A Two‐Dimensional Mesoporous Polypyrrole–Graphene Oxide Heterostructure as a Dual‐Functional Ion Redistributor for Dendrite‐Free Lithium Metal Anodes

Guiding the lithium ion (Li‐ion) transport for homogeneous, dispersive distribution is crucial for dendrite‐free Li anodes with high current density and long‐term cyclability, but remains challenging for the unavailable well‐designed nanostructures. Herein, we propose a two‐dimensional (2D) heterostructure composed of defective graphene oxide (GO) clipped on mesoporous polypyrrole (mPPy) as a dual‐functional Li‐ion redistributor to regulate the stepwise Li‐ion distribution and Li deposition for extremely stable, dendrite‐free Li anodes. Owing to the synergy between the Li‐ion transport nanochannels of mPPy and the Li‐ion nanosieves of defective GO, the 2D mPPy‐GO heterostructure achieves ultralong cycling stability (1000 cycles), even tests at 0 and 50 °C, and an ultralow overpotential of 70 mV at a high current density of 10.0 mA cm^?2, outperforming most reported Li anodes. Furthermore, mPPy‐GO‐Li/LiCoO₂ full batteries demonstrate remarkably enhanced performance with a capacity retention of >90 % after 450 cycles. Therefore, this work opens many opportunities for creating 2D heterostructures for high‐energy‐density Li metal batteries.     

Stable Conversion Chemistry‐Based Lithium Metal Batteries Enabled by Hierarchical Multifunctional Polymer Electrolytes with Near‐Single Ion Conduction

The low Coulombic efficiency and serious safety issues resulting from uncontrollable dendrite growth have severely impeded the practical applications of lithium (Li) metal anodes. Herein we report a stable quasi‐solid‐state Li metal battery by employing a hierarchical multifunctional polymer electrolyte (HMPE). This hybrid electrolyte was fabricated via in situ copolymerizing lithium 1‐[3‐(methacryloyloxy)propylsulfonyl]‐1‐(trifluoromethanesulfonyl)imide (LiMTFSI) and pentaerythritol tetraacrylate (PETEA) monomers in traditional liquid electrolyte, which is absorbed in a poly(3,3‐dimethylacrylic acid lithium) (PDAALi)‐coated glass fiber membrane. The well‐designed HMPE simultaneously exhibits high ionic conductivity (2.24×10^?3 S cm^?1 at 25 °C), near‐single ion conducting behavior (Li ion transference number of 0.75), good mechanical strength and remarkable suppression for Li dendrite growth. More intriguingly, the cation permselective HMPE efficiently prevents the migration of negatively charged iodine (I) species, which provides the as‐developed Li‐I batteries with high capacity and long cycling stability.     

Normalized Lithium Growth from the Nucleation Stage for Dendrite‐Free Lithium Metal Anodes

Inducing uniform deposition of lithium from the stage of metal crystallization nucleation is of vital importance to achieve dendrite‐free lithium anodes. Herein, using experiments and simulation, homogenization of Li nucleation and normalization of Li growth can be achieved on PNIPAM polymer brushes with lithiophilic functional groups modified Cu substrates. The lithiophilic functional groups of amide O can homogenize ion mass transfer and induce the uniform distribution of Li nucleation sites. What is more, the ultra‐small space between each brush can act as the channels for Li transportation and normalization growth. Owing to the synergistic effect of homogenization and normalization of electrodeposited Li, the obtained planar columnar Li anode exhibits excellent cycle stability at an ultra‐high current density of 20 mA cm^?2.     

