Li Metal Batteries Research Articles

Exploring optimal Li composite electrode anodes for lithium metal batteries through in situ X-ray computed tomography

The uncontrolled Li dissolution/deposition dynamics and rapid Li pulverizations hinder the widespread deployment of Li metal batteries (LMB). Designing a Li composite electrode possessing a mechanically robust and lithiophilic three-dimensional (3D) framework represents a promising strategy to address these challenges. This study involves the preparation of three uniquely tailored Li-B-Mg composites using a combined metallurgical process of melting, casting, and rolling, along with the synergistic application of in situ X-ray computed tomography (CT) and post-mortem failure analysis to explore the most promising composite electrode candidate for LMBs. During the in-depth investigation, the optimal 70Li-B-Mg composite electrode stands out due to its robust skeleton fiber structure, uniform Li dissolution/deposition characteristics and high capacity of free-Li. Its promising prospects for enabling high-performance LMBs are showcased by the superior performance of the built Li||O2, Li||LiFePO4, Li||NCM622 and Li||NCM811 battery systems. This work offers a novel approach for exploring universally applicable and robust Li composite electrodes to realize high-performance LMBs using in situ CT analysis.

Towards ultra-stable and dendrite-suppressed Li-metal batteries: Ion-regulating graphene-modified separators

The practical application of metallic lithium (Li) anodes is hindered by nonuniform Li deposition/dissolution, as well as poor electrochemical reversibility during cycling. To address these challenges, surface modification of polymer separators with functional materials has been extensively explored. In this study, two distinct surface-modifying layers composed of MnOx and polydopamine (PDA) are applied to modify the surface of graphene-coated polypropylene separators (G@PP). Both MnOx and PDA, which are formed through the graphene layer, significantly enhance the intrinsic electrolyte wettability of G@PP, resulting in a homogeneous Li-ion flux. Furthermore, the lithiophilic properties revealed by DFT and COMSOL analyses synergize with the hydrophilic characteristics, resulting in a more stable electrochemical performance in Li-metal batteries (LMBs). The enhanced electrolyte permeability of the coating layer allows Li–Cu cells with MnOx-modified graphene-coated PP (MG@PP) and PDA-modified graphene-coated PP (PG@PP) separators to exhibit significantly improved cycle stability compared with Li–Cu cells with G@PP separators. Interestingly, Li–S cells equipped with MG@PP and PG@PP separators exhibit also enhanced electrochemical performance compared with Li–S cells with G@PP separators. These results highlight that surface engineering of separator-coating materials along with hydrophilic and lithiophilic materials enhances both long-term cycle stability and electrochemical kinetics in LMBs.

Anti-perovskite nitrides as chemically stable lithiophilic materials for highly reversible Li plating/stripping

Constructing structured anodes with lithiophilic materials has emerged as an essential strategy to stabilize Li deposition and accomplish highly reversible Li metal batteries (LMBs). Nevertheless, a lithiophilic material, which meets the requirements of low cost, excellent electronic conductivity and especially chemical stability, is still absent. Herein, we report the discovery of a new class of lithiophilic anti-perovskite nitrides MNNi3 (M=Zn, Cu, In) that not only are cost-effective and highly conductive, but also possess excellent stability against Li metal. More specifically, electrochemical tests in combination with density functional theory (DFT) calculations reveal that the lithiophilicity of MNNi3 arises from unique chemical/physical adsorption rather than the previously proposed alloying or conversion reaction mechanisms. The MNNi3@CC enabled symmetric cells exhibit better rate capability and longer cycle life than the cells with pure carbon cloth and Ni3N@CC. More importantly, the excellent electrochemical performances of MNNi3 anodes are also verified by ZnNNi3@CC in a LiFePO4 coupled full cell with minimal capacity degradation of 28% in 1500 cycles under the charge/discharge current of 1C. Beyond offering a new type of non-reactive lithiophilic materials to outstanding achieve battery performance, this study deepens the understanding of the lithiophilic nature of different metal nitrides, which paves a way for developing highly reversible lithium metal anode.

Pulse Charge Suppressing Dendrite Growth at Low Temperature by Rapidly Replenishing Lithium Ion on Anode Surface.

