Lithium Dendrite Formation Research Articles

Dendrite-Free All-Solid-State Lithium Metal Batteries by In Situ Phase Transformation of the Soft Carbon-Li3N Interface Layer.

The accelerated formation of lithium dendrites has considerably impeded the advancement and practical deployment of all-solid-state lithium metal batteries (ASSLMBs). In this study, a soft carbon (SC)-Li3N interface layer was developed with both ionic and electronic conductivity, for which the in situ lithiation reaction not only lithiated SC into LiC6 with good electronic/ionic conductivity but also successfully transformed the mixed-phase Li3N into pure-phase β-Li3N with a high ionic conductivity/ion diffusion coefficient and stability to lithium metal. The mixed conductive interface layer facilitates fast Li+ transport at the interface and induces the homogeneous deposition of lithium metal inside it. This effectively inhibits the formation of lithium dendrites and greatly improves the performance of the ASSLMB. The ASSLMB assembled with the SC-Li3N interface layer exhibits high areal capacity (15 mA h cm-2), high current density (7.5 mA cm-2), and long cycle life (6000 cycles). These results indicate that this interface layer has great potential for practical applications in high-energy-density ASSLMBs.

Multifunctional COF design addresses Li-S organic electrode limitations

Lithium-sulfur (Li-S) batteries are restricted by cathode polysulfide shuttling and anode lithium dendrite formation. Jin, Zuo, and coworkers recently showed that Li-S batteries with high capacities and cycling stabilities emerge from intentionally designed covalent organic framework (COF) electrodes. This report highlights how COF design can address fundamental challenges in organic electrode engineering.

Lithium‐ion Battery Safety Enhancement via Internal Multi‐Parameter Simulation of Thermal and Pressure Conditions

AbstractSafety incidents with lithium‐ion batteries have impeded the battery industry‘s progress. As internal battery reactions often precede visible symptoms, and traditional electrical parameters are insufficient for comprehensive state assessment and hazard prediction, this study utilized multi‐physics simulations to analyze non‐electrical parameters, focusing on temperature and pressure dynamics. Partial validation of the simulation results was achieved through temperature monitoring experiments under varying charge/discharge rates. The findings indicated that internal temperature uniformly increased, with higher rates leading to more pronounced rises, and identified that lithium dendrite formation and mechanical stress could initiate thermal runaway. To mitigate these risks, specific operational guidelines were suggested. The study also established a positive correlation between pressure changes and temperature, influencing the battery‘s volume. Temperature monitoring further validated the simulations′ precision. This research deepens the understanding of non‐electrical parameter functions during battery operation and provides scientific evidence for the prediction and prevention of lithium‐ion battery safety risks.

Spatial Isolation of Oversized Lithium and Separator via Janus Carbon Fabric Anode for Safer and Steadier Lithium Metal Batteries

AbstractAlthough Li metal is regarded as a promising anode material, the undesired dendritic growth and continuous consumption of lithium during battery cycling result in severe safety risks and low Coulombic efficiency. Herein, a critical spatial‐isolation strategy is demonstrated to separate the originally adjacent lithium metal and separator for higher safety and stability of lithium metal batteries by designing a Janus carbon fabric (CF) anode. Transferring lithium from the anode/separator interface to CF bottom shuts down the prerequisite of lithium dendrite formation, while the oversized lithium at CF bottom can be also used to compensate for the loss of lithium during the charge‐discharge cycling. As a result, the Janus CF//Li anode exhibits an ultralong cyclic life of 450 h at 2 mA cm−2 and >250 h at 4 mA cm−2, which significantly exceeds the common CF//Li anodes. Full cells coupling the Janus CF//Li anodes demonstrate longer cycle life (550 cycles) than that of the CF//Li anodes (450 cycles) at 1C, along with higher rate capability, and excellent cyclic stability at 2C. The remarkable results, as a proof of concept, signify the superior anode structure for improving both battery safety and cyclic stability for the realistic application of lithium metal batteries.