A Sodiophilic Interphase‐Mediated,Dendrite‐Free Anode with Ultrahigh Specific Capacity for Sodium‐Metal Batteries

Despite efforts to stabilize sodium metal anodes and prevent dendrite formation, achieving long cycle life with high areal capacities remains difficult owing to a combination of complex failure modes that involve retardant uneven sodium nucleation and subsequent dendrite formation. Now, a sodiophilic interphase based on oxygen‐functionalized carbon nanotube networks is presented, which concurrently facilitates a homogeneous sodium nucleation and a dendrite‐free, lateral growth behavior upon recurring sodium plating/stripping processes. This sodiophilic interphase renders sodium anodes with an ultrahigh capacity of 1078 mAh g^?1 (areal capacity of 10 mAh cm^?2), approaching the theoretical capacity of 1166 mAh g^?1 of pure sodium, as well as a long cycle life up to 3000 cycles. Implementation of this anode allows for the construction of a sodium–air battery with largely enhanced cycling performance owing to the oxygen functionalization‐mediated, dendrite‐free sodium morphology.     

A Sodiophilic Interphase‐Mediated,Dendrite‐Free Anode with Ultrahigh Specific Capacity for Sodium‐Metal Batteries

Despite efforts to stabilize sodium metal anodes and prevent dendrite formation, achieving long cycle life with high areal capacities remains difficult owing to a combination of complex failure modes that involve retardant uneven sodium nucleation and subsequent dendrite formation. Now, a sodiophilic interphase based on oxygen‐functionalized carbon nanotube networks is presented, which concurrently facilitates a homogeneous sodium nucleation and a dendrite‐free, lateral growth behavior upon recurring sodium plating/stripping processes. This sodiophilic interphase renders sodium anodes with an ultrahigh capacity of 1078 mAh g^?1 (areal capacity of 10 mAh cm^?2), approaching the theoretical capacity of 1166 mAh g^?1 of pure sodium, as well as a long cycle life up to 3000 cycles. Implementation of this anode allows for the construction of a sodium–air battery with largely enhanced cycling performance owing to the oxygen functionalization‐mediated, dendrite‐free sodium morphology.     

Self‐Stabilized and Strongly Adhesive Supramolecular Polymer Protective Layer Enables Ultrahigh‐Rate and Large‐Capacity Lithium‐Metal Anode

Constructing a solid electrolyte interface (SEI) is a highly effective approach to overcome the poor reversibility of lithium (Li) metal anodes. Herein, an adhesive and self‐healable supramolecular copolymer, comprising of pendant poly(ethylene oxide) (PEO) segments and ureido‐pyrimidinone (UPy) quadruple‐hydrogen‐bonding moieties, is developed as a protection layer of Li anode by a simple drop‐coating. The protection performance of in‐situ‐formed LiPEO–UPy SEI layer is significantly enhanced owing to the strong binding and improved stability arising from a spontaneous reaction between UPy groups and Li metal. An ultrathin (approximately 70 nm) LiPEO–UPy layer can contribute to stable and dendrite‐free cycling at a high areal capacity of 10 mAh cm^?2 at 5 mA cm^?2 for 1000 h. This coating together with the promising electrochemical performance offers a new strategy for the development of dendrite‐free metal anodes.     

Columnar Lithium Metal Anodes

The rechargeable lithium metal anode is of utmost importance for high‐energy‐density batteries. Regulating the deposition/dissolution characteristics of Li metal is critical in both fundamental researches and practical applications. In contrast to gray Li deposits featured with dendritic and mossy morphologies, columnar and uniform Li is herein plated on lithium‐fluoride (LiF)‐protected copper (Cu) current collectors. The electrochemical properties strongly depended on the microscale morphologies of deposited Li, which were further embodied as macroscale colors. The as‐obtained ultrathin and columnar Li anodes contributed to stable cycling in working batteries with a dendrite‐free feature. This work deepens the fundamental understanding of the role of LiF in the nucleation/growth of Li and provides emerging approaches to stabilize rechargeable Li metal anodes.     

Columnar Lithium Metal Anodes

The rechargeable lithium metal anode is of utmost importance for high‐energy‐density batteries. Regulating the deposition/dissolution characteristics of Li metal is critical in both fundamental researches and practical applications. In contrast to gray Li deposits featured with dendritic and mossy morphologies, columnar and uniform Li is herein plated on lithium‐fluoride (LiF)‐protected copper (Cu) current collectors. The electrochemical properties strongly depended on the microscale morphologies of deposited Li, which were further embodied as macroscale colors. The as‐obtained ultrathin and columnar Li anodes contributed to stable cycling in working batteries with a dendrite‐free feature. This work deepens the fundamental understanding of the role of LiF in the nucleation/growth of Li and provides emerging approaches to stabilize rechargeable Li metal anodes.     