Dendrite growth of lithium (Li) metal anodes is considered as one of the most tough issues for Li metal batteries with a theoretically high energy density. This is attributed to the rapid exhaustion of Li ions at the electrode/electrolyte interface, which is even worse at low temperatures with poor diffusion kinetics of Li ions. Here, pulse charge with intermittent rest time during battery charging is proposed to handle the dendrite growth issue of Li metal anodes at low temperatures. The depleted Li ions near the interfaces can be rapidly replenished during the rest time, thus effectively suppressing the dendrites growth. Further investigation found that the large dendrites can be suppressed at the Li ion nucleation stage. The equivalent lifespan considering the rest time is proposed. At -10 °C, the lifespan of Li||Li batteries cycled under 3 mA cm-2 and 1 mAh cm-2 is increased from 24 h to equivalent 64 h. Li||LiNi0.5Co0.2Mn0.3O2 batteries with 80% capacity retention can be stably operated from 39 cycles to 56 cycles. This design presents an efficient and convenient strategy to regulate the deposition behaviors of Li metal anodes with a dendrite-free morphology.

Systematically evaluation of the cathodic performance of CrOBr with vacancies and partial substitutions on surface for Li metal batteries

Significant progress has been made in enhancing the kinetic and thermal stability of CrOBr. However, its full potential, especially regarding metal atom adsorption on its surface, remains largely unexplored. This study uses DFT to assess CrOBr's potential as a cathode material by evaluating its electronic structure and the interactions between metal atoms and the substrate, considering homologous substitution and vacancies. Although the investigation includes mixed cationic electrolytes (Li, Na, Mg, and Al), it primarily focuses on the behavior of Li, a common metal battery atom. Detailed calculations cover atom adsorption energy, diffusion energy barriers, band structures, density of states (DOS), and open circuit voltage (OCV) curves. The results show that Br vacancies enhance metal atom adsorption, reduce diffusion energy barriers, and maintain a high open-circuit voltage, making CrOBr a promising candidate for battery cathodes. Notably, the developed strategy for evaluating and improving CrOBr can also be applied to other electrode materials.

Concentrated precipitation electrolyte for reviving ultrathin lithium metal anode

Realizing high-performance lithium metal batteries requires the presence of a robust solid-electrolyte interphase (SEI) on the Li metal surface that forms before or during operation. Herein, high concentrations of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium nitrite (LiNO3) are employed to create a novel concentrated precipitation electrolyte (CPE) and form an inorganic-rich SEI. It is found that an ultrathin Li metal anode (thickness of 25 μ m) in the CPE remains highly reversible over 300 cycles with an average Coulombic efficiency (CE) of 97.21 % in an asymmetric Cu|Li cell. The CPE enables superior stability to the LiFePO4 (LFP) cathode at a high mass loading of ∼15 mg cm−2 and reaches a capacity retention of 82.8 % after 100 cycles with an average CE of 99.94 %. This study elucidates the mechanism of LiTFSI and LiNO3 in enhancing the physiochemical properties of the SEI surface layer. It is believed that this design concept and the findings can be broadened to optimize SEIs via electrolyte engineering for practical Li metal batteries.

Construction of flexible asymmetric composite polymer electrolytes for high-voltage lithium metal batteries with superior performance

The primary obstacle hindering the application of composite solid electrolytes lies in the varying demands posed by the Li metal anode and the cathode, which needs to be capable of suppressing dendrite growth and resisting high voltage simultaneously. In this work, a new asymmetric composite solid-state electrolyte prepared via electrospinning and in-situ polymerization is proposed to address these shortcomings. In this bilayer architecture, polyacrylonitrile (PAN) layer of high-voltage tolerance, polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) layer of robust mechanical strength and good compatibility towards Li-anode are constructed, and metal-organic-frameworks (MOFs) are pre-embedded within both layers. The unique design provides a wide electrochemical stability window meanwhile ensures uniform lithium deposition. Remarkably, it exhibits a superior lithium utilization of 41 mAh cm−2 using a lean polymer electrolyte precursor and a high critical current density of 2.2 mA cm−2 with a thickness of 40 μm. Beneficial from the formation of a self-adjustable gradient solid electrolyte interphase in the Li/PVDF-HFP interface, the asymmetric electrolyte endows Li||Li and Li||NCM811 cells with excellent cycling stability. Moreover, the solid-state pouch cell exhibits reliable operation under extreme conditions. This work provides inspiration for the design and fabrication of composite solid electrolytes for next-generation high-voltage Li metal batteries.

