Uncontrollable Dendrite Growth Research Articles

Customizing Component Regulated Dense Heterointerfaces for Crafting Robust Lithium‐Sulfur Batteries

AbstractLithium–sulfur (Li–S) batteries hold great promise for the next‐generation energy storage system. However, their commercial applications are severely hindered by myriads of drawbacks such as poor electrical conductivity of sulfur, sluggish redox reaction kinetics of sulfur species, “shuttling effect” of soluble lithium polysulfides (LiPSs) and uncontrollable dendritic Li growth. Herein, it is conceptually demonstrated that sluggish conversion kinetics of LiPSs is markedly stimulated by exquisite heterointerface modulation at nanoscale level over transition metal carbides and nitrides. In this scenario, N‐doped carbon coupled with molybdenum nitride/carbide (Mo2N‐MoC/NC) hybrid nanocomposites are designed through a one‐step carbonization‐nitridation process, wherein component regulation induced dense heterointerfaces are in situ produced. Benefiting from high electrical conductivity, strong chemical adsorption, and superior catalytic activity afforded by dense heterointerfaces, the Mo2N‐MoC/NC modified separators significantly restrict the soluble LiPSs shuttling and simultaneously suppress the Li dendrite generation. The assembled Li–S batteries with Mo2N‐MoC/NC modified separators exhibit remarkable electrochemical performance. Integrated experimental and theoretical results substantiate the boosted chemisorption and catalytic conversion of LiPSs endowed by such dense heterointerfaces. The work will open a new vista for rationally constructing multifarious heterostructured materials for the communities of Li‐S batteries.

A Semi-solid Zinc Powder-based Slurry Anode for Advanced Aqueous Zinc-ion Batteries.

The booming of aqueous zinc-ion batteries (AZIBs) draws the researchers' attention to issues of zinc metal anodes, such as uncontrollable dendrite growth, corrosion, and volume effects. Zinc powder anode is more suitable for the industrial application of AZIBs than the widely used zinc foil anode due to its low cost, tunability and processability. However, the related solutions are rarely studied because the above issues of zinc metal anode are more serious in zinc powder anode. Herein, for the first time, we design a semi-solid zinc slurry anode consisting of zinc powder and zincophilic tin additive dispersed in a conductive elastic rheological network. Zinc can be deposited homogeneously on the dispersed tin particles, which avoids agglomerative zinc deposition and alleviates volume change during repeated zinc stripping/plating. Moreover, the practical application of the full cell with slurry is very promising since its operating life can be easily extended by facile slurry renewal.

A Semi‐solid Zinc Powder‐based Slurry Anode for Advanced Aqueous Zinc‐ion Batteries

AbstractThe booming of aqueous zinc‐ion batteries (AZIBs) draws the researchers’ attention to issues of zinc metal anodes, such as uncontrollable dendrite growth, corrosion, and volume effects. Zinc powder anode is more suitable for the industrial application of AZIBs than the widely used zinc foil anode due to its low cost, tunability and processability. However, the related solutions are rarely studied because the above issues of zinc metal anode are more serious in zinc powder anode. Herein, for the first time, we design a semi‐solid zinc slurry anode consisting of zinc powder and zincophilic tin additive dispersed in a conductive elastic rheological network. Zinc can be deposited homogeneously on the dispersed tin particles, which avoids agglomerative zinc deposition and alleviates volume change during repeated zinc stripping/plating. Moreover, the practical application of the full cell with slurry is very promising since its operating life can be easily extended by facile slurry renewal.

Surface Bromination of Lithium‐Metal Anode for High Cyclic Efficiency

AbstractLithium‐metal batteries suffer from short cycle life and poor safety due to uncontrolled dendrite growth at Li anodes. An advanced solid‐electrolyte interphase (SEI) with homogeneous chemical composition and physical structure holds great promise to address the issues. Herein, a new surface bromination approach is proposed for stabilizing SEI of Li anode via a scalable dip‐coating method. A lithium bromide‐enriched SEI is readily created on Li metal from chemical passivation by bromooctane. In‐situ optical microscopy reveals the crucial role of LiBr in inhibiting dendritic Li growth. The mechanistic investigations suggest the crystal facet (111) of LiBr provides high adsorption energy and low diffusion barriers for Li+ ions. The incorporation of LiBr into SEI guarantees the stable cycling of Li irrespective of with ether or carbonate electrolytes, and the SEI is endurable at extremely low or high temperatures. The symmetric cell of the LiBr modified Li delivers a long lifespan of 2400 h with an overpotential less than 15 mV at 0.5 mA cm‐2, 1 mAh cm‐2. When paired with commercial cathodes, decent cycling retention and rate capability are available as well. This work demonstrates a feasible strategy for the development of stable Li‐metal batteries.

