Li Metal Batteries Research Articles

In Situ-Constructed Multifunctional Composite Anode with Ultralong-Life Toward Advanced Lithium-Metal Batteries.

Metallic lithium is the most competitive anode material for next-generation high-energy batteries. Nevertheless, the extensive volume expansion and uncontrolled Li dendrite growth of lithium metal not only cause potential safety hazards but also lead to low Coulombic efficiency and inferior cycling lifespan for Li metal batteries. Herein, a multifunctional dendrite-free composite anode (Li/SnS2) is proposed through an in situ melt-infusion strategy. In this configuration, the 3D cross-linked porous Li2S/Li22Sn5 framework facilitates the rapid penetration of electrolytes and accommodates the volume expansion during the repeated Li-plating process. Meanwhile, the lithiophilic Li2S phases with a low Li+ transport barrier ensure preferential Li deposition, effectively avoiding uneven electron distribution. Moreover, the Li22Sn5 electron conductors with appropriate Li+ bonding ability guarantee rapid charge transport and mass transfer. Most importantly, the steady multifunctional skeleton with sufficient inner interfaces (Li2S/Li22Sn5) in the whole electrode, not only realizes the redistribution of the localized free electron, contributing to the decomposition of Li clusters, but also induces a planar deposition model, thus restraining the generation of Li dendrites. Consequently, an unprecedented cyclability of over 6500h under an ultrahigh areal capacity of 10mAhcm-2 and a current rate of 20mAcm-2 is achieved for the prepared Li2S/Li22Sn5 composite anode. Moreover, the assembled Li/SnS2||LiFePO4 (LFP) pouch full-cells also demonstrate remarkable rate capability and a convincing cycling lifespan of more than 2000 cycles at 2 C.

Dual-Interphase-Stabilizing Sulfolane-Based Electrolytes for High-Voltage and High-Safety Lithium Metal Batteries.

High-voltage Li metal battery (HV-LMB) is one of the most promising energy storage technologies to achieve ultrahigh energy density. Nevertheless, electrolytes reported to date are difficult to simultaneously stabilize the Li metal anode and high-voltage cathode, especially without the assistance of expensive and corrosive high-concentration Li salts. Herein, a dual-interphase-stabilizing (DIS) and safe electrolyte that bypasses the high-concentration Li salt is reported. The electrolyte consists of high-flash-point sulfolane as solvent, molecular-orbital-engineered additives that enable stable B-F rich cathodic interphase, and unique C-F rich organic anodic interphase. The stable cycling of both Li metal anode and 4.75V-LiCoO2 cathode in the DIS electrolyte (> 500 cycles) is demonstrated. HV-LMB pouch cells of a high energy density (435Wh kg-1) can sustainably operate for more than 100 cycles. Moreover, the low cost and high thermal stability of the DIS electrolyte offer superior cost-effectiveness and safety for large-scale applications of HV-LMBs in the future.

Lithiophilic Protective Dual Layer Enabling Stable Electrodeposition of Lithium at High Current Density

Lithium (Li) is an ideal anode material for rechargeable batteries and thus manufacturing Li metal is crucial for the practical development of Li metal batteries. Electrodeposition is an efficient technique for producing ultrathin and scalable Li metal electrodes. However, the dendritic growth and the side reactions of Li with electrolyte during the electrodeposition are the main obstacles to overcome. In this study, we designed a pre-coated protective dual layer (PDL) composed of a poly(ethylene oxide)-based solid polymer electrolyte (SPE) and a polydopamine-coated cellulose membrane (PD-CM). The adhesive and ion-conductive SPE layer suppressed the growth of Li dendrites and side reactions with liquid electrolyte. The PD-CM layer with high porosity and lithiophilicity promoted a facile and uniform Li-ion flux. By applying the pre-coated PDL, Li was uniformly electrodeposited on the Ag-coated Cu at a high current density of 6 mA cm−2. The Li/LiFePO4 cell composed of an electrodeposited Li anode with PDL and a LiFePO4 cathode was assembled without an additional separator, and its cycling performance was evaluated. The cell initially delivered a high discharge capacity of 154.8 mAh g−1 at 45 °C and exhibited excellent cycling stability with a capacity retention of 97.0% after 200 cycles.

Trinitarian Design of Gradient Artificial Interphase Enables Colossal Granular Li Deposits for Stable Li-Metal Batteries.

