Li Dendrite Growth Research Articles

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.

A high-safety lithium-ion battery electrospun separator with Si3N4-assisted sulfonated poly(ether ether ketone) for regulating lithium flux

The uncontrolled lithium (Li) dendrite growth significantly impacts the safety performance of polymer separators. To mitigate this growth, this study introduces Si3N4 into sulfonated poly(ether Ether Ketone) (SPEEK) and prepares Si3N4/SPEEK composite separators via electrospinning. At the interface between the Si3N4/SPEEK separator and the Li anode, the Si nanowires that form impede Li dendrite growth, thereby enhancing the electrochemical performance of lithium-ion batteries (LIBs). The Li deposition test of the 10 % Si3N4/SPEEK separator can operate for 1000 h without short-circuiting. Additionally, the LiFePO4||Li cell with the 10 % Si3N4/SPEEK separator shows improved initial discharge capacity (157.8 mAh g−1 at 1C) and superior rate performance (125 mAh g−1 at 10C). Moreover, the nano-scale Si3N4 endows the separator with robust thermal and mechanical properties. The FLIR observations reveal that the 10 % Si3N4/SPEEK separator maintains uniform thermal distribution and structural integrity even at 300 °C, ensuring safe battery operation at high temperatures. The additional load of the 10 % Si3N4/SPEEK separator can reach 10.2 mN, which enhances the puncture resistance of the separator. This work provides a solid approach for the application of SPEEK as a high-safety and high-rate LIB separator.

An In Situ Generated Organic/Inorganic Hybrid SEI Layer Enables Li Metal Anodes with Dendrite Suppression Ability, High-Rate Capability, and Long-Life Stability.

High-quality solid electrolyte interphase (SEI) layers can effectively suppress the growth of Li dendrites and improve the cycling stability of lithium metal batteries. Herein, 1-(6-bromohexanoyl)-3-butylurea is used to construct an organic/inorganic hybrid (designated as LiBr-HBU) SEI layer that features a uniform and compact structure. The LiBr-HBU SEI layer exhibits superior electrolyte wettability and air stability as well as strong attachment to Li foils. The LiBr-HBU SEI layer achieves a Li+ conductivity of 2.75 × 10-4 S cm-1, which is ≈50-fold higher than the value measured for a native SEI layer. A Li//Li symmetric cell containing the LiBr-HBU SEI layer exhibits markedly improved cyclability when compared with the cell containing a native SEI layer, especially at a high current density (e.g., cycling life up to 1333h at 15mA cm-2). The LiBr-HBU SEI layer also improves the performance of lithium-sulfur cells, particularly the rate capability (548 mAh g-1 at 10C) and cycling stability (513 mAh g-1 at 0.5C after 500 cycles). The methodology described can be extended to the commercial processing of Li metal anodes as the artificial SEI layer also protects Li metal against corrosion.

ZnS Nanoseeds Sealed in N, P, S Co-Doped Carbon Hollow Rhombic Dodecahedra as a Superlithiophilic Host for Dendrite-Free Lithium Metal Anodes.

Lithium (Li) metal is considered ahopeful anode for next-generation Li-ion batteries thanks to its ultra-high theoretical specific capacity, extra-low theoretical density, and low negative potential. However, the uncontrolled growth of Li dendrites and volume fluctuation during plating/stripping processes severely hamper its commercial application. Herein, ZnS seeds sealed in N, P, S co-doped carbon hollow rhombic dodecahedra (ZnS@NPS-C HRD) is fabricated as a superlithiophilic host for Li metal anodes (LMAs) to solve the above problems. In addition, the Li nucleation and deposition mechanism on ZnS@NPS-C HRD is investigated by in situ optical microscopy, ex-situ X-ray diffraction, scanning electron microscopy, and theoretical calculations. Owing to the synergistic strategy of ZnS seeds-inducing nucleation and Li-limited growth, the as-prepared composite exhibits stability for 300 cycles in asymmetric cells and a long lifespan over 1100h in symmetric cells. Moreover, the ZnS@NPS-C HRD@Li|LiFePO4 full cell demonstrates a reversible capacity of 100.91mAhg-1 after 400 cycles at 1C.

