Dendrite-Free Potassium Metal Anodes in a Carbonate Electrolyte

Potassium (K) metal anodes suffer from a challenging problem of dendrite growth. Here, it is demonstrated that a tailored current collector will stabilize the metal plating–stripping behavior even with a conventional KPF₆-carbonate electrolyte. A 3D copper current collector is functionalized with partially reduced graphene oxide to create a potassiophilic surface, the electrode being denoted as rGO@3D-Cu. Potassiophilic versus potassiophobic experiments demonstrate that molten K fully wets rGO@3D-Cu after 6 s, but does not wet unfunctionalized 3D-Cu. Electrochemically, a unique synergy is achieved that is driven by interfacial tension and geometry: the adherent rGO underlayer promotes 2D layer-by-layer (Frank–van der Merwe) metal film growth at early stages of plating, while the tortuous 3D-Cu electrode reduces the current density and geometrically frustrates dendrites. The rGO@3D-Cu symmetric cells and half-cells achieve state-of-the-art plating and stripping performance. The symmetric rGO@3D-Cu cells exhibit stable cycling at 0.1–2 mA cm⁻², while baseline Cu prematurely fails when the current reaches 0.5 mA cm⁻². The half-cells cells of rGO@3D-Cu (no K reservoir) are stable at 0.5 mA cm⁻² for 10 000 min (100 cycles), and at 1 mA cm⁻² for 5000 min. The baseline 3D-Cu, planar rGO@Cu, and planar Cu foil fails after 5110, 3012, and 1410 min, respectively.     

Stable Potassium Metal Anodes with an All-Aluminum Current Collector through Improved Electrolyte Wetting

This is the first report of successful potassium metal battery anode cycling with an aluminum-based rather than copper-based current collector. Dendrite-free plating/stripping is achieved through improved electrolyte wetting, employing an aluminum-powder-coated aluminum foil “Al@Al,” without any modification of the support surface chemistry or electrolyte additives. The reservoir-free Al@Al half-cell is stable at 1000 cycles (1950 h) at 0.5 mA cm⁻², with 98.9% cycling Coulombic efficiency and 0.085 V overpotential. The pre-potassiated cell is stable through a wide current range, including 130 cycles (2600 min) at 3.0 mA cm⁻², with 0.178 V overpotential. Al@Al is fully wetted by a 4 m potassium bis(fluorosulfonyl)imide-dimethoxyethane electrolyte (θ_CA  = 0 ° ), producing a uniform solid electrolyte interphase (SEI) during the initial galvanostatic formation cycles. On planar aluminum foil with a nearly identical surface oxide, the electrolyte wets poorly (θ_CA  = 52 ° ). This correlates with coarse irregular SEI clumps at formation, 3D potassium islands with further SEI coarsening during plating/stripping, possibly dead potassium metal on stripped surfaces, and rapid failure. The electrochemical stability of Al@Al versus planar Al is not related to differences in potassiophilicity (nearly identical) as obtained from thermal wetting experiments. Planar Cu foils are also poorly electrolyte-wetted and become dendritic. The key fundamental takeaway is that the incomplete electrolyte wetting of collectors results in early onset of SEI instability and dendrites.     

Novel Organophosphate-Derived Dual-Layered Interface Enabling Air-Stable and Dendrite-Free Lithium Metal Anode

Lithium (Li) metal, as a promising candidate for next-generation energy storage systems, suffers from an extremely unstable interface that is prone to crack, causing serious corrosion of Li metal and dendrite growth. To address this, a novel dual-layered interface on the Li metal anode is reported, which is featured with organics ( COPO₃ ,  (CO)₂PO₂ , and  (CO)₃PO) on the top and inorganics (Li₃PO₄) at the bottom. The flexible organic layer with reduced Young's modulus (≈550 MPa) contributes to maintain structural integrity, while the rigid inorganic layer with improved Young's modulus of ≈12 GPa is beneficial to suppress the Li dendrite growth. Accordingly, the protected Li is stabilized to maintain successive electrodeposition over 800 cycles of plating/stripping process at a current density of 2 mA cm⁻². Furthermore, the uniform dual-layered interface tends to prevent the corrosion of air to Li metal, exhibiting almost the same performance as the Li metal treated in the inert atmosphere.     