The cycling lifespan of Li-metal batteries is compromised by the unstable solid electrolyte interphase (SEI) and the continuous Li dendrites, restricting their practical implementations. Given these challenges, establishing an artificial SEI holds promise. Herein, a trinitarian gradient interphase is innovatively designed through composite coatings of magnesium fluoride (MgF2), N-hexadecyltrimethylammonium chloride (CTAC), and polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) on Li-metal anode (LMA). Specifically, the MgF2/CTAC/PVDF-HFP SEI spontaneously forms a lithium fluoride (LiF)-rich PVDF-HFP-based SEI, along with lithium-magnesium (Li-Mg) alloy substrate as lithiophilic electronic conductor and positively charged CTAC during plating. Noticeably, the Li-Mg alloy homogenizes the distribution of electric field and reduce the internal resistance, while the electronically insulated LiF/PVDF-HFP composite SEI offers fast ion-conducting and mechanical flexibility, accommodating the volumetric expansion and ensuring stable Li-ion flux. Additionally, CTAC at the dendritic tip is pivotal for mitigating dendrites through its electrostatic shield mechanism. Innovatively, this trinitarian synergistic mechanism, which facilitates colossal granular Li deposits, constructs a dendrite-free LMA, leading to stable cycling performances in practical Li||LFP, popular Li||NCM811, and promising Li||S full cells. This work demonstrates the design of multifunctional composite SEI for comprehensive Li protection, thereby inspiring further advancements in artificial SEI engineering for alkali-metal batteries.

Isocyanurate‐Derivative Enables Highly Compatible Poly‐Dioxane Electrolyte for Dendrite‐Free Li Metal Batteries

AbstractThe Li+ transport kinetics and electrochemical stability of advanced solid‐state Li metal batteries (SLMBs) are seriously limited by the actual electrolyte compositions. Here, a novel polyether‐based electrolyte (PTGDOX) is presented through in situ co‐polymerization by integrating 1,3‐dioxane with a multifunctional 1,3,5‐triglycidyl isocyanurate additive. The isocyanurate group in PTGDOX not only provides abundant coordinating sites for Li+ transfer and restricts the movement of anions, but also prompts a beneficial inorganic‐rich solid electrolyte interface on the Li electrode. As a result, PTGDOX exhibits a remarkably increased ionic conductivity of 0.48 mS cm−1 at 30 °C and a reasonable Li‐ion transference number of 0.68, enabling the Li||Li symmetric cells to stably cycle for over 2000 h at 1 mAh cm−2. Meanwhile, the assembled Li||LiFePO4 exhibit a 97.4% capacity retention after 700 cycles at 3 C with excellent thermal stability. Moreover, PTGDOX also demonstrates excellent interfacial compatibility with high‐voltage LiNi0.8Co0.1Mn0.1O2 cathode. As such, this work provides a facile and accessible strategy for designing interface‐stable polymer electrolytes and achieving practical dendrite‐free SLMBs.

Facile self-assembled monolayer deposition on copper foil for high-performance lithium-metal batteries

Li metal is widely acknowledged as the optimal negative electrode material for high-energy-density Li rechargeable batteries. However, challenges arise owing to the formation of Li dendrites and poor surface stability, leading to reduced cycle life and energy efficiency, thereby limiting widespread application. In this study, we introduced a novel approach of a molecular single-layer surface modification onto a Cu foil using a self-assembled monolayer with hexamethyldisilane (HMDS) to enhance the performance of Li-metal electrodes. The deposition of a single molecular layer at the Å-level was achieved by a simple combination of precursor casting and heat treatment without greatly affecting the energy and power density. Furthermore, this process was both scalable and cost-effective, making it highly suitable for large-scale battery manufacturing. The molecular deposition of HMDS effectively mitigated electrolyte decomposition and promoted uniform Li deposition by enhancing the surface stability under repeated Li plating–stripping processes. Optical microscopy revealed the homogeneous Li plating even after extended cycling; the first cycle on the modified surface depicted uniform plating without blank spots owing to the reduced gas-phase by-products from electrolyte decomposition. Thus, HMDS modification greatly improved the cycle stability of Li-metal batteries by successfully mitigating polarization due to electrolyte decomposition. Such improvement improved the Coulombic efficiencies and enhanced the energy efficiency, especially over a wide current density range of 1–5 mA cm−2. Furthermore, full cells with LiFePO4 cathodes and HMDS-modified Cu foils exhibited extended cyclability with increased energy efficiencies.