Quantum-Sized Co Nanoparticles with Rich Vacancies Enabled the Uniform Deposition of Lithium Metal and Fast Polysulfide Conversion.

The notorious polysulfide shuttling and uncontrollable Li-dendrite growth are the main obstacles to the marketization of Li-S batteries. Herein, a dual-functional material consisting of vacancy-rich quantum-sized Co nanodots anchored on a mesoporous carbon layer (v-Co/meso-C) is proposed. This material exposes more active sites to improve its reaction performance and simultaneously realizes excellent lithiophilicity and sulfiphilicity characteristics in Li-S electrochemistry. As Li metal deposition hosts, v-Co/meso-C shows small nucleation overpotential, low polarization, and ultra-long cycling stability in both half and symmetric cells, as confirmed by experimental studies. On the S cathode side, experimental and theoretical calculations demonstrate that v-Co/meso-C enhances the adsorption of polysulfides and boosts their catalytic conversion rate. This, in turn, suppresses the shuttle effect of polysulfides and improves sulfur utilization efficiency. Finally, a shuttle-free and dendrite-free v-Co/meso-C@Li//v-Co/meso-C@S full cell is fabricated, exhibiting excellent rate performance (739 mAhg-1 at 5.0 C) and good cyclability (capacity decay rate is 0.033% and 0.035% per cycle at 2.0 and 5.0 C, respectively). Even a pouch cell with high sulfur loading (5.5mgcm-2) and lean electrolyte/sulfur (4.8µLmg-1) can still work 50 cycles with 80% capacity retention rate. This study shows far-reaching implications in the design of dendrite-free, shuttle-free Li-S batteries.

3D self-supporting core-shell silicon-carbon nanofibers-based host enables confined Li+ deposition for lithium metal battery

Three-dimensional (3D) porous hosts play pivotal roles in realizing dendrite-free lithium metal anodes (LMAs) owing to their high specific area. However, uneven local electric field and lack of lithiophilic sites on the reactive interface cause nonuniform lithium ion (Li+) deposition, leading to Li dendrite growth and parasitic reactions. These issues will inevitably incur short cycling life and severe safety hazards of lithium metal batteries. Herein, a 3D self-supporting host composed of hollow carbon nanofibers incorporated with silicon (Si) nanoparticles inside (Si-HCF) is constructed as Li metal host by a scalable coaxial electrospinning technique. During the first cycle, the Si nanoparticles is alloyed with Li+ to form lithiophilic Li-Si alloy, contributing to deliver a low nucleation overpotential and homogeneous surface potential confirmed by Kelvin probe force microscopy, finally guiding Li+ flux homogeneously throughout the fibrous mat. As expected, the Li metal can percolate through Si-HCF host reversibly without uncontrollable Li dendrites and the Si-HCF exhibits a stable cycle life of Li plating/stripping over 1400 h. Additionally, the full cell combined with LiFePO4 cathodes presents steady cycling over 400 cycles with a high average coulombic efficiency of 99.4 %. This work provides new insights for the synthesis of 3D hosts with controllable nucleation sites to homogenize Li+ deposition in LMAs.

Five Volts Lithium Batteries with Advanced Carbonate-Based Electrolytes: A Rational Design via a Trio-Functional Addon Materials.

Lithium metal batteries paired with high-voltage LiNi0.5Mn1.5O4 (LNMO) cathodes are a promising energy storage source for achieving enhanced high energy density. Forming durable and robust solid-electrolyte interphase (SEI) and cathode-electrolyte interface (CEI) and the ability to withstand oxidation at high potentials are essential for long-lasting performance. Herein, advanced electrolytes are designed via trio-functional additives to carbonate-based electrolytes for 5V Li||LNMO and graphite||LNMO cells achieving 88.3% capacity retention after 500 charge-discharge cycles. Theoretical calculations reveal that adding adiponitrile facilitates the presence of more hierarchical DFOB- and PF6 - dual anion structure in the solvation sheath, leading to a faster de-solvation of the Li cation. By combining both fluorine and nitrile additives, an efficient synergistic effect is obtained, generating robust thin inorganic SEI and CEI films, respectively. These films enhance microstructural stability; Li dendrite growth on the Li electrode is being suppressed at the anode side and transition-metals dissolution from the cathode is being mitigated, as evidenced by cryo-transmission electron microscopy and synchrotron studies.