Hexachloro-1,3-butadiene as a Functional Additive for Constructing an Efficient Solid Electrolyte Interface Layer for Long-Life Stable Li Anodes.

Lithium (Li) metal is considered as one of the attractive anodes for next-generation high-energy-density batteries due to its ultrahigh theoretical specific capacity and low potential. However, many great challenges including uncontrolled dendrite growth and undesired side reactions during repeated cycling still seriously hinder its practical application in Li metal secondary batteries. Herein, we report the hexachloro-1,3-butadiene (HCBD) molecule as a functional additive to stabilize the Li anode by forming a stable solid electrolyte interface (SEI) layer with high Li ion conductivity via in situ surface and electrochemical reactions. Density functional theory calculations demonstrate that HCBD can preferentially react with the Li anode, which generates an ionic conducting species (LiCl) into an SEI layer. The LiCl-rich SEI layer effectively regulates Li+ deposition/stripping kinetics and then induces uniform nucleation of Li+ and reduces the side reactions between the Li anode and electrolyte. With an optimal amount of HCBD in an ether-based electrolyte, an excellent cycling lifespan (7000 h) was achieved with a low hysteresis voltage of ∼10 mV at 1.0 mA cm-2 in a Li||Li symmetrical cell. Furthermore, the LiFePO4-based cell with the additive-functionalized Li anode displays obviously improved cycling stability (with a high specific capacity of 141.1 mAh g-1 after 350 cycles at 1 C).

Single‐atom electrocatalysts for lithium–sulfur chemistry: Design principle, mechanism, and outlook

AbstractLithium–sulfur batteries (LSBs) have been regarded as one of the promising candidates for the next‐generation “lithium‐ion battery beyond” owing to their high energy density and due to the low cost of sulfur. However, the main obstacles encountered in the commercial implementation of LSBs are the notorious shuttle effect, retarded sulfur redox kinetics, and uncontrolled dendrite growth. Accordingly, single‐atom catalysts (SACs), which have ultrahigh catalytic efficiency, tunable coordination configuration, and light weight, have shown huge potential in the field of LSBs to date. This review summarizes the recent research progress of SACs applied as multifunctional components in LSBs. The design principles and typical synthetic strategies of SACs toward effective Li–S chemistry as well as the working mechanism promoting sulfur conversion reactions, inhibiting the lithium polysulfide shuttle effect, and regulating Li+nucleation are comprehensively illustrated. Potential future directions in terms of research on SACs for the realization of commercially viable LSBs are also outlined.

Uniform Zn2+ distribution and deposition regulated by ultrathin hydroxyl-rich silica ion sieve in zinc metal anodes

Recently, the design of zinc metal anodes with high Coulombic efficiency and long lifespan remains a huge challenge due to the occurrence of uncontrollable dendrites growth and side reactions. Herein, a hydroxyl-decorated in-plane micro-mesoporous silica nanosheet is reported as ion sieve which can effectively regulate the plating/stripping behavior of zinc ion, ensuring uniform Zn2+ distribution and deposition. According to the COMSOL simulations and DFT calculations, the well-ordered micro-mesopores serves as the ion channels to homogenize the Zn-ion flux distribution and the hydroxyl group decreases the affinity of ion sieve to Zn which is beneficial to the planar Zn deposition. Thanks to the presence of the silica ion sieve, the assembled Zn//Zn cells demonstrates an extremely long cycle lifespan of over 3400 and 2500 h at 1 and 10 mA cm−2 respectively, which is approximately 25 and 20 times that of bare Zn//Zn cells. Impressively, the constructed Zn//NaV3O8·1.5H2O full cells and Zn//AC hybrid capacitors operates steadily for more than 1500 and 8300 (capacity retention of 100%) cycles even under high cathode loading of 5.8 and 31 mg cm−2, respectively. Moreover, this strategy can be conveniently extended to lithium metal anodes, suggesting its high versatility in inhibiting dendrite growth in metal anodes.

Advances in Nanofibrous Materials for Stable Lithium-Metal Anodes.

