Lithium loss, resistance growth, electrode expansion, gas evolution, and Li plating: Analyzing performance and failure of commercial large-format NMC-Gr lithium-ion pouch cells
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Gasper, Paul (ORCID:0000000188349458)↗
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Advancing Li-plating detection: Motivating a multi-signal correlation approach
Facilitating fast charging in lithium-ion batteries (LiBs) is often linked to Li-plating, which harms performance, longevity, and safety. Early detection of Li-plating is essential for rapid technological development and for preventing performance deterioration and ensuring safety during operation. Fast and real-time detection, using commonly collected measurements like voltage (V), current (I), temperature (T), and pressure (P), is highly desirable. Existing standalone methods relying on electrochemical and mechanical signatures, using half, smaller, or specially designed cells often operated at lower temperatures, fail to account for real-world fast-charging conditions. These signatures may also have inherent unreliability in aged LiBs, a phenomenon currently not-well understood. All these uncertainties have complicated practical implementation of a robust Li-plating detection technique. This study, through multiple case studies involving real-world fast-charging conditions using automotive-grade 11.6 Ah LiBs, shows that many single signal-based diagnostic techniques may be inadequate to detect Li-plating. Among various signatures, end-of-charge rest pressure, differential pressure-sensing, and end-of-charge rest voltage were identified as particularly useful in detecting Li-plating. Furthermore, A multi-signal-based detection technique is shown to be more robust in detecting Li-plating. Using both fresh and aged cells, the results and analysis highlight how detection capabilities are influenced by various factors, including battery design, size, charging speed, operating temperature, and degradation level. Adopting such a multi-signal Li-plating detection approach may be instrumental in the rapid development of battery technology in laboratories, as well as ensuring the enhanced safety of next-generation LiBs in real-world fast-charging applications.
25 ENERGY STORAGE↗
Neutron-Friendly Li-Ion Battery Coin Cell for In Situ 3D Visualization of Li Plating
Advanced battery characterization using in situ/operando neutron imaging is critical for uncovering degradation modes such as lithium (Li) plating in Li-ion batteries (LIBs). However, conventional LIBs hinder operando neutron radiography (NR) and in situ neutron micro-computed tomography (N-μCT) for visualizing Li plating near the graphite-separator interface due to strong attenuation from hydrogen-rich components like PP–PE–PP separators, electrolyte, and Fe-based spacers. In this work, we designed and tested a neutron-friendly battery (NFB) optimized for in situ Li detection during extreme fast charging (XFC). Guided by neutron attenuation cross-sections and material transmission, the NFB enables clear visualization at the graphite–separator interface, which is typically opaque in standard LIBs. Electrochemical tests show the NFB exhibits voltage/current responses like standard cells for up to 50 XFC cycles. However, its lower reversibility and capacity are likely due to Cu-coated Al spacer degradation from delamination or corrosion. We propose titanium spacers as a more stable alternative, albeit requiring custom machining. Using this optimized cell, we achieved simultaneous neutron tomography of multiple cells, capturing in situ 3D images of dead Li accumulation, particularly near graphite edges. These heterogeneous deposits and disconnected Li clusters suggest localized current density hotspots during XFC.
25 ENERGY STORAGE↗
Impact of Testing Method on Safety Assessment of Aged Li-Ion Cells: Part II – Aged Cells Without Li Plating
Understanding the safety profile of aged Li-ion batteries is essential for developing effective battery management and hazard mitigation strategies. However, most safety assessments have focused on fresh batteries, with just a few calorimetry studies on aged batteries with metal oxide positive electrodes. This study provides a broad assessment of commercial 18650-type Li-ion batteries with NCA, NMC, and LFP positive electrodes, both uncycled and aged under conditions that promoted solid electrolyte interphase (SEI) growth as the dominant degradation mechanism. The cells underwent mechanical (nail penetration, crush), electrical (overcharge, overdischarge), and thermal (accelerating rate calorimetry) abuse tests. Safety was rated on general characteristics such as mass loss, maximum temperature, and EUCAR (European Council for Automotive R&D) hazard level, as well as characteristics specific to individual abuse tests. Generally, aged cells with SEI growth exhibited similar or improved safety compared to uncycled cells, contrasting with our previous findings on NCA cells with Li plating as the dominant aging mechanism (Part I of this series). Yet, some tests and characteristics indicated reduced aged cell safety, such as earlier triggering of mechanical failure. These results emphasize the need to examine aged battery safety across diverse empirical techniques, degradation modes, and chemistries.