Chemo-electro-mechanical phase-field simulation of interfacial nanodefects and nanovoids in solid-state batteries

Solid electrolytes encompass various types of nanodefects, including grain boundaries and nanovoids at the Li-metal/solid electrolyte interface, where lithium dendrite penetration has been extensively observed. Despite the importance of ion transport near grain boundaries with different anisotropy and the combinatorial effects with interfacial nanovoids, a comprehensive understanding of these phenomena has remains elusive. Here, we develop a chemo-electro-mechanical phase-field model to elucidate how Li penetrates Li7La3Zr2O12 in the co-presence of grain boundaries and interfacial nanovoids. The investigation unveils a grain-boundary-anisotropy-dependent behavior for Li-ion transport correlated with the presence of interfacial nanovoids. Notably, the Σ1 grain boundary exhibits faster Li dendrite growth, particularly in the co-presence of interfacial nanovoids. The model quantitatively reveals whether interfacial electronic properties dominate Li dendrite morphology and penetration, providing a strategy for designing stable Li/solid electrolyte interfaces. These findings help prioritize approaches for optimally tailoring nanodefects and exploiting synergetic effects at the interface to prevent dendrite formation.

Anion‐Reduction‐Catalysis Induced LiF‐Rich SEI Construction for High‐Performance Lithium‐Metal Batteries

AbstractThe practical application of lithium‐metal batteries (LMBs) remains impeded by uncontrollable Li dendrite growth and unstable solid‐state electrolyte interphase (SEI) on lithium‐metal anodes. Constructing the inorganic‐rich SEI is considered as an effective strategy to realize the dense Li deposition and inhibit interfacial side reactions, thereby improving the lifespans of LMBs. Herein, an anion‐reduction‐catalysis mechanism is proposed to design a LiF‐rich SEI utilizing 2D tellurium (Te) nanosheets as catalysts, which are homogenously implanted on the substrate. Lithiophilic Te nanosheets can induce uniform Li nucleation and deposition through in situ lithiation reactions, while the resulting product Li2Te can reduce the energy barrier for anion decomposition and promote the generation of LiF in the SEI. Consequently, Li dendrite growth and interfacial side reactions are effectively suppressed, enabling long‐cycle‐life LMBs. The Te‐modified electrode in half‐cells delivers superior cycle life exceeding 500 cycles and a high average Coulombic efficiency of 97.8% at 5 mAh cm−2. The high‐energy‐density (405 Wh kg−1) pouch cells pairing the Te‐modified Li anodes with high‐mass‐loading LiNi0.9Co0.05Mn0.05O2 (NCM90) cathodes exhibit stable cycling performance with a high average Coulombic efficiency of 99.3% in carbonate electrolytes. This work provides a promising anion catalyst design for LiF‐rich SEI and paves the way for developing high‐energy‐density LMBs.

In Situ Self‐Polymerization of Thioctic Acid Enabled Interphase Engineering Towards High‐Performance Lithium–Sulfur Battery

AbstractLithium–sulfur (Li–S) batteries possess high theoretical energy density, whereas the shuttle effect of polysulfides and the uncontrollable lithium (Li) dendrites seriously reduce the reversible capacity and cycling lifespan. Constructing an interphase to address the issues in both the cathode and anode simultaneously is significant but still challenging. In this study, a strategy of functionalizing commercial polypropylene (PP) separators is proposed by in situ poly(thioctic acid) (PTA) polymerization. Compared with the conventional separator modifications, the ring‐opening polymerization methodology initiated by heat is more facile and environment‐friendly without changing the nanostructures among the porous separators. On the cathode side, the PTA‐coated separator (PTA‐PP) blocks the shuttle of polysulfides through the electrostatic interaction. On the anode side, the PTA‐coated generates a lithium fluoride (LiF)‐rich solid electrolyte interface (SEI), identified by cryo‐transmission electron microscopy (cryo‐TEM), to accelerate the Li+ diffusion and inhibit the growth of Li dendrites. Due to the interphases constructed by the PTA‐PP separator, the Li–S cells exhibit excellent long‐term cycling in which the capacity retention rate is more than 76% after 700 cycles at 0.5 C. The in situ elaborate modification strategy may provide insights into the high‐performance separator design to promote the potentially large‐scale applications of Li–S batteries.