Dendrite/Volume Expansion-Free Lithium Deposition Inside the Enclosed Nanoscale Space of Electrochemically Modified Graphite

Though over-lithiation of graphite can increase the initial specific capacity of the anodes, the cycling stability is unsatisfactory as metallic lithium depositing on the surface of graphite has poor reversibility. In this work, we utilize electrochemical co-intercalation of Li+ and diethylene glycol dimethyl ether (DEGDME) to prepare [Li-DEGDME]+-graphite co-intercalation compounds ([Li-DEGDME]-Gr) from pristine graphite. The expanded d-spacing and abundant cross-layer voids in the interlayer structure of [Li-DEGDME]-Gr owing to the co-intercalation of [Li-DEGDME]+ complex ions and parasitic chemical reactions between solvent molecules and graphene layers promotes the migration of bare Li+ and provides sufficient interior space for extra lithium-storage. As a result, a much higher lithium-storage capacity of 810 mAh g−1 can be successfully achieved. The extra lithium-storage is proved to originate from the deposition of lithium metal inside the enclosed nanoscale space of the as modified graphite, which inhibits the formation of lithium dendrites, isolates lithium metal from electrolytes and avoids volumetric expansion, enabling the [Li-DEGDME]-Gr electrodes to exhibit better cycling stability with high specific capacity. This work proposes a new strategy to enhance the reversibility of lithium metal plating/stripping by accommodating lithium deposition inside modified carbon materials, thus effectively increasing the reversible capacity of graphite-based anode materials.

Constructing stable electrode–electrolyte interfaces by sulfone-based additive to improve the high-voltage performance of LiCoO2

LiCoO2 battery can provide high reversible capacity at a high voltage of 4.6 V, however, maintaining its stability at high voltages remains a major challenge. To address this issue, ethyl methyl sulfone (EMS) is employed as an electrolyte additive to construct stable interfaces between the electrode and electrolyte under high-voltage condition. The characterization results indicate that the addition of EMS can inhibit the decomposition of the standard electrolyte (STD) and the dissolution of Co2+ from cathode, as well as the formation of lithium dendrites on the Li anode, thereby enhancing the stability of both cathode/electrolyte and anode/electrolyte interfaces. Consequently, the cycling performance of LiCoO2 battery using STD+3 %EMS is augmented by 16.9 % at 1 C under a cut-off voltage of 4.6 V over 100 cycles, delivering a specific capacity of 137 mA h g−1. This research provides novel insights into the design of electrolyte additives for high-voltage LiCoO2 batteries and contributes to the further development of high-voltage lithium-ion batteries.

Ga-polymer dual interfacial layer modified Li metal for high-energy Li metal batteries

Lithium metal is regarded as the ultimate anode material for its extremely exceptional theoretical capacity and low reduction potential. Unfortunately, its practical utility has been constrained by changings such as the formation of lithium dendrites, volume expansion resulting from host-free structure, and uncontrollable side reactions with electrolyte. To achieve long cycle life, conventional single artificial layer strategy fails to solve due to ununiform lithium deposition problem. Consequently, the adoption of dual interfacial layer on lithium metal has emerged as prevailing strategy. In this study, we present a design of dual interface protective layer that combines a Ga-based liquid metal with the organic polymer Poly (ethylene glycol) diacrylate (PEGDA). This innovative combination offers synergistic benefits, including alleviate the volume effect and suppressing undesired interface side reactions. In practical test, the Li || Li symmetrical cell assembled from PEGDA Li-Ga dual interfacial layer maintains a low overpotential of 36.8 mV after 1400 h (2 mA cm−2, 2mAh cm−2). Moreover, even at a high rate of 5C, Li || LiNi0.8Co0.1Mn0.1O2 (NCM811, 1.0 mAh cm−2) cell still delivers a discharge capacity of 120 mAh g1, 1.4 times higher than bare Li. Notably, when integrated into a pouch cell with a LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode (1.52 mAh cm−2), this dual interface layers ensures stable performance over 60 cycles, with a capacity retention of 82 %. In summary, this innovative dual interface layer design offers a promising approach to address the intricate challenges associated with lithium metal protection and interface modification.