Lithium-ion cells↗
Hydride-Based Interlayer for Solid-State Anode-Free Battery
Solid-state batteries (SSBs) are considered a promising approach to realizing an anode-free concept with high energy densities. However, the initial Coulombic efficiency (ICE) has remained insufficient for anode-free batteries using sulfide-based solid electrolytes (SEs). Herein, we incorporated a hydride-based interlayer, 3LiBH 4 -LiI (LBHI), between a typical sulfide SE, Li 6 PS 5 Cl, and the Cu current collector. Further, by investigating the Li plating and stripping behaviors and the (electro)chemical stability between SEs and plated Li, we demonstrated that LBHI can effectively improve interfacial stability, leading to an ICE exceeding 94% in anode-free half cells. This interlayer also improves Coulombic efficiencies and specific capacities in anode-free full cells. Furthermore, the utilization of LBHI enables one to study Li plating behaviors without interference from interfacial (electro)chemical instabilities. The analysis of stack pressure evolution during electrochemical cycling reveals that soft shorting in SSBs arises from both dendrite formation and deformation, offering insights into further optimizing solid-state anode-free batteries.
25 ENERGY STORAGE↗
Operando FTIR investigation of salt dynamics in Li-ion batteries during fast charging
Li-ion batteries, when charged at fast-charging rates ($>$2C), suffer from reduced lifetimes and can undergo catastrophic failure. During high-rate charging, Li-ions are unable to rapidly transport through high-loading electrodes ($>$4 mAh cm −2 ). This results in unequal charge distributions, potentials, and utilization of the active material, which can lead to Li plating. Li-ion concentration polarization, in which Li-ions deplete in the anode and accumulate in the cathode during charging, precedes Li plating. An operando FTIR-ATR graphite/NMC cell developed in this research captured Li-ion concentration polarization in real-time. During fast charging, decreases in Li-ion concentration ($>$95%) were measured at the back of the anode. This is the first verification of complete Li-ion depletion within the anode at high C-rates. The measurements also showed graphite stage transition. A P2D model was developed for comparison to the operando measurements. The measurements agreed with the model in some cases, but disparities existed at high C-rates and loadings. In the experiment, the Li-ion concentration often failed to recover to 1.2 M until several hours after charging, whereas the model Li-ion concentration rapidly recovered. The contrast between the model and experiment results indicates that further investigation is required to improve understanding of Li-ion concentration dynamics during fast charging.
25 - ENERGY STORAGE↗
Particle size effect of graphite anodes on performance of fast charging Li-ion batteries
Charging energy-dense lithium-ion batteries (LIBs) with thick graphite electrodes at high current densities are typically accompanied by poor performance and safety issues. The root cause is the onset of Li plating at the surface of graphite when lithiated to a high capacity within a short time period. Here, we investigated the behavior of graphite electrodes with various particle sizes under fast charge operations. Results from the electrochemical characterization on graphite electrodes exhibit the superiority of smaller particles over bigger particles in terms of suppressing the onset of Li plating and growth of plated Li particles. Observations from scanning electron microscopy also corroborate the presence of plated Li in electrodes with big graphite particles and its absence in graphite electrodes with small particles, when the cells were lithiated to 90% of the state of charge (SOC). Further, the improved performance of cells with the small particles might be associated with the low Li-ion concentration at the surface of graphite and thus reduced overpotential in graphite electrodes. The simulated results revealed that, compared to bigger particles, smaller particles have lower surface intercalation at any given cell SOC, which may significantly reduce the overpotential in the graphite electrodes and mitigate the onset of Li plating. This agrees well with experimental observations.
25 ENERGY STORAGE↗
Fast-charging lithium-ion batteries: Synergy of carbon nanotubes and laser ablation
Advancing lithium-ion battery (LiB) technology to achieve 10–15-min extreme fast charging (XFC) while maintaining high energy density and longevity poses a significant challenge. Addressing Li-plating is crucial, as it depletes useable Li, causing deterioration and safety issues. Here, this study explores a holistic approach incorporating Single-Wall Carbon Nanotubes (SWCNTs) and Laser Ablation (LA) to mitigate Li-plating while maintaining high charge acceptance under 10–15-min XFC. SWCNTs enhance the electrical conductivity and mechanical integrity of the positive electrode (PE), reducing overall cell overpotential at high charging rates. Concurrently, LA is applied to negative electrodes (NE) to reduce tortuosity of ion-diffusion pathways and increase surface wettability, improving Li-ion transport. Combining SWCNTs in the PE and LA on the NE, our experimental findings demonstrate a significant reduction in Li-plating and maintained high charge acceptance of ~84.33 % after 800 5C (12 min) charge cycles for cells having PE with ~3.3 mAh cm –2 and NE with 3.9 mAh cm –2 loadings. This study highlights the potential of combining SWCNTs and LA to address Li-plating in LiBs and opens new avenues for designing battery systems capable of achieving 10–15-min XFC.