3D structured lithiophilic current collector with lithiation nucleation overpotential near 0 V for dendrite-free lithium metal anode

The poor lithium affinity of most metal skeletons leads to uneven electric field distribution, resulting in the notorious Li dendrite growth. Herein, a 3D structured Cu mesh@Ag current collector is introduced using a simple chemical plating method to enable dendrite-free Li anode. The high electronic conductivity and matrix pore structure of Cu mesh can alleviate the local current density and provide buffer space for lithium deposition. The lithiophilic Ag can form infinite solid solution with Li while reducing the initial lithiation nucleation overpotential to about 0 V, achieving homogenous Li deposition. As a result, the symmetric cell can maintain a low polarization voltage (20 mV) after cycling at 0.5 mA cm-2 for 1300 h Full cells assembled with LiFePO4 cathode present a long-term cycling stability of 500 cycles at 1C with a capacity retention of 80.3%. This work provides a reliable approach to create stable Li-metal batteries.

Functional ternary salt construction enabling an in-situ Li3N/LiF-enriched interface for ultra-stable all-solid-state lithium metal batteries

Poly(ethylene oxide)-based polymer all-solid-state lithium metal batteries (ASSLBs) have received widespread attention due to their low cost, good process ability, and high energy density. Nevertheless, the growth of Li dendrites within polymer solid-state electrolytes damages the reversibility of Li anodes and still impedes their widespread application. One efficient strategy is to construct a superior solid electrolyte interface. Herein, a stable interface enriched with Li3N and LiF is in-situ formed between Li anode and a ternary salt electrolyte. This ternary salt electrolyte is innovatively designed by introducing lithium bis(trifluoromethane sulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), and LiNO3 to poly(ethylene oxide) matrix. Surface characterization indicates that LiNO3 and LiFSI contribute to forming a Li3N-LiF-enriched interface and meanwhile LiTFSI ensures excellent conductivity. Theoretically, among various Li compound components, Li3N has high ionic conductivity, which is beneficial for reducing overpotential, while LiF has high interfacial energy which can enhance nucleation energy and suppress the formation of Li dendrites. The experimental results show that ASSLBs coupled with LiFePO4 cathode display extremely excellent cycle stability approximately 2200 cycles at 2 C, with a final and corresponding discharge specific capacity of 96.7 mA h g−1. Additionally, a schematic illustration of the working mechanism for the Li3N-LiF interface is proposed.

Regulating Li+ transport behavior by cross-scale synergistic rectification strategy for dendrite-free and high area capacity polymeric all-solid-state lithium batteries

The inability to effectively inhibit the lithium (Li) dendrite growth is identified as the real culprit hindering the practical application of polyethylene oxide (PEO)-based electrolytes. Herein, a novel PEO composite electrolyte with ion rectifier is developed based on the cross-scale synergistic rectification strategy. At the micro-scale, the array structure of the ion rectifier suppresses the growth of PEO crystals and their distribution in the non-ionic conduction direction through space confinement, alleviating ion-migration crosstalk and enabling polymer chain rectification. Furthermore, the matrix contains abundant copper ions and oxygen-containing groups that inhibit anion conduction and accelerate Li+ migration at the nanoscale, respectively, to achieve ion flow rectification. Implementing this strategy results in a uniform, fast, and stable Li+ migration/diffusion behavior from the electrolyte to anode interface. The critical current density of the PEO electrolyte is increased to 2.5 mA cm−2, indicating a significant improvement in dendrite growth inhibition. Impressively, the composite electrolytes exhibit long-term stability (>4000 h at 0.2 mA cm−2) and ultra-high current-density tolerance (>200 h at 1 mA cm−2). Moreover, the composite electrolytes enable stable cycling of high-area-capacity (3.11 mAh cm−2, 20 mg cm−2) LiFePO4/Li pouch cells, highlighting the importance of this strategy for the practical application of PEO electrolytes.