Structure-Controlled Carbon Hosts for Dendrite-Free Aqueous Zinc Batteries

The surging demand for environmental-friendly and safe electrochemical energy storage systems has driven the development of aqueous zinc (Zn)-ion batteries (ZIBs). However, metallic Zn anodes suffer from severe dendrite growth and large volume change, resulting in a limited lifetime for aqueous ZIB applications. Here, it is shown that 3D mesoporous carbon (MC) with controlled carbon and defect configurations can function as a highly reversible and dendrite-free Zn host, enabling the stable operation of aqueous ZIBs. The MC host has a structure-controlled architecture that contains optimal sp²-carbon and defect sites, which results in an improved initial nucleation energy barrier and promotes uniform Zn deposition. As a consequence, the MC host shows outstanding Zn plating/stripping performance over 1000 cycles at 2 mA cm⁻² and over 250 cycles at 6 mA cm⁻² in asymmetric cells. Density functional theory calculations further reveal the role of the defective sp²-carbon surface in Zn adsorption energy. Moreover, a full cell based on Zn@MC900 anode and V₂O₅ cathode exhibits remarkable rate performance and cycling stability over 3500 cycles. These results establish a structure-mechanism-performance relationship of the carbon host as a highly reversible Zn anode for the reliable operation of ZIBs.     

Highly Stable Potassium Metal Anodes with Controllable Thickness and Area Capacity

K metal battery is a kind of high-energy-density storage device with economic advantages. However, due to the dendrite growth and difficult processing characteristics, it is difficult to prepare stable K metal anode with thin thickness and fixed area capacity, which severely limits its development. In this work, a multi-functional 3D skeleton (rGCA) is synthesized by simple vacuum filtration and thermal reduction, and K metal anodes with controllable thickness and area capacity (K content) can be fabricated by changing the raw material mass and graphene layer spacing of rGCA. Moreover, the graphene sheet layer of rGCA can relax stress and relieve volume expansion; carbon nanotubes can serve as the fast transport channel of electrons, reducing internal impedance and local current density; Ag nanoparticles can induce the uniform nucleation and deposition of K⁺. The K metal composite anodes (rGCA-K) based on the conductive skeleton can effectively suppress dendrites and exhibit excellent electrochemical performance in symmetric and full cells. The controllable fabrication process of stable K metal anode is expected to help K metal batteries move toward the stage of commercial production.     

Electrolyte Regulation of Bio-Inspired Zincophilic Additive toward High-Performance Dendrite-Free Aqueous Zinc-Ion Batteries

Aqueous zinc-ion batteries hold attractive potential for large-scale energy storage devices owing to their prominent electrochemical performance and high security. Nevertheless, the applications of aqueous electrolytes have generated various challenges, including uncontrolled dendrite growth and parasitic reactions, thereby deteriorating the Zn anode's stability. Herein, inspired by the superior affinity between Zn²⁺ and amino acid chains in the zinc finger protein, a cost-effective and green glycine additive is incorporated into aqueous electrolytes to stabilize the Zn anode. As confirmed by experimental characterizations and theoretical calculations, the glycine additives can not only reorganize the solvation sheaths of hydrated Zn²⁺ via partial substitution of coordinated H₂O but also preferentially adsorb onto the Zn anode, thereby significantly restraining dendrite growth and interfacial side reactions. Accordingly, the Zn anode could realize a long lifespan of over 2000 h and enhanced reversibility (98.8%) in the glycine-containing electrolyte. Furthermore, the assembled Zn||α-MnO₂ full cells with glycine-modified electrolyte also delivers substantial capacity retention (82.3% after 1000 cycles at 2 A g^-1), showing promising application prospects. This innovative bio-inspired design concept would inject new vitality into the development of aqueous electrolytes.     

