Dual‐Layered Film Protected Lithium Metal Anode to Enable Dendrite‐Free Lithium Deposition

Lithium metal batteries (such as lithium–sulfur, lithium–air, solid state batteries with lithium metal anode) are highly considered as promising candidates for next‐generation energy storage systems. However, the unstable interfaces between lithium anode and electrolyte definitely induce the undesired and uncontrollable growth of lithium dendrites, which results in the short‐circuit and thermal runaway of the rechargeable batteries. Herein, a dual‐layered film is built on a Li metal anode by the immersion of lithium plates into the fluoroethylene carbonate solvent. The ionic conductive film exhibits a compact dual‐layered feature with organic components (ROCO₂Li and ROLi) on the top and abundant inorganic components (Li₂CO₃ and LiF) in the bottom. The dual‐layered interface can protect the Li metal anode from the corrosion of electrolytes and regulate the uniform deposition of Li to achieve a dendrite‐free Li metal anode. This work demonstrates the concept of rational construction of dual‐layered structured interfaces for safe rechargeable batteries through facile surface modification of Li metal anodes. This not only is critically helpful to comprehensively understand the functional mechanism of fluoroethylene carbonate but also affords a facile and efficient method to protect Li metal anodes.     

Controlling Nucleation in Lithium Metal Anodes

Rechargeable batteries are regarded as the most promising candidates for practical applications in portable electronic devices and electric vehicles. In recent decades, lithium metal batteries (LMBs) have been extensively studied due to their ultrahigh energy densities. However, short lifespan and poor safety caused by uncontrollable dendrite growth hinder their commercial applications. Besides, a clear understanding of Li nucleation and growth has not yet been obtained. In this Review, the failure mechanisms of Li metal anodes are ascribed to high reactivity of lithium, virtually infinite volume changes, and notorious dendrite growth. The principles of Li deposition nucleation and early dendrite growth are discussed and summarized. Correspondingly, four rational strategies of controlling nucleation are proposed to guide Li nucleation and growth. Finally, perspectives for understanding the Li metal deposition process and realizing safe and high‐energy rechargeable LMBs are given.     

Lithium Foam for Deep Cycling Lithium Metal Batteries

Li metal anode has been recognized as the most promising anode for its high theoretical capacity and low reduction potential. But its large-scale commercialization is hampered because of the infinite volume expansion, severe side reactions, and uncontrollable dendrite formation. Herein, the self-supporting porous lithium foam anode is obtained by a melt foaming method. The adjustable interpenetrating pore structure and dense Li₃N protective layer coating on the inner surface enable the lithium foam anode with great tolerance to electrode volume variation, parasitic reaction, and dendritic growth during cycling. Full cell using high areal capacity (4.0 mAh cm⁻²) LiNi0.8Co0.1Mn0.1 (NCM811) cathode with the N/P ratio of 2 and E/C ratio of 3 g Ah⁻¹ can stably operate for 200 times with 80% capacity retention. The corresponding pouch cell has <3% pressure fluctuation per cycle and almost zero pressure accumulation.     

Enabling Rapid Charging Lithium Metal Batteries via Surface Acoustic Wave-Driven Electrolyte Flow

Both powerful and unstable, practical lithium metal batteries have remained a difficult challenge for over 50 years. With severe ion depletion gradients in the electrolyte during charging, they rapidly develop porosity, dendrites, and dead Li that cause poor performance and, all too often, spectacular failure. Remarkably, incorporating a small, 100 MHz surface acoustic wave device (SAW) solves this problem. Providing acoustic streaming electrolyte flow during charging, the device enables dense Li plating and avoids porosity and dendrites. SAW-integrated Li cells can operate up to 6 mA cm⁻² in a commercial carbonate-based electrolyte; omitting the SAW leads to short circuiting at 2 mA cm⁻². The Li deposition is morphologically dendrite-free and close to theoretical density when cycling with the SAW. With a 245 µm thick Li anode in a full Li||LFP (LiFePO₄) cell, introducing the SAW increases the uncycled Li from 145 to 225 µm, decreasing Li consumption from 41% to only 8%. A closed-form model is provided to explain the phenomena and serve as a design tool for integrating this chemistry-agnostic approach into batteries whatever the chemistry within.     

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。     

Nanostructured Silicon Anodes for Lithium Ion Rechargeable Batteries

Rechargeable lithium ion batteries are integral to today's information‐rich, mobile society. Currently they are one of the most popular types of battery used in portable electronics because of their high energy density and flexible design. Despite their increasing use at the present time, there is great continued commercial interest in developing new and improved electrode materials for lithium ion batteries that would lead to dramatically higher energy capacity and longer cycle life. Silicon is one of the most promising anode materials because it has the highest known theoretical charge capacity and is the second most abundant element on earth. However, silicon anodes have limited applications because of the huge volume change associated with the insertion and extraction of lithium. This causes cracking and pulverization of the anode, which leads to a loss of electrical contact and eventual fading of capacity. Nanostructured silicon anodes, as compared to the previously tested silicon film anodes, can help overcome the above issues. As arrays of silicon nanowires or nanorods, which help accommodate the volume changes, or as nanoscale compliant layers, which increase the stress resilience of silicon films, nanoengineered silicon anodes show potential to enable a new generation of lithium ion batteries with significantly higher reversible charge capacity and longer cycle life.     

