about 10 nm and a length of 30-50 nm, which absorb on the carbon nanotubes. The electrochemical properties of the product as cathode material for Li-MnO2 cell are evaluated by galvanostatic charge-discharge and electrochemical impedance spectroscopy （EIS）. Compared with pure MnO2 electrode, the MnO2/CNT composite delivers a much larger initial capacity of 275.3 mA-h/g and better rate and cycling performance.

All-solid-state lithium batteries with inorganic solid electrolytes:Review of fundamental science

The scientific basis of all-solid-state lithium batteries with inorganic solid electrolytes is reviewed briefly, touching upon solid electrolytes, electrode materials, electrolyte/electrode interface phenomena, fabrication, and evaluation. The challenges and prospects are outlined as well.

A review on the failure and regulation of solid electrolyte interphase in lithium batteries

Solid electrolyte interphase(SEI)has been widely recognized as the most important and the least understood component in lithium batteries.Considering the intrinsic instability in both chemical and mechanical,the failure of SEI is inevitable and strongly associated with the performance decay of practical working batteries.In this Review,the failure mechanisms and the corresponding regulation strategies of SEI are focused.Firstly,the fundamental properties of SEI,including the formation principles,and the typical composition and structures are briefly introduced.Moreover,the common SEI failure modes involving thermal failure,chemical failure,and mechanical failure are classified and discussed,respectively.Beyond that,the regulation strategies of SEI with respect to different failure modes are further concluded.Finally,the future endeavor in further disclosing the mysteries of SEI is prospected.

Status and challenges facing representative anode materials for rechargeable lithium batteries

Rechargeable lithium batteries have been widely regarded as a revolutionary technology to store renewable energy sources and extensively researched in the recent several decades.As an indispensable part of lithium batteries,the evolution of anode materials has significantly promoted the development of lithium batteries.However,since conventional lithium batteries with graphite anodes cannot meet the ever-increasing demands in different application scenarios(such as electric vehicles and large-scale power supplies)which require high energy/power density and long cycle life,various improvement strategies and alternative anode materials have been exploited for better electrochemical performance.In this review,we detailedly introduced the characteristics and challenges of four representative anode materials for rechargeable lithium batteries,including graphite,Li_(4)Ti_(5)O_(12),silicon,and lithium metal.And some of the latest advances are summarized,which mainly contain the modification strategies of anode materials and partially involve the optimization of electrode/electrolyte interface.Finally,we make the conclusive comments and perspectives,and draw a development timeline on the four anode materials.This review aims to offer a good primer for newcomers in the lithium battery field and benefit the structure and material design of anodes for advanced rechargeable lithium batteries in the future.

Decoding lithium batteries through advanced in situ characterization techniques

Given the energy demands of the electromobility market,the energy density and safety of lithium batteries(LBs)need to be improved,whereas its cost needs to be decreased.For the enhanced performance and decreased cost,more suitable electrode and electrolyte materials should be developed based on the improved understanding of the degradation mechanisms and structure–performance correlation in the LB system.Thus,various in situ characterization technologies have been developed during the past decades,providing abundant guidelines on the design of electrode and electrolyte materials.Here we first review the progress of in situ characterization of LBs and emphasize the feature of the multi-model coupling of different characterization techniques.Then,we systematically discuss how in situ characterization technologies reveal the electrochemical processes and fundamental mechanisms of different electrode systems based on representative electrode materials and electrolyte components.Finally,we discuss the current challenges,future opportunities,and possible directions to promote in situ characterization technologies for further improvement of the battery performance.

A thermoresponsive composite separator loaded with paraffin@SiO_(2) microparticles for safe and stable lithium batteries

Lithium-ion batteries (LIBs)-related accidents have been reported for years and safety issues are stumbling blocks for the practical applications of lithium metal batteries (LMBs) with higher energy density. More effective strategies to shut down the battery at the early stage of thermal runaway with less side effects on the electrochemical performance are greatly desired. In this work, the core–shell structural paraffin@SiO_(2) microparticles were synthesized by in situ emulsion interfacial hydrolysis and polycondensation and the paraffin@SiO_(2)-loaded separator (PSS) was prepared by a facile filtration method. The introduction of hydrophilic silica shells in paraffin@SiO_(2) enhanced the wettability of carbonate electrolyte with the composite separator and improved the processability of soft paraffin. As a result, when used in LMBs at room temperature, the cell with PSS inside had a more uniform deposition of lithium, a much lower overpotential and a more stable electrochemical performance than the cell with the blank separator or the conventional pure paraffin-loaded separator inside. More significantly, when a heating stimulation (i.e. 115 ℃) was subjected to the cell with PSS inside, the paraffin in the core of paraffin@SiO_(2) could be released, blocking the gaps between particles and the pores in the separator and efficiently stopping the transportation of Li+ between two electrodes, resulting in the thermally-induced shutdown of the cell below the melting temperature of PE (~135 ℃) in the Celgard2325 separator. The core–shell structure of paraffin@SiO_(2) enables the maintaining of each component’s benefits while avoiding each one’s drawbacks by elaborating microstructural design. Therefore, the conventional dilemma between the electrochemcial performance and safety of LMBs could be solved in the future.