Rhombohedral Li1-xZr2-xSbx(PO4)3 electrolytes with improved Li+ conductivity for high-performance solid-state Li-metal battery

Recent studies on solid electrolytes have promoted the development of solid-state Li-metal batteries (SSLBs). The NASICON-type LiZr2(PO4)3 (LZP) electrolyte has received less attention due to its low conductivity and the existence of several crystal forms, which have impeded the development of LZP-based materials for SSLBs. Herein, Li1-xZr2-xSbx(PO4)3 (LZSP) ceramics were synthesized by solid-state method, and the cycle performances of symmetrical cell and Li-metal battery using LZSP electrolyte were characterized for the first time. The Sb5+ doping stabilizes the rhombohedral phase at room temperature and results in distortions in the ZrO6 octahedron and PO4 tetrahedron, which lead to variations of bond length and bond angle. The room temperature total conductivity of Li0.94Zr1.94Sb0.06(PO4)3 (LZSP-0.06) increased to 6.53 × 10−5 S·cm−1. This rise can be attributed to a reduction of the Li+ ions transport barrier originated from variations of bond length, bond angle and Raman vibrations mode. The Li/LZSP-0.06/Li symmetrical cell maintains a stable cycle duration of 670 h at a current density of 0.12 mA cm−2. The specific capacity of Li/LZSP-0.06/LiFePO4 battery reaches 140.1 mAh g−1 at 0.5C and the coulombic efficiency is 99.8 %. This battery maintains 80 % capacity after 105 cycles. These results provide reference significance for the research on SSLBs using LZP-based electrolytes. In general, the Li0.94Zr1.94Sb0.06(PO4)3 ceramic appears to be a promising solid electrolyte for SSLBs.

Supramolecular polymer cross-linking gel electrolyte for highly stable quasi-solid-state lithium metal batteries

Lithium (Li) metal batteries have the advantage of high energy density, but the Li dendrites risk piercing the separator and causing a short circuit in the battery. Replacing the liquid electrolytes with gel electrolytes is considered an effective strategy to solve the issues. Herein, a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based gel electrolyte, improved with multifunctional supramolecular polymer (MSP), was prepared to enhance the cycling stability and energy density of quasi-solid-state Li metal batteries. The MSP addictive constructs a cross-linked network structure with PVDF-HFP matrix and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) through hydrogen bonding, improving the mechanical strength of the composite gel electrolyte (PH-10%MSP-GE) to against the growth of Li dendrites. Moreover, the pre-lithiated sulfonic acid groups, conductive polyether groups of MSP, and the attraction of TFSI– anions, promote the Li-ion transportation of the composite gel electrolyte. Finally, the Li||Li symmetric cell cycle stably for over 450 h. The Li||LiFePO4 full cell demonstrates a high energy density and excellent cycling stability for over 600 cycles, with a capacity retention rate of up to 98.7%. This work provides valuable insights into the preparation of multifunctional composite gel polymer electrolytes and competitive quasi-solid-state Li metal batteries.

Push-Pull Electrolyte Design Strategy Enables High-Voltage Low-Temperature Lithium Metal Batteries.

Lithium (Li) metal batteries hold significant promise in elevating energy density, yet their performance at ultralow temperatures remains constrained by sluggish charge transport kinetics and the formation of unstable interphases. In conventional electrolyte systems, lithium ions are tightly locked in the solvation structure, thereby engendering difficulty in the desolvation process and further exacerbating solvent decomposition. Herein, we propose a new push-pull electrolyte design strategy, utilizing molecular electrostatic potential (ESP) screening to identify 2,2-difluoroethyl trifluoromethanesulfonate (DTF) as an optimal cosolvent. Importantly, DTF exhibits a moderate ESP minimum (-21.0 kcal mol-1) to strike a balance between overly strong and overly weak Li ion affinity, which allows the sulfonyl group to effectively pull Li ions without disrupting the anion-rich solvation structure. Simultaneously, the difluoromethyl group, with a high ESP maximum (37.3 kcal mol-1), pushes solvent molecules via competitive hydrogen bonding. This design reconstructs existing solvation structures and expedites Li ion desolvation. Furthermore, fluorinated DTF demonstrates excellent stability at elevated voltage and facilitates the formation of robust inorganic-rich interphases. Impressively, rapid charge transfer kinetics can be achieved employing designed electrolyte, and the LiNi0.8Mn0.1Co0.1O2 (NMC811)||Li cells demonstrate excellent charge-discharge cycling stability with a high capacity exceeding 153 mAh g-1 even at -40 °C, retaining over 93% of initial capacity after 100 cycles under a 4.8 V charging cutoff. This work provides insights into the design of low-temperature electrolytes with a wide electrochemical window, advancing the development of batteries for extreme conditions.