A Diffusion‐‐Reaction Competition Mechanism to Tailor Lithium Deposition for Lithium‐Metal Batteries

Lithium metal is recognized as one of the most promising anode materials owing to its ultrahigh theoretical specific capacity and low electrochemical potential. Nonetheless, dendritic Li growth has dramatically hindered the practical applications of Li metal anodes. Realizing spherical Li deposition is an effective approach to avoid Li dendrite growth, but the mechanism of spherical deposition is unknown. Herein, a diffusion‐reaction competition mechanism is proposed to reveal the rationale of different Li deposition morphologies. By controlling the rate‐determining step (diffusion or reaction) of Li deposition, various Li deposition scenarios are realized, in which the diffusion‐controlled process tends to lead to dendritic Li deposition while the reaction‐controlled process leads to spherical Li deposition. This study sheds fresh light on the dendrite‐free Li metal anode and guides to achieve safe batteries to benefit future wireless and fossil‐fuel‐free world.     

The Three‐Dimensional Dendrite‐Free Zinc Anode on a Copper Mesh with a Zinc‐Oriented Polyacrylamide Electrolyte Additive

Rechargeable aqueous zinc‐ion batteries have been considered as a promising candidate for next‐generation batteries. However, the formation of zinc dendrites are the most severe problems limiting their practical applications. To develop stable zinc metal anodes, a synergistic method is presented that combines the Cu‐Zn solid solution interface on a copper mesh skeleton with good zinc affinity and a polyacrylamide electrolyte additive to modify the zinc anode, which can greatly reduce the overpotential of the zinc nucleation and increase the stability of zinc deposition. The as‐prepared zinc anodes show a dendrite‐free plating/stripping behavior over a wide range of current densities. The symmetric cell using this dendrite‐free anode can be cycled for more than 280 h with a very low voltage hysteresis (93.1 mV) at a discharge depth of 80 %. The high capacity retention and low polarization are also realized in Zn/MnO₂ full cells.     

Deep‐Eutectic‐Solvent‐Based Self‐Healing Polymer Electrolyte for Safe and Long‐Life Lithium‐Metal Batteries

The deployment of high‐energy‐density lithium‐metal batteries has been greatly impeded by Li dendrite growth and safety concerns originating from flammable liquid electrolytes. Herein, we report a stable quasi‐solid‐state Li metal battery with a deep eutectic solvent (DES)‐based self‐healing polymer (DSP) electrolyte. This electrolyte was fabricated in a facile manner by in situ copolymerization of 2‐(3‐(6‐methyl‐4‐oxo‐1,4‐dihydropyrimidin‐2‐yl)ureido)ethyl methacrylate (UPyMA) and pentaerythritol tetraacrylate (PETEA) monomers in a DES‐based electrolyte containing fluoroethylene carbonate (FEC) as an additive. The well‐designed DSP electrolyte simultaneously possesses non‐flammability, high ionic conductivity and electrochemical stability, and dendrite‐free Li plating. When applied in Li metal batteries with a LiMn₂O₄ cathode, the DSP electrolyte effectively suppressed manganese dissolution from the cathode and enabled high‐capacity and a long lifespan at room and elevated temperatures.     

Facile Generation of Polymer–Alloy Hybrid Layers for Dendrite‐Free Lithium‐Metal Anodes with Improved Moisture Stability

Lithium‐metal anodes are recognized as the most promising next‐generation anodes for high‐energy‐storage batteries. However, lithium dendrites lead to irreversible capacity decay in lithium‐metal batteries (LMBs). Besides, the strict assembly‐environment conditions of LMBs are regarded as a challenge for practical applications. In this study, a workable lithium‐metal anode with an artificial hybrid layer composed of a polymer and an alloy was designed and prepared by a simple chemical‐modification strategy. Treated lithium anodes remained dendrite‐free for over 1000 h in a Li–Li symmetric cell and exhibited outstanding cycle performance in high‐areal‐loading Li–S and Li–LiFePO₄ full cells. Moreover, the treated lithium showed improved moisture stability that benefits from the hydrophobicity of the polymer, thus retaining good electrochemical performance after exposure to humid air.     