In Situ Analysis of Interfacial Morphological and Chemical Evolution in All-Solid-State Lithium-Metal Batteries.

In situ analysis of Li plating/stripping processes and evolution of solid electrolyte interphase (SEI) are critical for optimizing all-solid-state Li metal batteries (ASSLMB). However, the buried solid-solid interfaces present a challenge for detection which preclude the employment of multiple analysis techniques. Herein, by employing complementary in situ characterizations, morphological/chemical evolution, Li plating/stripping dynamics and SEI dynamics were directly detected. As a mixed ionic-electronic conducting interface, Li|Li10GeP2S12 (LGPS) performed distinct interfacial morphological/chemical evolution and dynamics from ionic-conducting/electronic-isolating interface like Li|Li3PS4 (LPS), which were revealed by combination of in situ atomic force microscopy and in situ X-ray photoelectron spectroscopy. Though Li plating speed in LGPS was higher than LPS, speed of SSE decomposition was similar and ~85 % interfacial SSE turned into SEI during plating and remained unchanged in stripping. To leverage strengths of different SSEs, an LPS-LGPS-LPS sandwich electrolyte was developed, demonstrating enhanced ionic conductivity and improved interfacial stability with less SSE decomposition (25 %). Using in situ Kelvin probe force microscopy, Li-ion behavior at interface between different SSEs was effectively visualized, uncovering distribution of Li ions at LGPS|LPS interface under different potentials.

In Situ Analysis of Interfacial Morphological and Chemical Evolution in All‐Solid‐State Lithium‐Metal Batteries

AbstractIn situ analysis of Li plating/stripping processes and evolution of solid electrolyte interphase (SEI) are critical for optimizing all‐solid‐state Li metal batteries (ASSLMB). However, the buried solid‐solid interfaces present a challenge for detection which preclude the employment of multiple analysis techniques. Herein, by employing complementary in situ characterizations, morphological/chemical evolution, Li plating/stripping dynamics and SEI dynamics were directly detected. As a mixed ionic‐electronic conducting interface, Li|Li10GeP2S12 (LGPS) performed distinct interfacial morphological/chemical evolution and dynamics from ionic‐conducting/electronic‐isolating interface like Li|Li3PS4 (LPS), which were revealed by combination of in situ atomic force microscopy and in situ X‐ray photoelectron spectroscopy. Though Li plating speed in LGPS was higher than LPS, speed of SSE decomposition was similar and ~85 % interfacial SSE turned into SEI during plating and remained unchanged in stripping. To leverage strengths of different SSEs, an LPS‐LGPS‐LPS sandwich electrolyte was developed, demonstrating enhanced ionic conductivity and improved interfacial stability with less SSE decomposition (25 %). Using in situ Kelvin probe force microscopy, Li‐ion behavior at interface between different SSEs was effectively visualized, uncovering distribution of Li ions at LGPS|LPS interface under different potentials.

New Nitrate Additive Enabling Highly Stable and Conductive SEI for Fast‐Charging Lithium Metal Batteries

AbstractPolyester‐based electrolytes formed via in situ polymerization, have been regarded as one of the most promising solid electrolyte systems. Nevertheless, it is still a great challenge to address the issue of their high reactivity with metallic lithium anode by optimizing the components and properties of solid electrolyte interphase (SEI). Herein, a new class of N‐containing additive, isopropyl nitrate (ISPN) that can be miscible with ester solvents is demonstrated, and a chemically stable and ion‐conductive LiF‐Li3N composite SEI is constructed. In addition, ISPN can induce the formation of anion‐enriched solvation structures and reduces the desolvation barrier of Li+, resulting in fast transport of Li+. With the addition of ISPN, ionic conductivity of the electrolyte has nearly doubled, reaching as high as 5.3 × 10−4 S cm−1. What's more, the LiFePO4 (LFP)|ISPN‐PTA|Li cell exhibits exceptional cycle stability and fast charging capabilities, maintaining stable cycling for 850 cycles at 10 C rate. Even when paired with the high‐voltage cathode, the LiNi0.6Co0.2Mn0.2O2 (NCM622)|ISPN‐PTA|Li cell achieves an impressive capacity retention of 97.59% after 165 cycles at 5 C. This study offers a novel approach for ester‐based polymer electrolytes, paving the way toward the development of stable and high‐energy Li metal battery technologies.