24 POWER TRANSMISSION AND DISTRIBUTION↗
Voltage-Based Strategies for Preventing Battery Degradation under Diverse Fast-Charging Conditions
Maintaining safe operating conditions is a key challenge for high-performance lithium-ion battery applications. The lithium-plating reaction remains a risk during charging, but limited studies consider the highly variable charging conditions possible in commercial cells. Here we combine pseudo-2D electrochemical modeling with data visualization methods to reveal important relationships between the measurable cell voltage and difficult-to-predict Li-plating onset criteria. An extensively validated model is used to compute Li plating for thousands of multistep charging conditions spanning diverse rates, temperatures, states-of-charge, and cell aging. Here we observe an empirical cell operating voltage limit below which plating does not occur across all conditions, and this limit varies with the battery state-of-charge and aging. A model sensitivity analysis also indicates that, when comparing two charging voltage profiles, the capacity difference at 4.0 V correlates well with the difference in the plating onset capacity. These results encourage simple strategies for Li-plating prevention that are complementary to existing battery controls.
25 ENERGY STORAGE↗
Time-Evolved Hetero-Alkali Interphases Enable Long-Life Sulfide-Based Anode-Free Solid-State Batteries
Sulfide-based anode-free solid-state batteries (AFSSBs) offer compelling advantages in terms of energy density and safety, yet their practical implementation is severely hindered by undesirable interfacial reactions between sulfide solid electrolytes (SEs) and freshly plated lithium (Li), as well as non-uniform Li plating/stripping behavior. Herein, an effective interfacial stabilization strategy by incorporating sodium bis(fluorosulfonyl)imide (NaFSI) additive into the Li5.4PS4.4Cl1.6 (LPSC) is investigated. Unlike conventional Li-based additives that form static passivation layers, NaFSI introduces a transient hetero-alkali chemistry that kinetically governs interphase evolution during fresh Li plating. NaFSI induces a timesequenced interphase evolution: an initial NaF/LiF-rich layer that suppresses early sulfide reduction, followed by a LiF/Li3N-rich layer that optimizes Li⁺ transport during repeated anode-free cycling. This evolved robust and fast ion conducting layer mitigates interfacial impedance growth, enhances Li + transport kinetics, and suppresses localized Li growth and filamentary shorting. As a result, the anode-free full cell with NaFSI modified LPSC as the interlayer exhibits an excellent cycling stability over 500 cycles at 0.2 C with a capacity retention of 77.6%, whereas the cell with bare LPSC suffers from rapid capacity decay after 100 cycles, retaining only 32.1% of its initial capacity. This work establishes dynamic heteroalkali additive chemistry as a general strategy to kinetically program solid-solid interphases, guiding the interface design in anode-free solid-state batteries.
25 ENERGY STORAGE↗
Controlled large-area lithium deposition to reduce swelling of high-energy lithium metal pouch cells in liquid electrolytes
Lithium (Li) metal battery technology, renowned for its high energy density, faces practical challenges, particularly concerning large volume change and cell swelling. Despite the profound impact of external pressure on cell performance, there is a notable gap in research regarding the interplay between external pressure and the electroplating behaviours of Li+ in large-format pouch cells. Here we delve into the impact of externally applied pressure on electroplating and stripping of Li in 350 Wh kg –1 pouch cells. Employing a hybrid design, we monitor and quantify self-generated pressures, correlating them with observed charge–discharge processes. A two-stage cycling process is proposed, revealing controlled pouch cell swelling of less than 10%, comparable to state-of-the-art Li-ion batteries. Finally, the pressure distribution across the cell surface unveils a complex Li+ detour behaviour during electroplating, highlighting the need for innovative strategies to address uneven Li plating and enhance Li metal battery technology.