Building an Air Stable and Lithium Deposition Regulable Garnet Interface from Moderate‐Temperature Conversion Chemistry

Garnet‐type electrolytes suffer from unstable chemistry against air exposure, which generates contaminants on electrolyte surface and accounts for poor interfacial contact with the Li metal. Thermal treatment of the garnet at >700 °C could remove the surface contaminants, yet it regenerates the contaminants in the air, and aggravates the Li dendrite issue as more electron‐conducting defective sites are exposed. In a departure from the removal approach, here we report a new surface chemistry that converts the contaminants into a fluorinated interface at moderate temperature <180 °C. The modified interface shows a high electron tunneling barrier and a low energy barrier for Li⁺ surface diffusion, so that it enables dendrite‐proof Li plating/stripping at a high critical current density of 1.4 mA cm^?2. Moreover, the modified interface exhibits high chemical and electrochemical stability against air exposure, which prevents regeneration of contaminants and keeps high critical current density of 1.1 mA cm^?2. The new chemistry presents a practical solution for realization of high‐energy solid‐state Li metal batteries.     

Lithiophilic Sites in Doped Graphene Guide Uniform Lithium Nucleation for Dendrite‐Free Lithium Metal Anodes

Lithium (Li) metal is the most promising electrode for next‐generation rechargeable batteries. However, the challenges induced by Li dendrites on a working Li metal anode hinder the practical applications of Li metal batteries. Herein, nitrogen (N) doped graphene was adopted as the Li plating matrix to regulate Li metal nucleation and suppress dendrite growth. The N‐containing functional groups, such as pyridinic and pyrrolic nitrogen in the N‐doped graphene, are lithiophilic, which guide the metallic Li nucleation causing the metal to distribute uniformly on the anode surface. As a result, the N‐doped graphene modified Li metal anode exhibits a dendrite‐free morphology during repeated Li plating and demonstrates a high Coulombic efficiency of 98 % for near 200 cycles.     

Interfacial Design of Dendrite‐Free Zinc Anodes for Aqueous Zinc‐Ion Batteries

Aqueous zinc‐ion batteries have rapidly developed recently as promising energy storage devices in large‐scale energy storage systems owing to their low cost and high safety. Research on suppressing zinc dendrite growth has meanwhile attracted widespread attention to improve the lifespan and reversibility of batteries. Herein, design methods for dendrite‐free zinc anodes and their internal mechanisms are reviewed from the perspective of optimizing the host–zinc interface and the zinc–electrolyte interface. Furthermore, a design strategy is proposed to homogenize zinc deposition by regulating the interfacial electric field and ion distribution during zinc nucleation and growth. This Minireview can offer potential directions for the rational design of dendrite‐free zinc anodes employed in aqueous zinc‐ion batteries.     

Enhanced Performance of a Lithium–Sulfur Battery Using a Carbonate‐Based Electrolyte

The lithium–sulfur battery is regarded as one of the most promising candidates for lithium–metal batteries with high energy density. However, dendrite Li formation and low cycle efficiency of the Li anode as well as unstable sulfur based cathode still hinder its practical application. Herein a novel electrolyte (1 m LiODFB/EC‐DMC‐FEC) is designed not only to address the above problems of Li anode but also to match sulfur cathode perfectly, leading to extraordinary electrochemical performances. Using this electrolyte, lithium|lithium cells can cycle stably for above 2000 hours and the average Coulumbic efficiency reaches 98.8 %. Moreover, the Li–S battery delivers a reversible capacity of about 1400 mAh g^?1_sulfur with retention of 89 % for 1100 cycles at 1 C, and a capacity above 1100 mAh g^?1_sulfur at 10 C. The more advantages of this cell system are its outstanding cycle stability at 60 °C and no self‐discharge phenomena.     