Enhancing Interfacial Strength and Wettability for Wide-Temperature Sodium Metal Batteries

Development of high-performance sodium metal batteries (SMBs) with a wide operating temperature range (from −40 to 55 °C) is highly challenging. Herein, an artificial hybrid interlayer composed of sodium phosphide (Na₃P) and metal vanadium (V) is constructed for wide-temperature-range SMBs via vanadium phosphide pretreatment. As evidenced by simulation, the VP-Na interlayer can regulate redistribution of Na⁺ flux, which is beneficial for homogeneous Na deposition. Moreover, the experimental results confirm that the artificial hybrid interlayer possesses a high Young's modulus and a compact structure, which can effectively suppress Na dendrite growth and alleviate the parasitic reaction even at 55 °C. In addition, the VP-Na interlayer exhibits the capability to knock down the kinetic barriers for fast Na⁺ transportation, realizing a 30-fold decrease in impedance at −40 °C. Symmetrical VP-Na cells present a prolonged lifespan reaching 1200, 500, and 500 h at room temperature, 55 °C and −40 °C, respectively. In Na₃V₂(PO₄)₃||VP-Na full cells, a high reversible capacity of 88, 89.8, and 50.3 mAh g⁻¹ can be sustained after 1600, 1000, and 600 cycles at room temperature, 55 °C and −40 °C, respectively. The pretreatment formed artificial hybrid interlayer proves to be an effective strategy to achieve wide-temperature-range SMBs.     

Design Strategies to Enable the Efficient Use of Sodium Metal Anodes in High-Energy Batteries

Sodium-based batteries have attracted considerable attention and are recognized as ideal candidates for large-scale and low-cost energy storage. Sodium (Na) metal anodes are considered as one of the most promising anodes for next-generation, high-energy, Na-based batteries owing to their high theoretical specific capacity (1166 mA h g⁻¹) and low standard electrode potential. Herein, an overview of the recent developments in Na metal anodes for high-energy batteries is provided. The high reactivity and large volume expansion of Na metal anodes during charge and discharge make the electrode/electrolyte interphase unstable, leading to the formation of Na dendrites, short cycle life, and safety issues. Design strategies to enable the efficient use of Na metal anodes are elucidated, including liquid electrolyte engineering, electrode/electrolyte interface optimization, sophisticated electrode construction, and solid electrolyte engineering. Finally, the remaining challenges and future research directions are identified. It is hoped that this progress report will shape a consistent view of this field and provide inspiration for future research to improve Na metal anodes and enable the development of high-energy sodium batteries.     

Key Aspects of Lithium Metal Anodes for Lithium Metal Batteries

Rechargeable batteries are considered promising replacements for environmentally hazardous fossil fuel‐based energy technologies. High‐energy lithium‐metal batteries have received tremendous attention for use in portable electronic devices and electric vehicles. However, the low Coulombic efficiency, short life cycle, huge volume expansion, uncontrolled dendrite growth, and endless interfacial reactions of the metallic lithium anode are major obstacles in their commercialization. Extensive research efforts have been devoted to address these issues and significant progress has been made by tuning electrolyte chemistry, designing electrode frameworks, discovering nanotechnology‐based solutions, etc. This Review aims to provide a conceptual understanding of the current issues involved in using a lithium metal anode and to unveil its electrochemistry. The most recent advancements in lithium metal battery technology are outlined and suggestions for future research to develop a safe and stable lithium anode are presented.     