Lithium metal is regarded as the most potential anode material for improving the energy density of batteries due to its high specific capacity and low electrode potential. However, the practical application of lithium-metal anodes (LMAs) still faces severe challenges such as uncontrollable dendrites growth and large volume expansion. The development of functional nanomaterials has brought opportunities for the revival of LMAs. Among them, nanofibrous materials show great application potential for LMAs protection due to their distinct functional and structural features. Here, the latest research progress in nanofibrous materials for LMAs is systematically outlined. First, the problems existing in the practical application of LMAs are analyzed. Then, prospective strategies and recent research progress toward stable LMAs based on nanofibrous materials are summarized from the aspects of artificial protective layers, three-dimensional frameworks, separators, and solid-state electrolytes. Finally, the future development of nanofibrous materials for the protection of lithium-metal batteries is summarized and prospected. This review establishes a close connection between nanofibrous materials and LMA modification and provides insight for the development of high-safety lithium-metal batteries.

Lithiophilic and conductive framework of 2D MoN nanosheets enabling planar lithium plating for dendrite-free and minimum-volume-change lithium metal anodes

Lithium (Li) is a promising anode for high-energy rechargeable batteries but its practical implementation is impeded by uncontrollable dendrite growth and huge volume changes. Herein, we report a dendrite-free Li composite anode with minimum volume change, which is composed of 3D interpenetrating Li and lithiophilic MoN nanosheets prepared by mechanical rolling and folding. The conductive 2D MoN nanosheets boasting excellent lithiophilic affinity and small lattice mismatch with Li induce planar Li plating therefore suppressing dendrite growth along the perpendicular direction. The MoN nanosheets interwoven framwork provides abundant Li accommodation sites and the horizontally plated Li fills the nanoscale gaps between the MoN nanosheets, thus minimizing volume change during cycling. Li3N generated in situ by the surface reaction between MoN and Li enhances the ionic conductivity and interface stability. The Li-MoN anode shows a low Li plating overpotential of 15.0 mV and excellent stability for 2,500 h at 1 mA cm−2. Paired with the LiFePO4 cathode, the full cell shows 99.7 % Coulombic efficiency and 87.7 % capacity retention after 650 cycles at 170 mA g−1. The results provide insights into the design of 3D host enabling planar Li plating for dendrite-free and minimum-volume-change Li metal anodes.

In Situ Construction of Composite Artificial Solid Electrolyte Interphase for High-Performance Lithium Metal Batteries.

Lithium metal is considered as the most promising anode material for high energy density secondary batteries due to its high theoretical specific capacity and low redox potential. However, poor interfacial stability and uncontrollable dendrite growth seriously hinder the commercial application of Li metal anodes. Herein, we constructed a composite artificial solid-electrolyte interphase (ASEI) utilizing the in situ reaction between polyacrylic acid (PAA)/stannous fluoride (SnF2) and lithium metal, which spontaneously generates LiPAA, LiF, and Li5Sn2 alloys. The in situ formed LiPAA as a flexible matrix can accommodate the volume change of the lithium anode. Meanwhile, LiF and Li5Sn2 play the roles for improving the mechanical properties and boosting Li-ion flux in the interfacial layer, respectively. Benefiting from the ingenious design, the PAA-SnF2@Li anodes remain stable and dendrite-free morphology in symmetric cells for over 2000 h and exhibit excellent cycling stability in high-area loading (10.52 mg cm-2) Li||LiFePO4 full cells with a N/P of 1.68, which endures only 0.11% average capacity decay per cycle in 200 cycles. This simple and low-cost method supplies a route for the commercial application of lithium metal anodes with fresh eyes.

Developing a high-performance aqueous zinc battery with Zn2+ pre-intercalated V3O7·H2O cathode coupled with surface engineered metallic zinc anode