High‐Safety Anode Materials for Advanced Lithium‐Ion Batteries

Lithium‐ion batteries (LIBs) play a pivotal role in today's society, with widespread applications in portable electronics, electric vehicles, and smart grids. Commercial LIBs predominantly utilize graphite anodes due to their high energy density and cost‐effectiveness. Graphite anodes face challenges, however, in extreme safety‐demanding situations, such as airplanes and passenger ships. The lithiation of graphite can potentially form lithium dendrites at low temperatures, causing short circuits. Additionally, the dissolution of the solid‐electrolyte‐interphase on graphite surfaces at high temperatures can lead to intense reactions with the electrolyte, initiating thermal runaway. This review introduces two promising high‐safety anode materials, Li4Ti5O12 and TiNb2O7. Both materials exhibit low tendencies towards lithium dendrite formation and have high onset temperatures for reactions with the electrolyte, resulting in reduced heat generation and significantly lower probabilities of thermal runaway. Li4Ti5O12 and TiNb2O7 offer enhanced safety characteristics compared to graphite, making them suitable for applications with stringent safety requirements. This review provides a comprehensive overview of Li4Ti5O12 and TiNb2O7, focusing on their material properties and practical applicability. It aims to contribute to the understanding and development of high‐safety anode materials for advanced LIBs, addressing the challenges and opportunities associated with their implementation in real‐world applications.

Fast Interfacial Defluorination Kinetics Enables Stable Cycling of Low-Temperature Lithium Metal Batteries.

The development of low-temperature lithium metal batteries (LMBs) encounters significant challenges because of severe dendritic lithium growth during the charging/discharging processes. To date, the precise origin of lithium dendrite formation still remains elusive due to the intricate interplay between the highly reactive lithium metal anode and organic electrolytes. Herein, we unveil the critical role of interfacial defluorination kinetics of localized high-concentration electrolytes (LHCEs) in regulating lithium dendrite formation, thereby determining the performance of low-temperature LMBs. We investigate the impact of solvation structures of LHCEs on low-temperature LMBs by employing tetrahydrofuran (THF) and 2-methyltetrahydrofuran (2-MeTHF) as comparative solvents. The combination of comprehensive characterizations and theoretical simulations reveals that the THF-based LHCE featured with a strong solvation strength exhibits fast interfacial defluorination reaction kinetics, thus leading to the formation of an amorphous and inorganic-rich solid-electrolyte interphase (SEI) that can effectively suppress the growth of lithium dendrites. As a result, the highly reversible Li metal anode achieves an exceptional Coulombic efficiency (CE) of up to ∼99.63% at a low temperature of -30 °C, thereby enabling stable cycling of low-temperature LMB full cells. These findings underscore the crucial role of electrolyte interfacial reaction kinetics in shaping SEI formation and provide valuable insights into the fundamental understanding of electrolyte chemistry in LMBs.

High-performance lithium metal anode enhanced by multifunctional film of PAN@AgNWs with antimicrobial activity

Lithium metal is expected to be the perfect anode material for the next generation of rechargeable batteries owing to its ultra-high theoretical specific capacity, low density and the lowest redox potential. However, the practical application of lithium metal batteries faces serious challenges, including uneven lithium deposition, negative electrode volume expansion, and short circuits brought by dendritic protrusions. Although the 3D structure of silver nanowires is effective in inhibiting lithium dendrite growth and lithium metal volume expansion, it still suffers from lithium inhomogeneity caused by uneven distribution of silver nanowires and complicated preparation. Therefore, PAN@AgNWs collector was prepared by a simple suction filtration method, and uniform dispersion of silver nanowires and uniform deposition of lithium were achieved. Lithium nucleation overpotential and lithium dendrite formation can be effectively reduced by PAN@AgNWs hosts due to the reduction of local current density by 3D collectors and the improved lithiophilicity of silver nanowires. With low voltage hysteresis, the symmetric battery constructed with its composite anode may cycle steadily for 4500 h at 1 mA cm−2 and 1 mAh cm−2. At the same time, the Li-PAN@AgNWs||LFP full cell still possesses a reversible of 144.18 mAh g−1 after 500 cycles at 1C. Moreover, due to large specific surface area and high surface energy of 3D silver nanowires, it exhibits excellent antimicrobial properties, with an inactivation efficiency of 96.3 % after contacting with E. coli for 2.5 h. This work shows the possibility of using PAN@AgNWs in a large scale for LMBs, and paves the way for development of high-performance antimicrobial materials.