Horizontal Lithium Electrodeposition on Atomically Polarized Monolayer Hexagonal Boron Nitride.

Both uncontrolled Li dendrite growth and corrosion are major obstacles to the practical application of Li-metal batteries. Despite numerous attempts to address these challenges, effective solutions for dendrite-free reversible Li electrodeposition have remained elusive. Here, we demonstrate the horizontal Li electrodeposition on top of atomically polarized monolayer hexagonal boron nitride (hBN). Theoretical investigations revealed that the hexagonal lattice configuration and polarity of the monolayer hBN, devoid of dangling bonds, reduced the energy barrier for the surface diffusion of Li, thus facilitating reversible in-plane Li growth. Moreover, the single-atom-thick hBN deposited on a Cu current collector (monolayer hBN/Cu) facilitated the formation of an inorganic-rich, homogeneous solid electrolyte interphase layer, which enabled the uniform Li+ flux and suppressed Li corrosion. Consequently, Li-metal and anode-free full cells containing the monolayer hBN/Cu exhibited improved rate performance and cycle life. This study suggests that the monolayer hBN is a promising class of underlying seed layers to enable dendrite- and corrosion-free, horizontal Li electrodeposition for sustainable Li-metal anodes in next-generation batteries.

Phase-field investigation of dendrite suppression strategies for all-solid-state lithium metal batteries

All-solid-state Li metal batteries are widely considered as the most promising technologies to realize the increasing safety and capacity requirements for the next generation of Li batteries. However, it is experimentally demonstrated that the penetration of stiff solid electrolytes by Li dendrites seems even more severe than that of liquid electrolytes and the abnormal failure behavior of soft Li metal penetrating hard SEs is quite elusive. In the present work, a multi-coupling phase field model of Li electrodeposition is further developed to incorporate the elasto-plastic mechanical behavior and the significant size effect of Li metal. Then, the established approach is utilized to specifically evaluate the different mechanisms of Li electrodeposition and stripping in liquid electrolytes and hard solid electrolytes with various governing factors including applied voltage, external stress, ionic conductivity, SEI inhomogeneity and interfacial porosity. Especially, we summarize the accurate quantification of the regularity of external stress mechanisms which determine whether the external stress can either promote or demote the nonuniformity of Li/ solid electrolytes interface. This research provides a theoretical perspective of mechanical mechanism to reveal the conflict of experimental optimization strategies and may be instructive for the Li/ solid electrolytes interface design of all-solid-state Li metal batteries.

Soy protein as a dual-functional bridge enabling high performance solid electrolyte for Li metal batteries

A high-performance solid electrolyte is critical for all-solid-state Li metal batteries which possess good safety and high energy densities. In this study, inspired by the unique ionic transport function and excellent adhesive properties of natural proteins, we successfully generated a novel solid electrolyte by applying soy protein as a dual-functional bridge to enable additional ion-conduction pathways and improve mechanical performance. The solid electrolyte with soy protein that interacts with both SiO2 nanofabrics and polypolyethylene oxide (PEO) exhibits high ionic conductivity of 10−5 S cm−1 (vs. 10−6 S cm−1 of SiO2/PEO), improved Li+ transference number of 0.550 (vs. 0.446 of SiO2/PEO), high Young's modulus of 1.862 MPa (vs. 0.356 MPa of SiO2/PEO) and excellent flexibility. As a result, the solid-state batteries with LiFePO4 as cathode demonstrate a stable discharge capacity. This work provides a new strategy to advance the performance of solid electrolytes for achieving long-lifespan all-solid-state batteries.

In-situ analysis of cathode and anode impedances to probe the performance degradation of lithium–sulfur batteries

Improving the performance of Li-metal batteries with sulfur cathodes while maintaining high sulfur loading (>4 mg cm−2) and low electrolyte-to-sulfur ratio (<10 mg μL−1) is a significant challenge. These conditions often result in poor battery cycle life and sudden capacity failure during charge-discharge processes. To address this challenge, we investigate Li–S batteries in a three-electrode (3E) configuration, utilizing optimized materials and geometries for the reference electrode. This configuration allows us to independently track the in-situ variations in cathode and anode resistances, along with the electrode potential difference, unveiling the root causes of abrupt battery failure during cycling. Our 3E approach uncovers previously unnoticed distortion phenomena in the electrochemical impedance spectra of both the cathode and anode, providing essential indicators of imminent micro-short circuiting. Supported by simulations using the finite element method and equivalent circuit analysis software, these insights clarify that the primary reason for battery failure is the growth of Li dendrites and their subsequent contact with the cathode, rather than a sudden increase in cell impedance. By substituting traditional Li foil with a specially designed Li anode less susceptible to Li dendrite growth, we achieve reduced anode resistance and improved battery capacity and cycle life stability. This research reveals the potential of the 3E configuration for precise in-situ impedance monitoring, which is valuable for devising strategies to enhance cycle stability.