Protected Lithium‐Metal Anodes in Batteries: From Liquid to Solid

High‐energy lithium‐metal batteries are among the most promising candidates for next‐generation energy storage systems. With a high specific capacity and a low reduction potential, the Li‐metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li‐metal anodes. Recent studies have shown that the performance and safety of Li‐metal anodes can be significantly improved via organic electrolyte modification, Li‐metal interface protection, Li‐electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid‐state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li‐metal batteries. Inspired by the bright prospects of solid Li‐metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li‐metal batteries, such as low ionic conductivity of the electrolyte and Li–electrolyte interfacial problems. Here, the approaches to protect Li‐metal anodes from liquid batteries to solid‐state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li‐metal anodes are discussed to facilitate the practical application of Li‐metal batteries.     

Defect Engineering on Electrode Materials for Rechargeable Batteries

The reasonable design of electrode materials for rechargeable batteries plays an important role in promoting the development of renewable energy technology. With the in-depth understanding of the mechanisms underlying electrode reactions and the rapid development of advanced technology, the performance of batteries has significantly been optimized through the introduction of defect engineering on electrode materials. A large number of coordination unsaturated sites can be exposed by defect construction in electrode materials, which play a crucial role in electrochemical reactions. Herein, recent advances regarding defect engineering in electrode materials for rechargeable batteries are systematically summarized, with a special focus on the application of metal-ion batteries, lithium–sulfur batteries, and metal–air batteries. The defects can not only effectively promote ion diffusion and charge transfer but also provide more storage/adsorption/active sites for guest ions and intermediate species, thus improving the performance of batteries. Moreover, the existing challenges and future development prospects are forecast, and the electrode materials are further optimized through defect engineering to promote the development of the battery industry.     

Dendrite‐Free Sodium‐Metal Anodes for High‐Energy Sodium‐Metal Batteries

Sodium (Na) metal is one of the most promising electrode materials for next‐generation low‐cost rechargeable batteries. However, the challenges caused by dendrite growth on Na metal anodes restrict practical applications of rechargeable Na metal batteries. Herein, a nitrogen and sulfur co‐doped carbon nanotube (NSCNT) paper is used as the interlayer to control Na nucleation behavior and suppress the Na dendrite growth. The N‐ and S‐containing functional groups on the carbon nanotubes induce the NSCNTs to be highly “sodiophilic,” which can guide the initial Na nucleation and direct Na to distribute uniformly on the NSCNT paper. As a result, the Na‐metal‐based anode (Na/NSCNT anode) exhibits a dendrite‐free morphology during repeated Na plating and striping and excellent cycling stability. As a proof of concept, it is also demonstrated that the electrochemical performance of sodium–oxygen (Na–O₂) batteries using the Na/NSCNT anodes show significantly improved cycling performances compared with Na–O₂ batteries with bare Na metal anodes. This work opens a new avenue for the development of next‐generation high‐energy‐density sodium‐metal batteries.     

High Capacity,Dendrite‐Free Growth,and Minimum Volume Change Na Metal Anode

Na metal anode attracts increasing attention as a promising candidate for Na metal batteries (NMBs) due to the high specific capacity and low potential. However, similar to issues faced with the use of Li metal anode, crucial problems for metallic Na anode remain, including serious moss‐like and dendritic Na growth, unstable solid electrolyte interphase formation, and large infinite volume changes. Here, the rational design of carbon paper (CP) with N‐doped carbon nanotubes (NCNTs) as a 3D host to obtain Na@CP‐NCNTs composites electrodes for NMBs is demonstrated. In this design, 3D carbon paper plays a role as a skeleton for Na metal anode while vertical N‐doped carbon nanotubes can effectively decrease the contact angle between CP and liquid metal Na, which is termed as being “Na‐philic.” In addition, the cross‐conductive network characteristic of CP and NCNTs can decrease the effective local current density, resulting in uniform Na nucleation. Therefore, the as‐prepared Na@CP‐NCNT exhibits stable electrochemical plating/stripping performance in symmetrical cells even when using a high capacity of 3 mAh cm^?2 at high current density. Furthermore, the 3D skeleton structure is observed to be intact following electrochemical cycling with minimum volume change and is dendrite‐free in nature.     