Group transfer radical polymerization for the preparation of carbon-chain poly(α-olefins).

Radical polymerization is a powerful technique for producing a variety of polymeric materials. However, the chain transfer reaction impedes the formation of polymers from many common α-olefins such as propene and 1-butene using this method. Consequently, poly(α-olefins) are predominantly produced via coordination polymerization. To address this limitation, we have devised a strategy involving group transfer radical polymerization (GTRP) to facilitate the radical homopolymerization to access carbon-chain poly(α-olefins). This approach enables the precise construction of a diverse array of carbon-chain poly(α-olefins) with high molecular weights. Furthermore, by using nonconventional monomers, we extend the applicability of this technique to the copolymerization of α-olefins with acrylonitrile, paving the way for the synthesis of copolymers with different monomers. To investigate the properties of the polymers obtained by this method, one of the poly(α-olefins) is studied as an interphase layer material in anode-free Li metal batteries, and the results indicate the potential of the polymer in energy storage applications.

Designing a Refined Multi-Structural Polymer Electrolyte Framework for Highly Stable Lithium-Metal Batteries.

Rational structural designs of solid polymer electrolytes featuring rich interface-phase morphologies can improve electrolyte connection and rapid ion transport. However, these rigid interfacial structures commonly result in diminished or entirely inert ionic conductivity within their bulk phase, compromising overall electrolyte performance. Herein, a multi-component ion-conductive electrolyte was successfully designed based on a refined multi-structural polymer electrolyte (RMSPE) framework with uniform Li+ solvation chemistry and rapid Li+ transporting kinetics. The RMSPEis constructed via polymerization-induced phase separation based on a rational combination of lithiophilic components and rigid/flexible chain units with significant hydrophobic/hydrophilic contrasts. Further refined by coating a robust polymer network, this all-organic design endows a homogenous micro-nano porous structure, providing a novel framework favorable for rapid ion transport in both its soft interfacial and bulk phases. The RMSPE exhibited excellent ion conductivity of 1.91 mS cm-1 at room temperature and a high Li+ transference number of 0.7. Assembled symmetrical Li cells realized stable cycling for over 2400 h at 3.0 mA cm-2. LiFePO4 full batteries demonstrated a long lifespan of 3300 cycles with a capacity retention of 93.5% and stable cycling performance at -35 °C. This innovative design concept offers a promising perspective for achieving high-performance polymer-based Li metal batteries.

Molecular Design of Solid Polymer Electrolytes with Enthalpy-Entropy Manipulation for Li Metal Batteries with Aggressive Cathode Chemistry.

Solid polymer electrolytes (SPEs) with high ion conductivity, high Li+ transference number, and a wide electrochemical window are promising for the next-generation high-energy Li metal batteries (LMBs). Here we describe an enthalpy-entropy manipulation strategy enabling a class of polycarbonate-based copolymeric electrolytes (PCCEs) with regulated cation/anion solvation via a molecular design of the polymer backbone. By integrating a weakly solvating linear carbonate with another strongly solvating cyclic carbonate segment in the polymer backbone, the cation-dipole coordination for Li+ ions (with two types of carbonyl groups) is weakened (low enthalpy penalty) and nondirectional (high entropy penalty), which enables a weak solvation and rapid diffusion of Li+. We further introduce a bis-acrylamide-based cross-linking segment which, other than imparting high mechanical strength, exhibits dihydrogen bonding with the difluoro(oxalate) borate anions, which is strong (high enthalpy penalty) and directional (low entropy penalty), thus restricting the migration of anions. As a result, the PCCE delivers a high ionic conductivity of 0.66 mS cm-1 with a high Li+ transference number (0.76) at 25 °C, as well as high oxidation stability. By an in situ polymerization approach, the PCCE enables LMBs using high-nikel LiNi0.8Co0.1Mn0.1O2 cathodes with a high capacity retention of 82.2% over 800 cycles with a cutoff voltage of 4.5 V and further LMBs using aggressive LiNi0.5Mn1.5O4 cathodes with a 96.4% capacity retention over 300 cycles with a cutoff voltage of 5.0 V. The described enthalpy-entropy manipulation approach offers a unique perspective for the molecular design of high-performance SPEs for high-energy Li metal batteries.