Ti3C2Tx MXene enhanced PEO/SN-based solid electrolyte for high-performance Li metal battery

Succinonitrile has shown significant promise for application in polymer electrolytes for solid-state lithium metal batteries due to its high ionic conductivity at low-temperature. However, the use of Succinonitrile is limited due to its corrosion of Li metal. Herein, we report a solid polymer electrolyte with high ionic conductivity (2.17 × 10−3 S cm−1, 35 °C) enhanced by Ti3C2Tx. Corrosion of the Li anode is prevented due to the Succinonitrile molecules being efficiently anchored by Ti3C2Tx. Meanwhile, the coordination environment of Li+ is weakened due to the introduction of competitive coordination induction effects into the polymer electrolyte, resulting in efficient Li+ conduction. Furthermore, the mechanical properties of the electrolyte are enhanced by modulating the ratio of Ti3C2Tx to suppress the growth of Li dendrites. Therefore, Li||Li symmetric batteries deliver stable cycling up to 8000 h at 28 °C. LiFePO4||Li full batteries exhibit excellent cycling stability of 151.7 mAh g−1 with a capacity retention of 99.3% after 300 cycles. This work not only presents a new idea to suppress the corrosion of the Li anode by Succinonitrile but also provides a simple, feasible, and scalable strategy for high-performance Li metal batteries.

Zein protein-functionalized separator through a viable method for trapping polysulfides and regulating ion transport in Li[sbnd]S batteries

Commercialization of lithium‑sulfur (LiS) batteries as a promising energy storage system, is primarily impeded by polysulfide shuttling and uncontrollable lithium dendrite growth. To address the issues for improving the performance of LiS batteries, we decorate the separator with zein (corn protein) via a simple soaking process. Owing to strong zein–polysulfide interactions, the zein-soaked separator effectively enhances the polysulfide-trapping capability. Moreover, abundant functional groups of zein also stabilize Li-ion deposition, and thus suppresses the growth of Li dendrites. As a result, the resulting LiS batteries exhibited enhanced electrochemical performance in terms of cycling stability, capacity retention, and rate capability. The soaking method used for coating zein on pristine separator offers a scalable solution for generating multifunctional separators toward commercialization.

Thickness regulation of electric double layer via electronegative separator to realize High-Performance Lithium-Metal batteries

Lithium metal anode is considered as a promising electrode material for next-generation energy storage systems due to their high theoretical capacity and a low redox potential. However, the uncontrollable growth of Li dendrites severely hindered its practical application. Separators, a vital component in batteries, offer a promising solution to this issue, which can regulate the transport of lithium ions (Li+) and guide the homogenous deposition of Li+. In this study, a three-dimensional porous structure coating layer is constructed on the surface of the commercial polyethylene separator by polymer-induced phase separation (PIPS) and UV-induced cross-linking reactions. The incorporation of synthetized sulfonated SiO2 particles (S-SiO2) enable the successful construction of a negatively charged separator (PE@S-SiO2) based on negatively charged moieties on the surface, which compresses the thickness of the electric double layer (EDL) to optimize the Li+ transport dynamics and suppress dendritic growth. The resulting PE@S-SiO2 separator displays superior electrolyte wettability, much higher thermal resistance, high lithium transference number (0.86), and ionic conductivity (1.15 mS/cm). Consequently, when assembled into lithium metal batteries, the negatively charged separator endows stable cycling over 800 h at a current density of 1 mA cm−2.

Scalable Production of Thin and Durable Practical Li Metal Anode for High-Energy-Density Batteries.