The construction of concentration gradient inducing low resistance for Li7La3Zr2O12-based thermal battery

Ta-doped Li7La3Zr2O12 (LLZTO) electrolytes not only show considerable potentials in solid-state Li metal batteries, but also display great possibility in thermal battery working at elevated temperature with high security. However, the great resistance of the single cell has hindered its practical application for the large interfacial resistance and high Li+ transport pressure. Herein, a new effective approach to construct intense interface and distinct concentration gradient of O2– and Cl- through pre-discharge state at small current (PDS) was successfully employed to decline the resistance of the LLZTO-based thermal battery under thermal and electric field. The formed intense interface is conductive under the thermal field than the pristine poor contact at the interface. The obtained significant and distinct concentration gradient of O2– and Cl- under the joint function of thermal and electric field achieves larger effective charge transport after PDS, suggesting lower polarization and resistance of the single cell owing to the relaxing burden of Li+. Consequently, the resistance of the single cell decreases to 2.4 Ω from 3.7 Ω, coming with larger specific energy at 500 °C (from 444 Wh kg−1 to 1038 Wh kg−1). This work provides a facile strategy to decline the resistance of the battery through the construction of concentration gradient, which is also promising to be used for battery whose materials are sensitive to electric or thermal field.

Garnet-Based Solid Li-Metal Batteries Operable under High External Pressure with HCOOH-Induced Electron-Blocking and Lithiophilic Interlayer.

Despite good compatibility with Li metal, garnet solid electrolytes suffer from severe electron-attack-induced Li-metal penetration and large interfacial resistance. Here, a formic acid (HCOOH)-induced electron-blocking and lithiophilic interlayer is created via a spontaneous reaction with surface Li2CO3 contamination on the garnet electrolyte (LLZTO) pellet. Unlike previous methods that involved immersing LLZTO in acidic solutions, this study employs a volatile small-molecule organic acid that is easily removable, condensed, and recyclable, thus circumventing the environmental drawbacks associated with acid waste. The Li symmetric cell assembled with HCOOH-treated LLZTO exhibits a low interfacial impedance (3 Ω cm2) and a high critical current density (1.7 mA cm-2) at room temperature, enabling the cell to cycle continuously for over 1000 h at 0.2 mA cm-2. Furthermore, under a stacking pressure of 2 MPa, stable lithium plating/stripping was achieved at a current density of 0.3 mA cm-2 with the assistance of HCOOH treatment. Additionally, the battery paired with a LiFePO4 cathode delivers a high capacity of 151.7 mAh g-1 at 1 C and maintains 88.5% of the initial capacity after 500 cycles, suggesting the feasibility of this interfacial engineering strategy for garnet-based solid Li-metal batteries.

Mixed conductive layer formed by ZnO–graphite conversion–reaction enables dendrite–free all–solid–state lithium metal batteries

Largescale application of sulfide solid electrolytes (SSEs) in nextgeneration allsolidstate Limetal batteries is currently limited by an unstable Li/SSEs interface and fast Lidendrite formation/growth during charging. This work has addressed these challenges by introducing ZnO and graphite composite to the surface of lithium metal, creating a multifunctional conductive composite layer with Ligraphite and LiZn alloy. This interfacial layer enhances Liion transport and minimizes side reactions at the Li/SSEs interface. As a result, the interfacial resistance of Li/SSEs decreased from 14.2 to 11.7 Ω cm², and the critical current density (CCD) significantly improved from 0.8 to 2.7 mA cm2. Moreover, the protective layer enables stable cycling of both Li/Li symmetric and LiNi0.8Mn0.1Co0.1O2/Li cells even at high current densities.

Charge-Delocalized Triptycene-Based Ionic Porous Organic Polymers as Quasi-Solid-State Electrolytes for Lithium Metal Batteries.