Self‐Suppression of Lithium Dendrite in All‐Solid‐State Lithium Metal Batteries with Poly(vinylidene difluoride)‐Based Solid Electrolytes

Polymer‐based electrolytes have attracted ever‐increasing attention for all‐solid‐state lithium (Li) metal batteries due to their ionic conductivity, flexibility, and easy assembling into batteries, and are expected to overcome safety issues by replacing flammable liquid electrolytes. However, it is still a critical challenge to effectively block Li dendrite growth and improve the long‐term cycling stability of all‐solid‐state batteries with polymer electrolytes. Here, the interface between novel poly(vinylidene difluoride) (PVDF)‐based solid electrolytes and the Li anode is explored via systematical experiments in combination with first‐principles calculations, and it is found that an in situ formed nanoscale interface layer with a stable and uniform mosaic structure can suppress Li dendrite growth. Unlike the typical short‐circuiting that often occurs in most studied poly(ethylene oxide) systems, this interface layer in the PVDF‐based system causes an open‐circuiting feature at high current density and thus avoids the risk of over‐current. The effective self‐suppression of the Li dendrite observed in the PVDF–LiN(SO₂F)₂ (LiFSI) system enables over 2000 h cycling of repeated Li plating–stripping at 0.1 mA cm^?2 and excellent cycling performance in an all‐solid‐state LiCoO₂||Li cell with almost no capacity fade after 200 cycles at 0.15 mA cm^?2 at 25 °C. These findings will promote the development of safe all‐solid‐state Li metal batteries.     

静电纺丝法制备氧化锰纳米丝电极及其电化学性能

利用静电纺丝技术成功制备了φ60～80nm的氧化锰纳米纤维丝,并构建了三维纳米丝网状结构电极,应用于锂离子二次电池. 使用扫描电子显微镜、X射线衍射、循环伏安和电池充放电等研究手段,表征了纳米纤维丝的结构和电化学性能. 研究结果发现:氧化锰构建的纳米丝在嵌锂和脱锂的过程中没有出现纳米纤维丝的结构塌陷问题,在高能量密度下表现出较大的可逆循环容量,放电容量达到160mAh/g. 经过50次循环后, 容量可达132.5mAh/g, 平均每次循环的容量衰减在1%以下. 这些结果表明了氧化锰纳米纤维丝可作为三维锂离子电池中的阴极材料.     

Nanocellulose Modified Polyethylene Separators for Lithium Metal Batteries

Poor cycling stability and safety concerns regarding lithium (Li) metal anodes are two major issues preventing the commercialization of high‐energy density Li metal‐based batteries. Herein, a novel tri‐layer separator design that significantly enhances the cycling stability and safety of Li metal‐based batteries is presented. A thin, thermally stable, flexible, and hydrophilic cellulose nanofiber layer, produced using a straightforward paper‐making process, is directly laminated on each side of a plasma‐treated polyethylene (PE) separator. The 2.5 µm thick, mesoporous (≈20 nm average pore size) cellulose nanofiber layer stabilizes the Li metal anodes by generating a uniform Li⁺ flux toward the electrode through its homogenous nanochannels, leading to improved cycling stability. As the tri‐layer separator maintains its dimensional stability even at 200 °C when the internal PE layer is melted and blocks the ion transport through the separator, the separator also provides an effective thermal shutdown function. The present nanocellulose‐based tri‐layer separator design thus significantly facilitates the realization of high‐energy density Li metal‐based batteries.     

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.     

锂离子二次电池多孔集流体的制备与应用

金属基负极材料具有超高的理论容量,是新一代锂离子二次电池理想的负极材料。但是,金属基负极材料在充放电过程中会产生严重的体积膨胀,从而导致负极材料的粉化和脱落,使其循环性能迅速恶化。采用多孔集流体能够充分利用三维连通的孔隙和高的比表面积来显著提高锂离子二次电池的循环性能和能量密度,是缓解金属基负极材料体积膨胀的有效方法之一。本文总结了近年来微米多孔、纳米多孔和双尺度多孔集流体的制备方法及其在锂离子二次电池中的应用。     

Dual‐Phase Single‐Ion Pathway Interfaces for Robust Lithium Metal in Working Batteries