Utilization of thin Li metal is the ultimate pathway to achieving practical high-energy-density Li metal batteries (LMBs), but its practical implementation has been significantly impeded by formidable challenges of poor thinning processability, severe interphase instability and notorious dendritic Li growth. Here we report a practical thin (10-40 μm) Li/Mo/Li2Se with concurrently modulated interphase and mechanical properties, achieved via a scalable mechanical rolling process. The in-situ generated Li2Se and Mo not only enhance the mechanical strength enabling the scalable fabrication of thin Li metal, but also promote homogenous Li electrodeposition. Significantly, the Li/Mo/Li2Se demonstrates ultrahigh-rate performance (15 mA cm-2) and ultralong-lifespan cycling sustainability (2700 cycles) with exceptional anti-pulverization capability. The Li|LiFePO4 cells show substantially prolonged cyclability over 1200 cycles with an ultralow decay rate of ~0.01% per cycle. Moreover, the Li|LiNi0.8Co0.1Mn0.1O2 pouch cells deliver enhanced cycling stability even under the extremely harsh conditions of low negative-to-positive-capacity (N/P) ratio of ~1.2 and lean electrolyte of ~0.95 g Ah-1, showing an exceptional energy density of 329.2 Wh kg-1. This work sheds light on facile pathway for scalable production of durable thin Li metal anode toward reliable practicability.

Rolling strategy for highly efficient preparation of phosphating interface enabled the stable lithium anode

Lithium metal anode has an ultra-high theoretical specific capacity and the lowest reduction potential, regarded as the next-generation anode material for high-energy-density batteries. However, the lithium metal anode suffers from the severe side reaction and Li dendrite growth caused by the inhomogeneous deposition of Li+ on the anode during the electrochemical cycling. Herein, a strategy is proposed to design an artificial solid electrolyte interface (SEI) by rolling with the organic phosphating lubricant. The obtained phosphating interface with high surface energy and surface Young’s modulus significantly induces the dense deposition of Li+ and results in a stable cycling. The phosphating interface enables the symmetric cells to cycle stably for 750 h at 1 mA cm−2 with 1 mA h cm−2 and for 450 h at 3 mA cm−2 with 3 mA h cm−2 using ester-based electrolyte. The full cell with high single-side mass loading (10 mg cm−2) of LiCoO2 achieves a capacity retention rate of 77.7 % after 165 cycles at 1 C and 75.6 % after 120 cycles at 2 C. This work paves a path to construct a green fluorine-free interface and provide a large-scale modification for practical lithium strips.

Lewis-basic nitrogen-rich covalent organic frameworks enable flexible and stretchable solid-state electrolytes with stable lithium-metal batteries

Designing flexible and stretchable solid-state electrolytes (SSEs) holds promise but challenge in flexible all-solid-state lithium-metal batteries (LMBs) owing to their insufficient ion conductivity and mechanical strength. Herein, we develop nitrogen-rich covalent organic frameworks (NCOF) with abundant Lewis-basic N atoms as lithiophilic sites to incorporate Lewis-acidic Li+ into its inner order structure for fabricating flexible and stretchable PEO-LI+@NCOF SSEs with the crosslinking of polyethylene oxide (PEO). The SSE film displays high mechanical strain (2.2 MPa), Young's modulus (689 MPa), stretchability (1000 %), ion conductivity (2.4 × 10–4 S cm-1), good flame resistance, and wide electrochemical window (4.8 V). Owing to the rich Lewis-basic N atoms with strong Li+ adsorption energy, orderly nanochannels, and negative charge environment within NCOFs, the SSE film endows orderly and rapid ion migration, low Li-ion diffusion barrier, and significantly enhanced ion conductivity for uniform lithium plating/stripping and suppressing Li-dendrite growth. The crosslinking of Li+@NCOF with PEO greatly enhances the mechanical stretchability, flame resistance, and electrochemical window of PEO-based SSEs. Consequently, the Li/PEO-LI+@NCOF/Li symmetrical cell exhibits stable cycling without short-circuiting for 1200 h at 0.1 mA cm-2/0.1 mAh cm-2. The LiFePO4/PEO-LI+@NCOF/Li battery exhibits a 500-cycle long lifespan at 1 C (78 % capacity retention), and its pouch cell verifies promising applications in flexible all-solid-state LMBs. Therefore, introducting Lewis-basic N-rich COFs verifies an effective strategy to design a flexible and stretchable SSE film with high mechanical strength, superior ion conductivity and flame resistance.

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.