25 ENERGY STORAGE↗
Controlled lithium stripping enables a stable interface for long-cycling anode-free solid-state batteries
Anode-free solid-state batteries (AFSSBs) are a promising route toward achieving high energy density. In these cells, the anode contains no pre-stored lithium (Li). Instead, the entire Li inventory originates from the cathode and is freshly deposited onto a bare current collector during charging. However, achieving uniform and defect-free Li plating on this bare current collector remains a major challenge, often resulting in low Li plating/stripping efficiency and rapid capacity decay. Here, for the first time, operando neutron imaging is employed to visualize Li plating/stripping behavior in an anode-free full cell with LiNi0.82Mn0.07Co0.11O2 (NMC) as the cathode. Operando measurements reveal that complete stripping of Li leaves isolated Li residues on the current collector, which degrades the interfacial contact between the current collector and the solid-state electrolyte. To mitigate this interfacial issue and promote more uniform Li deposition, we implement a discharge-cutoff-voltage strategy that intentionally retains a thin residual Li layer after stripping. This preserved Li-containing interfacial reservoir not only improves interfacial contact but also serves as an in situ formed seed layer that enables more homogeneous subsequent Li plating. As a result, the optimized anode-free cell with limited stripping depth exhibits excellent long-term cycling stability, maintaining a discharge capacity of 112.1 mAh g−1 with a capacity retention of 80.6% and an average coulombic efficiency of approximately 99.9% after 500 cycles at 0.25 C. In contrast, the cell with a conventional discharge cutoff voltage of 2.8 V exhibits rapid capacity decay, retaining only 59.7 mAh g−1 after 50 cycles with a capacity retention of 40.7%. This work demonstrates that limiting deep stripping to preserve a thin Li-containing interfacial layer can effectively improve the cycling stability of sulfide-based AFSSBs.
Wang, Jiwei [Northeastern University, Boston]↗
Dimolybdenum Paddlewheel Complexes with Cation Binding Sites as Electrolyte Additives to Manipulate the Solid-Electrolyte Interphase at Lithium Metal Anodes
The use of electrolyte additives at millimolar loadings to control the surface chemistry of lithium metal anodes (LMAs) is a leading strategy to improve lithium metal batteries and promote electrosynthetic reactions. Whereas previous studies employed either inorganic or organic additives, in this study, we report the first organometallic additive, Mo 2 (mea) 4 [1, mea = 2-(2-methoxyethoxy)acetate], a dimolybdenum paddlewheel complex that is stable under Li plating conditions and features cation binding sites in the second coordination sphere that promote reversible Li + coordination. Binding of Li + ions to 1 induces immobilization of cationically charged aggregates (or products thereof) into the solid electrolyte interphase (SEI), imparting multiple beneficial functions. The modified SEI was found to protect the LMA against parasitic side reactions, produce modest but measurable improvements to Li plating properties (e.g., overpotential, surface structure, and Coulombic efficiency), and improve interfacial charge transport properties. Furthermore, the most notable benefit to battery cycling performance appears in calendar aging tests, which show that the presence of the additive protects the LMA from parasitic side reactions that would otherwise decrease overall cell cycling efficiency over time. Collectively, these data disclose a tactic for designing electrolyte additives using principles of organometallic synthesis.
Additives↗
Characterization of Cycle-Aged Commercial NMC and NCA Lithium-ion Cells: I. Temperature-Dependent Degradation
Lithium-ion batteries are widely used in applications from consumer electronic devices to stationary energy storage. Appropriate management of batteries is challenging due to limited data on their performance and materials degradation. Previous studies have focused on characterization of single cells under specific operating conditions. In the present work, commercial 18650 lithium-ion cells with LiNi x Mn y Co 1-x-y O 2 (NMC) and LiNi x Co y Al 1-x-y O 2 (NCA) positive electrodes were characterized by a wide range of electrochemical and materials techniques after cycling at 15, 25, or 35 °C to ∼80% capacity. The NCA cells exhibit weak temperature dependence in their cycle aging and materials degradation. The NMC cells exhibited increased capacity fade and materials degradation as ambient temperature decreased. All cells exhibited loss of lithium inventory as their primary degradation mode. However, the NCA cells only showed evidence of solid electrolyte interphase (SEI) growth whereas the NMC cells showed signs of Li plating at 15 °C, transitioning to SEI growth at 35 °C. The NMC cells displayed signs of loss of active material at the positive electrode at lower temperatures, suggesting that Li plating is correlated to additional processes that increase the rate of degradation. These results highlight the importance of avoiding broad generalizations about Li-ion battery temperature dependence.