The lithium (Li) metal anode is confronted by severe interfacial issues that strongly hinder its practical deployment. The unstable interfaces directly induce unfavorable low cycling efficiency, dendritic Li deposition, and even strong safety concerns. An advanced artificial protective layer with single‐ion pathways holds great promise for enabling a spatially homogeneous ionic and electric field distribution over Li metal surface, therefore well protecting the Li metal anode during long‐term working conditions. Herein, a robust dual‐phase artificial interface is constructed, where not only the single‐ion‐conducting nature, but also high mechanical rigidity and considerable deformability can be fulfilled simultaneously by the rational integration of a garnet Al‐doped Li_6.75La₃Zr_1.75Ta_0.25O₁₂‐based bottom layer and a lithiated Nafion top layer. The as‐constructed artificial solid electrolyte interphase is demonstrated to significantly stabilize the repeated cell charging/discharging process via regulating a facile Li‐ion transport and a compact Li plating behavior, hence contributing to a higher coulombic efficiency and a considerably enhanced cyclability of lithium metal batteries. This work highlights the significance of rational manipulation of the interfacial properties of a working Li metal anode and affords fresh insights into achieving dendrite‐free Li deposition behavior in a working battery.     

Interlayered Dendrite‐Free Lithium Plating for High‐Performance Lithium‐Metal Batteries

For its high theoretical capacity and low redox potential, Li metal is considered to be one of the most promising anode materials for next‐generation batteries. However, practical application of a Li‐metal anode is impeded by Li dendrites, which are generated during the cycling of Li plating/stripping, leading to safety issues. Researchers attempt to solve this problem by spatially confining the Li plating. Yet, the effective directing of Li deposition into the confined space is challenging. Here, an interlayer is constructed between a graphitic carbon nitrite layer (g‐C₃N₄) and carbon cloth (CC), enabling site‐directed dendrite‐free Li plating. The g‐C₃N₄/CC as an anode scaffold enables extraordinary cycling stability for over 1500 h with a small overpotential of ≈80 mV at 2 mA cm^?2. Furthermore, prominent battery performance is also demonstrated in a full cell (Li/g‐C₃N₄/CC as anode and LiCoO₂ as cathode) with high Coulombic efficiency of 99.4% over 300 cycles.     

锂离子电池炭负极材料结构及嵌锂机理研究进展

炭材料取代金属锂作为负极后,锂离子电池在商业应用上取得了成功,并以其高能量密度在各种电子设备上广泛使用.锂离子电池的性能很大程度上取决于炭负极材料的微观结构,不同种类的炭材料其电化学性能有很大差别.对近几年所研究的可逆储锂炭材料进行了综述,着重总结了炭负极材料的种类、结构及其嵌锂机理,并展望了锂离子电池炭负极材料的研究进展.     

锂离子电池高容量硅负极嵌锂过程中的表面成膜研究

采用交流阻抗法、EDS与XPS成分分析对锂离子电池高容量硅负极在首次嵌锂过程中的表面成膜行为进行了研究, 并对膜组分进行了详细测试与分析. 交流阻抗分析发现硅负极的表面成膜现象出现在较低的嵌锂电位下, 膜厚随着嵌锂过程的进行而增加, 其组分以LiF和Li₂CO₃为主. 通过Ar离子流对硅负极表面的深度刻蚀的XPS分析发现, 其表面的膜层为非均质层, 暴露于电解液中一侧的膜层组分中碳酸盐含量较高, 而随着深度的增加, LiF的相对含量增加, 靠近电极一侧的膜层可能存在着少量硅的氧化物及其与电解液的反应产物. 少量Si由于不可逆反应形成的化合物也存在于SEI膜的膜层中.     

High-Safety and High-Energy-Density Lithium Metal Batteries in a Novel Ionic-Liquid Electrolyte

Rechargeable lithium metal batteries are next generation energy storage devices with high energy density, but face challenges in achieving high energy density, high safety, and long cycle life. Here, lithium metal batteries in a novel nonflammable ionic-liquid (IL) electrolyte composed of 1-ethyl-3-methylimidazolium (EMIm) cations and high-concentration bis(fluorosulfonyl)imide (FSI) anions, with sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a key additive are reported. The Na ion participates in the formation of hybrid passivation interphases and contributes to dendrite-free Li deposition and reversible cathode electrochemistry. The electrolyte of low viscosity allows practically useful cathode mass loading up to ≈16 mg cm⁻². Li anodes paired with lithium cobalt oxide (LiCoO₂) and lithium nickel cobalt manganese oxide (LiNi_0.8Co_0.1Mn_0.1O₂, NCM 811) cathodes exhibit 99.6–99.9% Coulombic efficiencies, high discharge voltages up to 4.4 V, high specific capacity and energy density up to ≈199 mAh g⁻¹ and ≈765 Wh kg⁻¹ respectively, with impressive cycling performances over up to 1200 cycles. Highly stable passivation interphases formed on both electrodes in the novel IL electrolyte are the key to highly reversible lithium metal batteries, especially for Li–NMC 811 full batteries.