• Zn 2+ intercalation capacity in V 3 O 7 ,nH 2 O could be significantly increased with Zn(II) chemical preinsertion. • Nanocarbon derived from candle shoot has been employed as artificial SEI to protect metallic Zn anode. • Nano carbon as SEI reduce the Zn 2+ plating/stripping overpotential and regulates dendrite less Zn 2+ plating. • C@Zn//Zn-V 3 O 7 ·H 2 O full cell showed improved cycling performance over Zn//Zn-V 3 O 7 ,nH 2 O. Herein we demonstrate a high-performance full cell aqueous zinc ion battery with structurally engineered V 3 O 7 ·H 2 O cathode and surface modified metallic zinc anode. We demonstrate that the capacity, rate performance and stability of V 3 O 7 ·H 2 O cathode can be significantly improved via Zn 2+ pre-intercalation, which acts as a pillaring agent to stabilize the cathode against structural degradation. The pre-intercalated V 3 O 7 ·H 2 O cathode showed an improved specific capacity (404 mAh/g at 0.1 A/g) and rate capability (235 mAh/g at 2 A/g), which was much higher than the pristine V 3 O 7 ·H 2 O, which showed specific capacity of 316 mAh/g and 141 mAh/g at 0.1 A/g and 2 A/g, respectively. Further we demonstrate that the Zn 2+ plating stripping overpotential and the uncontrollable dendrite growth at the metallic zinc anode can be significantly reduced with surface engineering of metallic zinc with a thin layer of carbon coating. We followed a simple and economical approach to obtain the nanocarbon from candle shoot, which could be coated uniformly onto the metallic zinc with controllable thickness. We demonstrate the efficacy of the C@Zn as anode by coupling it with both Zn-V 3 O 7 ·H 2 O and V 3 O 7 ·H 2 O cathode, which showed much improved cycling stability compared to that of unprotected metallic zinc.

Facile design of alloy-based hybrid layer to stabilize lithium metal anode

Lithium (Li) metal has been considered a promising anode candidate for next-generation energy-storage applications due to its ultrahigh capacity. However, the uncontrolled dendrite growth and continuous side reactions challenge the cycle life and practical application. Herein, by a facile and mild solution method, we build a compact LiZn alloy-based hybrid layer on the Li-metal surface. This hybrid layer exhibits favorable chemical stability, excellent wettability to electrolyte, and enhanced thermodynamic affinity to Li. As a result, the hybrid layer modified lihtium metal anode (HL-Li) enables accelerated Li-ion diffusion kinetics and dense Li deposition. Through the operando cell evaluation, moreover, we demonstrate that the hybrid layer restricts the Li dendrite growth of Li metal anodes effectively by reducing the volume expansion to half. Endowed with both thermodynamic and kinetic superiority, HL-Li exhibits low overpotential and prolonged cycles in both symmetric cells and full cells. Our work confirms the lithiophilic hybrid layer obtained by a facile solution process to enable dendrite-free deposition, providing a guidance for the synthesis of high-performance Li metal anode materials.

Hierarchically Porous Ferroelectric Layer with the Aligned Dipole Moment for a High-Performance Aqueous Zn Metal Battery.

Rechargeable aqueous Zn metal batteries (AZMBs) are desirable because of the advantages of metallic Zn and aqueous media. However, AZMBs suffer from limited cyclability and low Coulombic efficiency, originating from uncontrolled dendrite growth and side reactions such as hydrogen gas evolution and corrosion. A hierarchically porous poly(vinylidene difluoride) (PVDF) protection layer with ferroelectric β-phases is formed on the Zn metal using a simple electrospinning method. This suppresses Zn metal failure modes such as side reactions and dendrite growth and supports rapid electrolyte accessibility. The synergetic effect of hierarchically porous structures and ferroelectricity not only facilitates a supporting matrix to form uniform nucleation sites for Zn deposition but also inhibits corrosion, allowing dendrite-free Zn deposition. This multifunctional PVDF film significantly improves the cyclability of Zn symmetric cells, allowing for up to 850 h of repeated plating/stripping cycles. Moreover, it exhibits an excellent cycle life of 1000 cycles under harsh conditions and high current densities of 4.0-10.0 mA cm-2, which are 62-fold higher than those that the bare Zn electrode tolerates.

Conductive Iodine-Doped Red Phosphorus Enabled Dendrite-Free Lithium Deposition on MXene Matrix.

The highest theoretical capacity and lowest redox potential of lithium metal make lithium-based batteries the "holy grail" of the next-generation batteries. However, the uncontrollable dendrite growth and infinite volume change of lithium seriously hinder the real-world implementation of lithium-based batteries. Herein, a flexible MXene@iodine-doped red phosphorus (MXene@RP) paper with iodine-doped red phosphorous particles evenly distributed on the surface and interlayer of MXene matrix is designed by a simple vapor condensation reduction approach. The MXene@RP paper can be used as an efficient matrix to enable dendrite-free lithium deposition. On the one hand, the iodine doping alleviates the low conductivity shortcoming of red phosphorus, making it facilitate homogeneous lithium nucleation, thus promoting uniform lithium deposition and suppressing dendrite growth. On the other hand, the unique layered structure of conductive MXene paper provides ion transport channels and free spaces for lithium loading, alleviating the volume change induced structural damage. As a result, the MXene@RP paper with preloaded lithium exhibits long-term cycling stability. Particularly, a full cell based on Li-MXene@RP anode can maintain 81.4% of the initial capacity after 600 cycles at 4 C. The MXene@RP-based anode increases the potential applications of MXene and provides a guide for the design of dendrite-free lithium hosts.