Investigation of Li accumulations in LLZO based solid state batteries via operando neutron imaging and ex-situ correlative structural and chemical analysis

In this study, we present a comprehensive analysis of lithium dendrite formation in half-cells with lithium garnet-type solid-state electrolyte Li7La3Zr2O12 (LLZO) utilizing operando neutron imaging and subsequent ex-situ correlative structural and chemical analysis. The operando experiment involves cycling a solid-state symmetric half-cell (Li|LLZO|Li) until short-circuit failure, all while being irradiated with neutrons, providing invaluable insights into the dynamic processes within the symmetric half-cell. Post-mortem investigations were carried out, comprising two techniques: 1) secondary electron imaging for structural analysis and 2) secondary ion mass spectrometry (SIMS) for chemical mapping. This multifaceted approach creates complementary datasets, bridging the gap between neutron radiography, known for its quantitative transmission capabilities, and high-resolution, high-sensitivity structural and chemical imaging via scanning electron microscopy (SEM) and SIMS.Central to our investigation is the design and development of an operando neutron imaging approach, enabling the study of lithium penetration during the electrochemical cycling. Furthermore, structural, and chemical analyses through correlative SEM/SIMS unveil various morphologies of lithium accumulations. Specifically, regions with dense LLZO reveal intergranular lithium accumulations, while low-density areas within the LLZO pellet, such as pores and cracks, exhibit distinct types of lithium accumulations (e.g. whiskers).Notably, neutron analysis reveals an accumulation of lithium in selected regions, with a maximum increase of up to 3.6 vol.-%. These regions primarily correspond to the roughened LLZO/Li interface, as observed through neutron imaging, although the SEM/SIMS analysis unequivocally confirms the presence of lithium dendrites (with sizes at or below the resolution limit of neutron imaging) also within the bulk of LLZO.This work offers a comprehensive examination of the intricate dynamics of lithium dendrite formation and behaviour in LLZO-based solid-state half-cells, emphasizing the potential of operando techniques to advance our understanding of critical issues (e.g. degradation, dendrite formation, …) in battery research.

Conformal thioaluminate/aluminate polymer protective layer enables dendrite-free lithium metal batteries

Dendrite growth associated with highly reactive surface are the primary challenges for Li metal anode. Herein, an effective thioaluminate/aluminate polymer is developed as an artificial protective layer for stabilizing Li metal anode. This protective layer, enriched with aluminium-sulfur (Al-S) and aluminium-oxygen (Al-O) polar bonds, exhibits remarkable lithium ions transference number (tLi+ = 0.7), high exchange current density, superior electrolyte wettability and high-volume adaptability. This allows for the uniform flow of lithium ions and effectively inhibits the formation of lithium dendrites. This approach affords a hermetic Li metal anode with high columbic efficiency of 99.86 % and extended plating/striping reversibility for 3000 h at 2 mA cm−2@1 mAh cm−2 or 1200 h at 5 mA cm−2@5 mAh cm−2. The protected Li metal anode delivers a prolonged lifespan and rate capability in the LiFePO4 full batteries, showcasing its potential for practical application.

Nanostructured S@VACNTs Cathode with Lithium Sulfate Barrier Layer for Exceptionally Stable Cycling in Lithium-Sulfur Batteries

Lithium-sulfur technology garners significant interest due to sulfur’s higher specific capacity, cost-effectiveness, and environmentally friendly aspects. However, sulfur’s insulating nature and poor cycle life hinder practical application. To address this, a simple modification to the traditional sulfur electrode configuration is implemented, aiming to achieve high capacity, long cycle life, and rapid charge rates. Binder-free sulfur cathode materials are developed using vertically aligned carbon nanotubes (CNTs) decorated with sulfur and a lithium sulfate barrier layer. The aligned CNT framework provides high conductivity for electron transportation and short lithium-ion pathways. Simultaneously, the sulfate barrier layer significantly suppresses the shuttle of polysulfides. The S@VACNTs with Li2SO4 coating exhibit an extremely stable reversible areal capacity of 0.9 mAh cm−2 after 1600 cycles at 1 C with a capacity retention of 80% after 1200 cycles, over three times higher than lithium iron phosphate cathodes cycled at the same rate. Considering safety concerns related to the formation of lithium dendrite, a full cell Si-Li-S is assembled, displaying good electrochemical performances for up to 100 cycles. The combination of advanced electrode architecture using 1D conductive scaffold with high-specific-capacity active material and the implementation of a novel strategy to suppress polysulfides drastically improves the stability and the performance of Li-S batteries.