25 ENERGY STORAGE↗
Electrolyte Design for Fast‐Charging Lithium‐Based Batteries
Fast charging is essential for the widespread adoption of lithium (Li)-ion batteries, but it is fundamentally limited by sluggish interfacial kinetics, Li plating, and electrolyte instability at high current densities. Over the past decade, electrolyte engineering has emerged as a key strategy to address these challenges. This review summarizes the development of fast-charging electrolytes over the past ten years and outlines a design framework. Electrolyte formulations are first deconstructed into their main components—solvents, salts, and functional additives—and representative strategies for tuning solvation structure and interphase chemistry are discussed to suppress Li plating and improve interfacial kinetics. The discussion then extends to advanced electrolyte systems, particularly localized high-concentration electrolytes (LHCEs), and their compatibility with different anode chemistries. Advanced characterization techniques are also summarized and categorized based on destructiveness, spatial and temporal resolution, quantitative analysis, and the chemical species or processes probed across multiple length scales. Recent progress in AI-enabled electrolyte discovery and battery management system (BMS) strategies for optimized fast-charging protocols is further highlighted. Finally, perspectives are presented on translating electrolyte innovations from academic research to practical applications, with emphasis on cell format, realistic operating conditions, and manufacturability.
25 ENERGY STORAGE↗
Design principles of heterointerfacial redox chemistry for highly reversible lithium metal anode
High electrochemical reversibility is required for the application of high-energy-density lithium (Li) metal batteries; however, inactive Li formation and SEI (solid electrolyte interface)-instability-induced electrolyte consumption cause low Coulombic efficiency (CE). The prior interfacial chemical designs in terms of alloying kinetics have been used to enhance the CE of Li metal anode; however, the role of its redox chemistry at heterointerfaces remains a mystery. Herein, the relationship between heterointerfacial redox chemistry and electrochemical transformation reversibility is investigated. It is demonstrated that the lower redox potential at heterointerface contributes to higher CE, and this enhancement in CE is primarily due to the regulation of redox chemistry to Li deposition behavior rather than the formation of SEI films. Low oxidation potential facilitates the formation of the surface with the highly electrochemical binding feature after Li stripping, and low reduction potential can maintain binding ability well during subsequent Li plating, both of which homogenize Li deposition and thus optimize CE. In particular, Mg hetero-metal with ultra-low redox potential enables Li metal anode with significantly improved CE (99.6%) and stable cycle life for 700 cycles at 3.0 mA cm -2 . This work provides insight into the heterointerfacial design principle of next-generation negative electrodes for highly reversible metal batteries.
25 ENERGY STORAGE↗
A Modified Sand’s Time Incorporating Li-Ion Transport Across the SEI: Basis for Understanding Li Dendrite Formation and Li-Metal Battery Electrolyte Selection
Abstract Understanding the initiation of lithium dendrites remains elusive, largely due to the intricate role of the solid electrolyte interphase (SEI) which forms on the Li surface during electrodeposition. Many studies have utilized the classical Sand’s equation to estimate the onset time when lithium dendrites begin to form. The Sand’s equation provides the time when the cation (Li+) concentration at the electrode-electrolyte interface approaches zero under diffusion-limited conditions in galvanostatic Li electrodeposition. However, recent experimental studies have revealed that the observed lithium dendrite onset time deviates considerably from the Sand’s time. Here, we show that this deviation from classical theory is likely due to the transport of Li+ ions through the SEI - a transport limitation that is much more dominant in controlling dendrite formation. We develop a ‘modified’ Sand's equation, incorporating the SEI layer and the diffusional transport across it to predict Li dendrite onset times. To validate this approach, we conducted Li electrodeposition experiments at various current densities using two distinct organic electrolytes. Analysis of the results demonstrates that the modified Sand's equation provides a more accurate prediction of dendrite onset times, highlighting the importance of incorporating SEI into transport models of Li plating in next-generation rechargeable Li-metal batteries.
Ma, Yuanman (ORCID:0000000200444811)↗
Cell-Format-Dependent Mechanical Damage in Silicon Anodes
Strong binders can be counterproductive for silicon anodes. Here, we show that stresses from cycling Si-based electrodes can cause permanent stretching and wrinkling of the current collector. Furthermore, this deformation damages the electrode coating and accelerates cell aging due to the inactivation of Si domains and facilitation of Li plating. Interestingly, we demonstrate that the formation of wrinkles is size-dependent, being present in pouch cells but absent from coin cells. This size-dependent performance decay indicates that, in extreme cases, testing outcomes are highly dependent on scale and that the validation of battery materials may require testing at larger cell formats.
25 ENERGY STORAGE↗