Rational Design of an Artificial SEI: Alloy/Solid Electrolyte Hybrid Layer for a Highly Reversible Na and K Metal Anode.

The practical application of a Na/K-metallic anode is intrinsically hindered by the poor cycle life and safety issues due to the unstable electrode/electrolyte interface and uncontrolled dendrite growth during cycling. Herein, we solve these issues through an in situ reaction of an oxyhalogenide (BiOCl) and Na to construct an artificial solid electrolyte interphase (SEI) layer consisting of an alloy (Na3Bi) and a solid electrolyte (Na3OCl) on the surface of the Na anode. As demonstrated by theoretical and experimental results, such an artificial SEI layer combines the synergistic properties of high ionic conductivity, electronic insulation, and interfacial stability, leading to uniform dendrite-free Na deposition beneath the hybrid SEI layer. The protected Na anode presents a low voltage polarization of 30 mV, achieving an extended cycling life of 700 h at 1 mA cm-2 in the carbonate-based electrolyte. The full cell based on the Na3V2(PO4)3 cathode and hybrid SEI-protected Na anode shows long-term stability. When this strategy is applied to a K metal anode, the protected K anode also reaches a cycling life of over 4000 h at 0.5 mA cm-2 with a low voltage polarization of 100 mV. Our work provides an important insight into the design principles of a stable artificial SEI layer for high-energy-density metal batteries.

Ultraconformal Horizontal Zinc Deposition toward Dendrite‐Free Anode

Aqueous zinc (Zn)‐ion batteries (ZIBs) have been considered as the most promising candidate for large‐scale energy storage system. However, the severe and uncontrollable dendrite growth of Zn anodes hinders the practical application. Herein, an ultraconformal horizontal Zn deposition is achieved, which is profiting from the epitaxial interface (InGaZn6O9) formed via spontaneously alloying between liquid Ga–In alloy (EGaIn) and Zn. The exposed (0016) plane of InGaZn6O9 matches well with (002) plane of Zn, inducing horizontal and dense Zn deposition. The resultant anode endows with prolonged cycling stability, and the full battery paired with MnO2 exhibits a stable lifespan over 4400 cycles at 5 A g−1. Meanwhile, the self‐formed ultraconformal interface realizes 360° no dead angle protection of anode, which is promising in flexible electronics. And there is no obvious capacity recession of the pouch cell even after bending 180°, demonstrating impressive flexibility. More importantly, the interface can be simply fabricated over a large area, displaying the large‐scale viability. The tailored approach delivers a constructive guideline for dendrite‐free Zn anode, showing great potential in the industrial production.

Intercalation-deposition mechanism induced by aligned carbon fiber toward dendrite-free metallic potassium batteries

Metallic potassium (K) anodes are highly desirable for high energy density batteries. However, challenges lie in uncontrollable dendrite growth and/or inevitable generation of dead K. Here, composite anodes are constructed by covering a layer of aligned carbon fiber on the surface of each metallic K anode (K-ACF). Symmetrical K-ACF//K-ACF cells can work stably without short circuit for over 600 h, which is quite longer than cells using composite anodes with unaligned carbon fiber (K-UCF) and bare metallic K anodes. Comprehensive characterizations reveal a stepwise intercalation-deposition process on the K-ACF anode during the K plating, and the intercalation is proved to be necessary for the uniform K+ flux due to the improved potassiophility of potassiated ACF. Besides, the aligned structure of ACF offers a uniform current density and K+ ion flux on the surface of composite anodes, promoting the stable K stripping/plating. The K-ACF//Prussian blue (PB) cell exhibits a high discharge capacity of 83.6 mAh g−1 (267.4 Wh kg−1 based on the mass of PB) under a charge/discharge rate of 200 mA g−1 with a capacity loss rate of 0.044% per cycle. This work opens up a new avenue toward high energy and dendrite-free potassium batteries.