Failure Mechanism and Thermal Runaway in Batteries during Micro-Overcharge Aging at Different Temperatures.

This paper provides insights into the four key behaviors and mechanisms of the aging to failure of batteries in micro-overcharge cycles at different temperatures, as well as the changes in thermal stability. The test results from a scanning electron microscope (SEM) and an energy-dispersive spectrometer (EDS) indicate that battery failure is primarily associated with the rupture of cathode materials, the fracturing and pulverization of electrode materials on the anode current collector, and the formation of lithium dendrites. Additionally, battery safety is influenced by environmental temperatures and the battery's state of health (SOH), with failed batteries exhibiting the poorest stability and the highest mass loss rates. Under isothermal conditions, micro-overcharge leads to battery failure without thermal runaway. Thus, temperature stands out as the most influential factor in battery safety. These insights hold significant theoretical and practical value for the development of more precise and secure battery management systems.

Functional metal-organic framework membranes with uniform unsaturated pyridine-nitrogen sites as separators for high-performance lithium metal batteries

Lithium metal batteries are a promising successor to lithium-ion batteries due to high specific capacity, low density, and low electrochemical reduction potential. However, inhomogeneous lithium deposition on the Li surface will result in the formation of lithium dendrites and eventually puncture the separator and cause a short circuit. Herein, a functional metal-organic framework membrane with uniform unsaturated pyridine-nitrogen sites is synthesized via coating UiO-67-BPY (2,2 -bipyridine- 5,5 -dicarboxylic acid, named as BPY) on a commercial polypropylene (PP) separator. By replacing the benzene ring with a pyridine ring, the functionalization and porosity of MOF is fully utilized while maintaining the excellent porosity and pore size of MOF. The Li-ion transference number (tLi+) with the functional separator is 0.69 and the ionic conductivity is improved by order of magnitude compared to a plain PP separator. The N atom of the pyridine ring on the UiO-67-BPY has a strong electrostatic interaction force, and a weak coordination bond (N–Li bonding lattice) is formed between N and Li, which leads to an increase in the concentration of free lithium ions and makes their distribution more uniform. This allows lithium ions to migrate more smoothly, which is conducive to ionic conductivity and hinders dendrite formation.

Nitrogen doped sulfide solid electrolytes with enhanced air stability and lithium metal compatibility

AbstractCompared with oxide, halide, and polymer‐based solid electrolytes, Li‐ion conducting sulfide solid electrolytes exhibit remarkable ionic conductivity, electronic conductivity, and exceptional thermal and mechanical properties. Despite these advantages, the susceptibility of sulfide electrolytes to air and the formation of lithium dendrites on the anode hinder their large‐scale commercial application. In this study, we propose a doping strategy involving the nitrogen (N) element in sulfide electrolyte Li5.5PS4.5Cl1.5 (LPSCl) with inherently high ionic conductivity. We have successfully synthesized Li5.5+xPS4.5−xNxCl1.5(x = .025, .05, .07, .10) solid electrolytes by enhancing their air stability through doping. The modified electrolyte material demonstrates stable cycling performance exhibiting superior air stability compared to Li5.5PS4.5Cl1.5. The results indicate that the doped sulfide solid electrolyte effectively suppresses the growth of lithium dendrites, thereby enhancing the compatibility between the lithium metal anode and sulfide solid electrolyte.

Dual-functional Separators Regulating Ion Transport Enabled by 3D-Reinforced Polyimide Microspheres Protective Layer for Dendrite-Free and High-Temperature Lithium Metal Batteries.