MOF-derived multifunctional filler reinforced polymer electrolyte for solid-state lithium batteries

Solid-state lithium batteries(SSLBs) have attracted great interest from researchers due to their inherent high energy density and high safety performance.In order to develop SSLBs,the following two key problems should be solved:(1) Improving the lithium ion conductivity of solid electrolyte at room temperature;and(2) improving the interface between the electrode and the electrolyte.Herein,we propose a new multifunctional filler for reinforcing polymer electrolytes.The composite solid electrolytes(CSEs)mainly contain a MOF-derived Co-doped hollow porous carbon nanocage,which absorbs Li~+ containing ionic liquid(Li-ILs@HPCN),polyethylene oxide(PEO) and lithium bis(trifluoromethanesulfonyl)imide.By optimizing the composition of the CSEs,the CSEs membrane with high ionic conductivity(1.91×10^(-4) S cm^(-1) at 30℃),wide electrochemical stability(5.2 V) and high mobility of lithium ion(0.5) was obtained.Even at a current density of 0.2 mA cm^(-2),the PILH electrolyte possesses excellent interfacial stability against Li metal in Li symmetrical batteries exceeds 1600 h.Finally,the SSLBs(LFP/PILH/Li) showed excellent cycle stability,and the capacity was maintained at 152.9 and140.0 mA h g^(-1) after 150 cycles at a current density of 0.2 C and 0.5 C.This work proposes a completely new strategy for building high-performance SSLBs.

Nano-crystalline FeOOH mixed with SWNT matrix as a superior anode material for lithium batteries

Nano-crystalline FeOOH particles （5-10 nm） have been uniformly mixed with electric matrix of single-walled carbon nanotubes （SWNTs） for forming FeOOH/SWNT composite via a facile ultrasonication method. Directly using the FeOOH/SWNT composite （containing 15 wt% SWNTs） as anode material for lithium battery enhances kinetics of the Li＋ insertion/extraction processes, thereby effectively improving re- versible capacity and cycle performance, which delivers a high reversible capacity of 758 mAh.g-1 under a current density of 400 mA.g-1 even after 180 cycles, being comparable with previous reports in terms of electrochemical performance for FeOOH anode. The good electrochemical performance should be ascribed to the small particle size and nano-crystalline of FeOOH, as well as the good electronic conductivity of SWNT matrix.

Core-shell structured 1,4-benzoquinone@TiO_2 cathode for lithium batteries

Organic carbonyl compounds are considered as promising candidates for lithium batteries due to theirhigh capacity and environmental friendliness, However, they suffer from serious dissolution in the elec-trolyte, leading to fast capacity decay. Here we report core-shell structured 1,4-benzoquinone@titaniumdioxide （BQ@TiO2） composite as cathode for lithium batteries. The composite cathode can deliver a highdischarge capacity of 441.2 mA h/g at 50 mA/g and a high capacity retention of 80.7% after 100 cycles. Thegood cycling performance of BQ@TiO2 composite can be attributed to the suppressed dissolution of BQ,which results from the physical confinement effect of Ti02 shell and the strong interactions between BQand Ti02. Moreover, the combination of ex situ infrared spectra and density functional theory calculationsreveals that the active redox sites of BQ are carbonyl groups. This work provides an alternative way tomitigate the dissolution of small carbonyl compounds and thus enhance their cycling stability.

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.

Heterogeneous electrolyte membranes enabling double-side stable interfaces for solid lithium batteries

The solid polymer electrolyte(SPE) is one of the most promising candidates for building solid lithium batteries with high energy density and safety due to its advantages of flexibility and light-weight.However,the conventional monolayered electrolytes usually exhibit unstable contacts with either high-voltage cathodes or Li-metal anodes during cell operation.Herein,heterogeneous dual-layered electrolyte membranes(HDEMs) consisting of the specific functional polymer matrixes united with the designed solid ceramic fillers are constructed to address the crucial issues of interfacial instability.The electrolyte layers composed of the high-conductivity and oxidation-resistance polyacrylonitrile(PAN) combined with Li_(0.33)La_(0.557)TiO_(3) nanofibers are in contact with the high-voltage cathodes,achieving the compatible interface between the cathodes and the electrolytes.Meanwhile,the electrolyte layers composed of the highstability and dendrite-resistance polyethylene oxide(PEO) with Li_(6.4)La_(3) Zr_(1.4)Ta_(0.6)O_(12) nanoparticles are in contact with the Li-metal anodes,aiming to suppress the dendrite growth,as well as avoid the passivation between the PAN and the Li-metal.Consequently,the solid LiNi_(0.6)Co_(0.2)Mn_(0.2)O2‖Li full cells based on the designed HDEMs show the good rate and cycling performance,i.e.the discharge capacity of 170.1 mAh g^(-1) with a capacity retention of 78.2% after 100 cycles at 0.1 C and 30℃.The results provide an effective strategy to construct the heterogeneous electrolyte membranes with double-side stable electrode/-electrolyte interfaces for the high-voltage and dendrite-free solid lithium batteries.