Copper Nitride Nanowires Printed Li with Stable Cycling for Li Metal Batteries in Carbonate Electrolytes

The practical implementation of the lithium metal anode is hindered by obstacles such as Li dendrite growth, large volume changes, and poor lifespan. Here, copper nitride nanowires (Cu₃N NWs) printed Li by a facile and low-cost roll-press method is reported, to operate in carbonate electrolytes for high-voltage cathode materials. Through one-step roll pressing, Cu₃N NWs can be conformally printed onto the Li metal surface, and form a Li₃N@Cu NWs layer on the Li metal. The Li₃N@Cu NWs layer can assist homogeneous Li-ion flux with the 3D channel structure, as well as the high Li-ion conductivity of the Li₃N. With those beneficial effects, the Li₃N@Cu NWs layer can guide Li to deposit into a dense and planar structure without Li-dendrite growth. Li metal with Li₃N@Cu NWs protection layer exhibits outstanding cycling performances even at a high current density of 5.0 mA cm⁻² with low overpotentials in Li symmetric cells. Furthermore, the stable cyclability and improved rate capability can be realized in a full cell using LiCoO₂ over 300 cycles. When decoupling the irreversible reactions of the cathode using Li₄T_i5O₁₂, stable cycling performance over 1000 cycles can be achieved at a practical current density of ≈2 mA cm⁻².     

Lithiophilic LiC6 Layers on Carbon Hosts Enabling Stable Li Metal Anode in Working Batteries

Lithium (Li) metal‐based battery is among the most promising candidates for next‐generation rechargeable high‐energy‐density batteries. Carbon materials are strongly considered as the host of Li metal to relieve the powdery/dendritic Li formation and large volume change during repeated cycles. Herein, we describe the formation of a thin lithiophilic LiC₆ layer between carbon fibers (CFs) and metallic Li in Li/CF composite anode obtained through a one‐step rolling method. An electron deviation from Li to carbon elevates the negativity of carbon atoms after Li intercalation as LiC₆, which renders stronger binding between carbon framework and Li ions. The Li/CF | Li/CF batteries can operate for more than 90 h with a small polarization voltage of 120 mV at 50% discharge depth. The Li/CF | sulfur pouch cell exhibits a high discharge capacity of 3.25 mAh cm^?2 and a large capacity retention rate of 98% after 100 cycles at 0.1 C. It is demonstrated that the as‐obtained Li/CF composite anode with lithiophilic LiC₆ layers can effectively alleviate volume expansion and hinder dendritic and powdery morphology of Li deposits. This work sheds fresh light on the role of interfacial layers between host structure and Li metal in composite anode for long‐lifespan working batteries.     

Anode Interface Engineering and Architecture Design for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are considered as one of the most promising options to realize rechargeable batteries with high energy capacity. Previously, research has mainly focused on solving the polysulfides' shuttle, cathode volume changes, and sulfur conductivity problems. However, the instability of anodes in Li–S batteries has become a bottleneck to achieving high performance. Herein, the main efforts to develop highly stable anodes for Li–S batteries, mainly including lithium metal anodes, carbon‐based anodes, and alloy‐based anodes, are considered. Based on these anodes, their interfacial engineering and structure design are identified as the two most important directions to achieve ideal anodes. Because of high reactivity and large volume change during cycling, Li anodes suffer from severe side reactions and structure collapse. The solid electrolyte interphase formed in situ by modified electrolytes and ex situ artificial coating layers can enhance the interfacial stability of anodes. Replacing common Li foil with rationally designed anodes not only suppresses the formation of dendritic Li but also delays the failure of Li anodes. Manipulating the anode interface engineering and rationally designing anode architecture represents an attractive path to develop high‐performance Li–S batteries.     