Ideal solid electrolytes for lithium (Li) metal batteries should conduct Li+ rapidly with low activation energy, exhibit a high Li+ transference number, form a stable interface with the Li anode, and be electrochemically stable. However, the lack of solid electrolytes that meet all of these criteria has remained a considerable bottleneck in the advancement of lithium metal batteries. In this study, we present a design strategy combining all of those requirements in a balanced manner to realize quasi-solid-state electrolyte-enabled Li metal batteries (LMBs). We prepared Li+-coordinated triptycene-based ionic porous organic polymers (Li+@iPOPs). The Li+@iPOPs with imidazolates and phenoxides exhibited a high conductivity of 4.38 mS cm-1 at room temperature, a low activation energy of 0.627 eV, a high Li+ transference number of 0.95, a stable electrochemical window of up to 4.4 V, excellent compatibility with Li metal electrodes, and high stability during Li deposition/stripping cycles. The high performance is attributed to charge delocalization in the backbone, mimicking the concept of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), which facilitates the diffusion of coordinated Li+ through the porous space of the triptycene-based iPOPs. In addition, Li metal batteries assembled using Li+@Trp-Im-O-POPs as quasi-solid-state electrolytes and a LiFePO4 cathode showed an initial capacity of 114 mAh g-1 and 86.7% retention up to 200 cycles.

In Situ Formed Gel Polymer Electrolytes Enable Stable Solid Electrolyte Interface for High-Performance Lithium Metal Batteries.

Carbonate-based electrolytes show distinct advantages in high-voltage cathodes but generate nonuniform and mechanically fragile solid-electrolyte interphase (SEI) in lithium (Li) metal batteries. Herein, we propose a LiF-rich SEI incorporating an in situ polymerized poly(hexamethylene diisocyanate)-based gel polymer electrolyte (GPE) to improve the homogeneity and mechanical stability of SEI. Fluoroethylene carbonate (FEC) as a fluorine-based additive for building LiF-rich SEI on Li metal electrodes. With this strategy, the assembled Li symmetric batteries cycled stably for 700 h, and the formation of byproducts on the Li electrode surface was significantly inhibited. The Li/LiFePO4 battery delivered significant capacity retention (91% retention after 800 cycles) at 1 C. With high-voltage LiNi0.8Co0.1Mn0.1O2 (NCM811) as cathode, the Li/GPE-FEC/NCM811 cell delivered a discharge capacity of 168.9 mAh g-1 with a capacity retention of 82% after 300 cycles at 0.5 C. From the above, the work could assist the rapid development of high-energy-density rechargeable Li metal batteries toward remarkable performance.

High-Throughput Combinatorial Analysis of the Spatiotemporal Dynamics of Nanoscale Lithium Metal Plating.

The development of Li metal batteries requires a detailed understanding of complex nucleation and growth processes during electrodeposition. In situ techniques offer a framework to study these phenomena by visualizing structural dynamics that can inform the design of uniform plating morphologies. Herein, we combine scanning electrochemical cell microscopy (SECCM) with in situ interference reflection microscopy (IRM) for a comprehensive investigation of Li nucleation and growth on lithiophilic thin-film gold electrodes. This multimicroscopy approach enables nanoscale spatiotemporal monitoring of Li plating and stripping, along with high-throughput capabilities for screening experimental conditions. We reveal the accumulation of inactive Li nanoparticles in specific electrode regions, yet these regions remain functional in subsequent plating cycles, suggesting that growth does not preferentially occur from particle tips. Optical-electrochemical correlations enabled nanoscale mapping of Coulombic Efficiency (CE), showing that regions prone to inactive Li accumulation require more cycles to achieve higher CE. We demonstrate that electrochemical nucleation time (tnuc) is a lagging indicator of nucleation and introduce an optical method to determine tnuc at earlier stages with nanoscale resolution. Plating at higher current densities yielded smaller Li nanoparticles and increased areal density, and was not affected by heterogeneous topographical features, being potentially beneficial to achieve a more uniform plating at longer time scales. These results enhance the understanding of Li plating on lithiophilic surfaces and offer promising strategies for uniform nucleation and growth. Our multimicroscopy approach has broad applicability to study nanoscale metal plating and stripping phenomena, with relevance in the battery and electroplating fields.