Constructing Donor–Acceptor-Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li+ Migration in Quasi-Solid-State Battery

HighlightsDonor–acceptor-linked covalent organic framework (COF)-based electrolyte can not only fulfill highly-selective Li+ conduction, but also offer a crucial opportunity to understand the role of electronic density in quasi-solid-state Li metal batteries.Donor–acceptor-linked COF electrolyte results in Li+ transference number 0.83, high ionic conductivity 6.7 × 10–4 S cm−1 and excellent cyclic ability in Li metal batteries.In situ characterizations, density functional theory calculation and time-of-flight secondary ion mass spectrometry are adopted to expound the mechanism of the rapid migration of Li+ in the “donor–acceptor” electrolyte system.

Regulating the Manganese Valence State Improves the Kinetic Properties of Manganese‐Based Cathodes

AbstractManganese (Mn)‐based lithium (Li)‐ion batteries with high energy density and low cost have recently attracted considerable attention. One drawback of Mn‐based batteries is the severe capacity attenuation caused by the Jahn‐Teller effect, which distorts the crystal structure and reduces the kinetics of Li‐ion insertion/extraction in the cathodes. In this study, the Mn valence state is regulated on the surface of Mn‐based oxide particles and oxygen vacancies are introduced to facilitate rapid Li‐ion transport and charge storage by adding succinonitrile (SN) to Mn‐based cathodes. Because of the reaction between SN and Mn‐based cathode particles, the contents of Mn3+ ions and oxygen vacancies increase, leading to an improvement in the Li‐ion kinetic properties of the cathodes as well as a reduction in the dissolution of Mn from the cathodes. By regulating the Mn valence state, Li‐ion and Li metal batteries with LiMn2O4 or Li‐rich Mn‐based layered oxide cathodes show significantly enhanced discharge capacity and improved cyclic performance. This study demonstrates that regulating the valence state of Mn ions is an effective strategy for enhancing the electrochemical performance of Mn‐based Li batteries and that adding SN to the cathodes is a cost‐effective method for mass production.

Unveiling Cu Nanoparticles Formed During Li Deposition in Anode-Free Batteries.

Developing high-energy-density Li metal batteries is essential for sustainable progress, necessitating in-depth studies of complex battery reactions. The presence of metallic Cu impurities detrimentally impacts battery performance, leading to issues such as self-discharging and internal soft short-circuit. Nevertheless, their formation mechanism and structural characteristics have not been revealed clearly. Here the formation of single-crystalline Cu nanoparticles during the Li deposition process in anode-free cells was identified by transmission electron microscopy. Through investigation of the chemical state of Cu before and after Li deposition, the formation of Cu NPs was attributed to the reduction of the oxide layers formed on the surface of Cu current collectors. Additionally, it was observed that Cu nanoparticles can be formed inside of deposited Li metal. This work reveals the formation pathway and microstructural characteristics of Cu nanoparticles appearing during Li deposition, underscoring the importance of nanoscale investigations into the underlying battery reactions.

Interfacial challenges and recent advances of solid‐state lithium metal batteries

AbstractGrowing market demands on portable electronics, electric vehicles, and energy storage system calls for the development of high‐energy density lithium (Li) batteries. Li metal is considered as a promising anode material owing to their high capacity and low electrochemical potential. However, high reactivity of Li metal with conventional flammable liquid electrolytes easily forms Li dendrites, which may cause short‐circuit and even catching fire, obstructing the wide application of Li metal batteries. Although non−/less‐flammable solid electrolytes have replaced the conventional liquid electrolytes, solid‐state Li metal batteries (SSLMBs) suffer from lower Li+ conductivities, chemical/electrochemical incompatibilities toward Li metal, and inhomogeneous Li+ flux at the interfaces. Therefore, many researchers have devoted themselves to solve these problems. For a better understanding on the current issues and recent advances, this article provides (1) a review on various solid electrolytes with high Li+ conductivity and their interfacial issues in SSLMBs, and (2) recent progress in stabilization of the interface between the Li node and solid electrolytes, including an electrolyte modification (e.g., composition, additives) and introduction of an interlayer.