面向可充电电池的锂金属负极的枝晶生长:理论基础、影响因素和抑制方法

在全球能源与环境问题日趋紧迫的大背景下,可再生能源的获取与利用途径及高效安全的储能技术的研发一直是工业界和科学界关注的热点之一。锂离子二次电池作为能量存储器件,拥有高比能量、长循环寿命等优点,近十几年来其研究取得了长足进展,并在各类便携式电子设备和电动交通工具中获得了广泛应用。然而,随着各种高性能设备的不断涌现,商业化的锂离子电池越来越难以满足其在能量密度、循环稳定性和安全性等方面的要求。为了进一步提高锂离子电池的能量密度,需要开发出高比容量的负极材料(硅、锡和锂等)以取代传统石墨负极。硅、锡等新式负极材料通过与锂离子反应形成含锂化合物的原理来存储与释放锂离子,完成电池的一个充放电过程。这个过程往往伴随着负极材料体积的剧烈变化,经历较长时间循环使用后会导致负极材料的粉化甚至从集流体上剥离,引起电池容量迅速衰减甚至失效。而锂负极通过锂在负极上的溶解和沉积来完成电池的充放电过程,该过程不存在反应相变所导致的体积变化。另外,锂金属负极材料具有极高的质量比容量(3 860mAh/g)、低密度(0.59g/cm3)和低的还原电位(-3.04V,相比于氢标准电极),被认为是一种理想的可充电电池负极材料。然而,锂的枝晶生长、锂金属电池低的库伦效率和锂的无主体沉积引起的体积膨胀等一些关键问题长期以来制约着锂负极的商业应用。锂的每次沉积都会产生枝晶,在充放电循环中,锂枝晶会导致电池内部短路甚至发生爆炸,带来严重的安全问题。除此之外,锂枝晶还会增加负极表面积,新暴露的锂金属会与电解液反应生成固态电解质膜(Solid electrolyte interface,SEI),这会损耗活性材料以及降低电池的库伦效率。为了解决以上问题,研究者们对锂金属电极进行了许多探索,尤其是在锂枝晶生长的机理及其抑制方法方面。一些理论模型如扩散模型、SEI保护模型、电荷诱导生长模型和薄膜生长模型等,以及与这些模型相对应的一些抑制方法如均匀锂离子流法、SEI膜保护法、稳定沉积主体法和静电屏蔽保护法等被提出。这些抑制方法能够在一定程度上缓解锂枝晶的生长问题,但都未能达到商业化应用的要求。本文总结了近几年研究人员针对锂离子电池锂金属负极的一些重要研究,系统地介绍了业内较为认同的枝晶生长模型和影响因素,并着重叙述了抑制枝晶生长的方法及成效,最后就锂金属负极将来的研究方向给出一些建议。     

Recent Advances in Energy Chemical Engineering of Next-Generation Lithium Batteries

Rechargeable lithium-ion batteries (LIBs) afford a profound impact on our modern daily life. However, LIBs are approaching the theoretical energy density, due to the inherent limitations of intercalation chemistry; thus, they cannot further satisfy the increasing demands of portable electronics, electric vehicles, and grids. Therefore, battery chemistries beyond LIBs are being widely investigated. Next-generation lithium (Li) batteries, which employ Li metal as the anode and intercalation or conversion materials as the cathode, receive the most intensive interest due to their high energy density and excellent potential for commercialization. Moreover, significant progress has been achieved in Li batteries attributed to the increasing fundamental understanding of the materials and reactions, as well as to technological improvement. This review starts by summarizing the electrolytes for next-generation Li batteries. Key challenges and recent progress in lithium-ion, lithium–sulfur, and lithium–oxygen batteries are then reviewed from the perspective of energy and chemical engineering science. Finally, possible directions for further development in Li batteries are presented. Next-generation Li batteries are expected to promote the sustainable development of human civilization.