High-energy-density lithium metal batteries (LMBs) are confronted with crucial concerns of security and a short cycle lifespan caused by the uncontrollable formation of lithium (Li) dendrites. The poor thermal stability and heterogeneous Li deposition of conventional polyolefin separators often cause battery short circuiting and thermal runaway in LMBs. Herein, a novel dual-functional PE composite separator (PI-COOH/PE) coated by carboxyl polyimide (PI) microspheres is fabricated by an etching-acidification method. The three-dimensional (3D) high-temp PI microsphere with rich carboxyl groups on the surface improve the security of LMBs at extremely high temperatures and facilitate the formation of a stable and uniform SEI layer, which contributes to accelerating the Li+ transport and stabilizing the formation of the SEI layer. Consequently, the Li symmetric cell assembled with the (PI-COOH)/PE separator exhibits stable overpotential over 3000 h, and the corresponding Li//NCM811 full cells also show a high-level discharge capacity of 146.6 mAh g-1 at 5 C. Meanwhile, it also demonstrates outstanding cycling stability and thermal safety, which can survive continuously over 160 min at 140 °C (vs 21 min for PE). The above results indicate the (PI-COOH)/PE separator constructed by a low-cost and industrial-friendly strategy simultaneously addresses high-temperature stability and dendrite resistance.

A CA-LBM framework for simulating the lithium dendrite growth process

The Lithium metal batteries with high energy density are limited for further commercial applications by the formation of Lithium dendrites, which is difficult to regulate due to its complex growth mechanism. In order to investigate the relationship between the dendritic morphology inside the electrode and the external operation conditions, a two-dimensional simulation framework based on the cellular automaton (CA) and the Lattice Boltzmann method (LBM) is proposed. In this framework, the simulation region is divided into discrete grids and each grid includes a cell to record the phase state and the concentration at the position. Meanwhile, the phase transition rule is set in the CA model and the concentration field is solved by LBM. Based on this framework, the impact of the applied voltage and the diffusion coefficient on the dendritic morphology is investigated. The simulation results indicate that the growth rate and the bifurcation rate of Lithium dendrites can both be reduced by applying lower operating voltage and higher diffusion coefficient which is critical in regulating the morphology of Lithium dendrites.

Lithiophilic ZnCu alloy sites on copper current collector for high performance Li metal anode

Lithium (Li) metal has been widely regarded as the optimal anode material for the high-energy density rechargeable batteries, due to its ultrahigh theoretical specific capacity and lowest electrochemical potential. However, the formation of Li dendrites presents a significant safety concern, which limits its practical application. In this paper, to address this issue, an efficient and cost-effective strategy was proposed to prepare a zinc-copper composite collector (ZCC) with outstanding electrochemical performance, which can effectively suppress the formation of lithium dendrites. The lithophilic surface with ZnCu alloy nanoparticles was achieved through physical vapor deposition followed by annealing treatment. The ZCC collector enables dendrite-free deposition of Li due to its negligible nucleation overpotential. Even at high area capacity of 3 mAh cm−2 at 1 mA cm−2 in half-cells, the ZCC exhibits exceptional cycling performance and high coulomb efficiency. Preloaded with Li, the composite electrode (Li/ZCC) delivers an enhanced lifespan with low overpotential evidently. Matched with LiFePO4 (LFP) cathode, LFP||Li/ZCC full cells reveal a superior cycling stability with enhanced capacity retention of 85 % (after 1000 cycles at 1 C) and 87 % (after 800 cycles at 3 C) respectively.

A Healable Quasi-Solid Polymer Electrolyte with Balanced Toughness and Ionic Conductivity.

Solid polymer electrolytes (SPEs) have garnered extensive attention as potential alternatives to traditional liquid electrolytes, primarily due to their prowess in curbing lithium dendrite formation and preventing electrolyte leaks. The quest for SPEs that are both mechanically robust and exhibit superior ionic conductivity has been vigorous. However, achieving a harmonious balance between these two attributes remains a significant challenge. In this study, we introduce a novel quasi-solid electrolyte, ingeniously crafted from a poly(urethane-urea) network, enriched with lithium salts and plasticizers. This innovative composition not only boasts remarkable toughness but also ensures commendable ionic conductivity. Our post-gelation method yields gel polymer electrolytes that undergo rigorous evaluation, leading to an optimized version that stands out with its exceptional room-temperature ionic conductivity (2.94×10-4 S cm-1) and outstanding toughness (11.9 MJ m-3). Moreover, it demonstrates a broad electrochemical window (4.73 V), remarkable stability across a 600-hour cycle test, a high capacity retention exceeding 80 % after 100 cycles at 0.2 C, and a noteworthy self-healing capability. This quasi-solid polymer electrolyte emerges as a promising contender to replace current liquid electrolyte solutions.