A Flexible Solid Electrolyte Interphase Layer for Long‐Life Lithium Metal Anodes

Lithium (Li) metal is a promising anode material for high‐energy density batteries. However, the unstable and static solid electrolyte interphase (SEI) can be destroyed by the dynamic Li plating/stripping behavior on the Li anode surface, leading to side reactions and Li dendrites growth. Herein, we design a smart Li polyacrylic acid (LiPAA) SEI layer high elasticity to address the dynamic Li plating/stripping processes by self‐adapting interface regulation, which is demonstrated by in situ AFM. With the high binding ability and excellent stability of the LiPAA polymer, the smart SEI can significantly reduce the side reactions and improve battery safety markedly. Stable cycling of 700 h is achieved in the LiPAA‐Li/LiPAA‐Li symmetrical cell. The innovative strategy of self‐adapting SEI design is broadly applicable, providing opportunities for use in Li metal anodes     

High‐Temperature Formation of a Functional Film at the Cathode/Electrolyte Interface in Lithium–Sulfur Batteries: An In Situ AFM Study

Lithium–sulfur (Li–S) batteries have been attracting wide attention for their promising high specific capacity. A deep understanding of Li–S interfacial mechanism including the temperature (T) effect is required to meet the demands for battery modification and systematic study. Herein, the interfacial behavior during discharge/charge is investigated at high temperature (HT) of 60 °C in an electrolyte based on lithium bis(fluorosulfonyl) imide (LiFSI). By in situ atomic force microscopy (AFM), dynamic evolution of insoluble Li₂S₂ and Li₂S is studied at the nanoscale. An in situ formed functional film can be directly monitored at 60 °C after Li₂S nucleation. It retards side reactions and facilitates interfacial redox. The insight into the interfacial processes at HT provides direct evidence of the existence of the film and reveals its dynamic behavior, providing a new avenue for electrolyte design and performance enhancement.     

Active‐Oxygen‐Enhanced Homogeneous Nucleation of Lithium Metal on Ultrathin Layered Double Hydroxide

The development of safe lithium‐metal anodes is crucial for the next‐generation rechargeable batteries. To stabilize Li metal anodes, pre‐planting Li nucleation seeds on lithiophilic substrates is an efficient strategy to regulate initial nucleation process of Li metal. Now, activated ultrathin layered double hydroxide (U‐LDHs) are reported as a promising lithiophilic 2D material to realize the uniform deposition of Li metal. The experimental studies and DFT calculations reveal that the active oxygen on U‐LDHs provides abundant atomic‐scale active sites for Li homogeneous nucleation and plating. Moreover, the lithiophilic properties of active oxygen is also related to its coordination environments. This work opens up an opportunity to more accurate regulation and understanding of Li nucleation from atomic‐scale based on 2D ultrathin materials.     

Revisiting the Electroplating Process for Lithium‐Metal Anodes for Lithium‐Metal Batteries

Electroplating has been studied for centuries, not only in the laboratory but also in industry for machinery, electronics, automobile, aviation, and other fields. The lithium‐metal anode is the Holy Grail electrode because of its high energy density. But the recyclability of lithium‐metal batteries remains quite challenging. The essence of both conventional electroplating and lithium plating is the same, reduction of metal cations. Thus, industrial electroplating knowledge can be applied to revisit the electroplating process for lithium‐metal anodes. In conventional electroplating, some strategies like using additives, modifying substrates, applying pulse current, and agitating electrolyte have been explored to suppress dendrite growth. These methods are also effective in lithium‐metal anodes. Inspired by that, we revisit the fundamental electroplating theory for lithium‐metal anodes in this Minireview, mainly drawing attention to the theory of electroplating thermodynamics and kinetics. Analysis of essential differences between traditional electroplating and plating/stripping of lithium‐metal anodes is also presented. Thus, industrial electroplating knowledge can be applied to the electroplating process of lithium‐metal anodes to improve commercial lithium‐metal batteries and the study of lithium plating/stripping can further enrich the classical electroplating technique.