Few-layered graphene from cathodic exfoliation in binary solvents and application as a protective layer for lithium metal anodes

Electrochemical exfoliation is a top-down method recognized for its environmentally friendly and scalable approach for producing solution-processable graphene. Among its variation, cathodic exfoliation stands out for its potential in generating few-layer graphene with minimal defects. In this study, we developed a cathodic exfoliation method for graphite foil using a binary solvent system to produce graphene with a reduced number of layers. By employing a 0.1 M LiClO4 solution in a dimethyl sulfoxide and dimethyl carbonate solvents mixture at a 1:2 vol ratio, we enhanced the intercalation of solvated lithium ions into graphite, successfully exfoliating graphene with 5–6 layers. The exfoliated graphene exhibited a low defect density (ID/IG ∼0.05) and a C/O ratio of 33.2. Furthermore, when used as a coating on a separator, the exfoliated few-layered graphene (FLG) sheets demonstrated notable performance as a protective layer for Li metal anode in Li metal battery technology.

Dynamic interface layer enables epitaxial Li deposition for anode-free Li metal batteries

Anode-free Li-metal batteries are the best high-energy-density Li-ion batteries. However, the lack of active Li on anode side exacerbates dendritic Li growth, dead Li formation and parasitic reactions. In this study, we develop a lithiophilic Mg modification layer on Cu foil surface using magnetron sputtering. The epitaxial and dense Li deposition are manipulated, attributing to excellent Li affinity, favorable charge transfer and self-diffusion kinetics of the functional layer. Consequently, the coulombic efficiency of Li deposition/stripping on the Mg-coated Cu substrate remains at 83.7 % even after 50 cycles under 0.5 mA cm−2. Importantly, this approach enable the pouch cells paired with LiFePO4 cathodes to achieve a lifespan of over 70 cycles under 0.5 mA cm−2 without experiencing a significant capacity drop. This straightforward strategy is promising for developing long-lasting anode-free Li batteries.

Li2ZnCu3 modified Cu current collector to regulate Li deposition

Rationally designing a current collector that can maintain low lithium (Li) porosity and smooth morphology while enduring high‐loading Li deposition is crucial for realizing the high energy density of Li metal batteries, but it is still challengeable. Herein, a Li2ZnCu3 alloy‐modified Cu foil is reported as a stable current collector to fulfill the stable high‐loading Li deposition. Benefiting from the in‐situ alloying, the generated numerous Li2ZnCu3@Cu heterojunctions induce a homogeneous Li nucleation and dense growth even at an ultrahigh capacity of 12 mAh cm‐2. Such a spatial structure endows the overall Li2ZnCu3@Cu electrode with the manipulated steric hindrance and outmost surface electric potential to suppress the side reactions during Li stripping and plating. The resultant Li||Li2ZnCu3@Cu asymmetric cell preserves an ultrahigh average Coulombic efficiency of 99.2% at 3 mA cm‐2/6 mAh cm‐2 over 200 cycles. Moreover, the Li‐Li2ZnCu3@Cu||LiFePO4 cell maintains a cycling stability of 87.5% after 300 cycles. After coupling with the LiCoO2 cathode (4 mAh cm‐2), the cell exhibits a high energy density of 407.4 Wh kg‐1 with remarkable cycling reversibility at an N/P ratio of 3. All these findings present a doable way to realize the high‐capacity, dendrite‐free, and dense Li deposition for high‐performance Li metal batteries.

Li2ZnCu3 Modified Cu Current Collector to Regulate Li Deposition.

Rationally designing a current collector that can maintain low lithium (Li) porosity and smooth morphology while enduring high-loading Li deposition is crucial for realizing the high energy density of Li metal batteries, but it is still challengeable. Herein, a Li2ZnCu3 alloy-modified Cu foil is reported as a stable current collector to fulfill the stable high-loading Li deposition. Benefiting from the in situ alloying, the generated numerous Li2ZnCu3@Cu heterojunctions induce a homogeneous Li nucleation and dense growth even at an ultrahigh capacity of 12 mAh cm-2. Such a spatial structure endows the overall Li2ZnCu3@Cu electrode with the manipulated steric hindrance and outmost surface electric potential to suppress the side reactions during Li stripping and plating. The resultant Li||Li2ZnCu3@Cu asymmetric cell preserves an ultrahigh average Coulombic efficiency of 99.2 % at 3 mA cm-2/6 mAh cm-2 over 200 cycles. Moreover, the Li-Li2ZnCu3@Cu||LiFePO4 cell maintains a cycling stability of 87.5 % after 300 cycles. After coupling with the LiCoO2 cathode (4 mAh cm-2), the cell exhibits a high energy density of 407.4 Wh kg-1 with remarkable cycling reversibility at an N/P ratio of 3. All these findings present a doable way to realize the high-capacity, dendrite-free, and dense Li deposition for high-performance Li metal batteries.