In situ growth of S-doped ZnO thin film enabling dendrite-free zinc anode for high-performance aqueous zinc-ion batteries

Aqueous rechargeable zinc-ion batteries (AZIBs) have gained extensive attentions due to their high volumetric capacity, low cost, and intrinsic safety. Nonetheless, their zinc metal anodes have been suffered from many issues, such as uncontrollable dendrite growth and undesired side reactions, which eventually degrade the capacity and cycle life. Herein, a thin sulfur-doped zinc oxide artificial interface film (≈200 nm) was in situ grown on zinc foil (ZnO:S@Zn) by a simple chemical bath deposition method. The density functional theory calculations revealed that the electronic conductivity of zinc oxide could be improved after sulfur doping. Characterization analyses and electrochemical measurements showed that this unique film could enhance the electrical conductivity of zinc anode inhibit the side reaction and induce Zn 2+ uniform deposition. As a result, the ZnO:S@Zn symmetric cell was stably cycled for 1700 h at 0.5 mA cm −2 with a stable voltage hysteresis of ~20 mV, and the full-cell pairing with MnO 2 cathode exhibited an excellent reversible capacity of 297.46 mAh g −1 after 300 cycles. This work offers a simple and effective way to fabricate a stable Zn metal anode for high performance AZIBs. • S-doped zinc oxide film was grown on commercial zinc foil in situ. • The zinc dendrites and corrosion reactions were suppressed by the film. • The cells displayed prolonged cycling stability and lower voltage hysteresis.

Zincophilic polymer semiconductor as multifunctional protective layer enables Dendrite-Free zinc metal anodes

Zinc (Zn) metal is considered as one of the most promising anodes for aqueous zinc-ion batteries due to its high theoretical capacity, low cost, and environmental benignity. However, the uncontrolled dendrite growth and parasitic side-reactions lead to low Coulombic efficiency and limited lifespan, severely affecting their applications. Herein, a stable and robust g-C3N4 is constructed on the surface of metallic Zn anode (g-C3N4@Zn), serving as a multifunctional protective layer. The nitrogen (N)-rich g-C3N4 layer exhibits inherent zincophilic properties, in which zinc ions can be bonded with N to form Zn-N bonds, resulting in homogenous nucleation and inhibiting dendrite growth. In addition, the hydrogen evolution reaction and the formation of by-products can be effectively relieved, which are attributed to the polymer layer blocking water from the Zn surface. More importantly, in-situ optical real-time monitoring, density functional theory calculations, and molecular dynamic simulations demonstrate the effectiveness of the zincophilic g-C3N4 layer in improving stability. As expected, the g-C3N4@Zn anode achieves a remarkable cycling lifespan of around 2900 h (up to four months) in symmetric cells, together with high cycling stability (1000 cycles) for g-C3N4@Zn//V3O7 H2O full batteries. Significantly, the new finding of the zincophilic g-C3N4 protective layer points to an alternative effective pathway to regulate Zn metal anodes for practical applications.

In situ generation of Li3N concentration gradient in 3D carbon-based lithium anodes towards highly-stable lithium metal batteries

The uncontrolled dendrite growth of lithium metal anodes (LMAs) caused by unstable anode/electrolyte interface and uneven lithium deposition have impeded the practical applications of lithium metal batteries (LMBs). Constructing a robust artificial solid electrolyte interphase (SEI) and regulating the lithium deposition behavior is an effective strategy to address these issues. Herein, a three-dimensional (3D) lithium anode with gradient Li3N has been in-situ fabricated on carbon-based framework by thermal diffusion method (denoted as CC/Li/Li3N). Density functional theory (DFT) calculations reveal that Li3N can effectively promote the transport of Li+ due to the low energy barrier of Li+ diffusion. As expected, the Li3N-rich conformal artificial SEI film can not only effectively stabilize the interface and avoid parasitic reactions, but also facilitate fast Li+ transport across the SEI layer. The anode matrix with uniformly distributed Li3N can enable homogenous deposition of Li, thus preventing Li dendrite propagation. Benefiting from these merits, the CC/Li/Li3N anode achieves ultralong-term cycling for >1000 h at a current density of 2 mA cm−2 and dendrite-free Li deposition at an ultrahigh rate of 20 mA cm−2. Moreover, the full cells coupled with LiFePO4 cathodes show extraordinary cycling stability for >300 cycles in liquid-electrolyte-based batteries and display a high-capacity retention of 96.7% after 100 cycles in solid-state cells, demonstrating the promising prospects for the practical applications of LMBs.