高性能锂金属电池负极结构设计及界面强化研究进展

锂离子电池(LIBs)作为目前使用最广泛的二次电池,绝大多数以理论比容量较低的石墨(372 m Ah/g)为负极,已无法满足人们日益增长的对电池储能性能的要求。金属锂因其超高的理论比容量(3 860 m Ah/g)和最低的还原电势(-3.04 V,相比于氢标准电极)被看作是下一代高能量密度可充电锂电池最理想的负极材料。尤其是当金属锂与硫、氧组成锂-硫或锂-氧电池体系时,其理论能量密度远超锂离子电池,受到研究者的广泛关注。然而,库伦效率低和稳定性差一直是限制锂金属电池商业化应用的关键因素。当金属锂直接用作电池负极时,其易与电解液反应,在其表面形成一层脆弱的固态电解质中间相(SEI)膜。电池循环时,负极体积膨胀会破坏SEI膜,诱导锂枝晶和“死锂”形成,造成不可逆的容量损失。此外,锂枝晶生长至一定程度后会刺穿隔膜,导致电池内部短路甚至发生爆炸,引发严重的安全问题。为了解决上述问题,研究者们在锂金属负极失效机制、结构设计及界面强化等方面进行了许多探索。一些研究枝晶生长的理论模型如Chazalviel-Brissot模型、Yamaki模型和静电屏蔽模型等已受到广泛认可。在此基础上,研究者们尝试通...     

电解液化学保护锂金属电池负极的研究进展

锂金属电池被认为是最具潜力的高能量密度储能器件之一,但是锂金属电池负极低库仑效率及不可控的枝晶生长等问题阻碍了其商业化进程.在锂金属电池中,电解液会直接参与固态电解质界面膜(SEI)的形成,对锂金属负极的库仑效率、枝晶生长等产生重要影响.传统LiPF6基酯类电解液中,锂金属库仑效率低,且锂枝晶现象严重.近年来通过电解液添加剂、溶剂、锂盐以及锂盐浓度等途径调控电解液化学,在锂金属负极保护上取得了显著效果.例如,采用与锂金属负极兼容性更佳的醚类溶剂,可以降低电解液与锂金属的反应性;采用多种添加剂与新型锂盐复配可以有效抑制锂枝晶的形成;采用高浓度锂盐电解液,可以形成稳定SEI膜等.本文综述了锂枝晶的生长原理以及通过溶剂、锂盐、添加剂和高浓度电解液等策略调控电解液化学保护锂金属电池负极的研究现状,总结了各种途径的优势及局限性.并对锂金属电池电解液的发展提出了新的见解,以激发新的策略面对锂金属电池后续的挑战.     

构建亲锂铜基3D集流体实现金属锂的均匀沉积

锂金属负极以其最高的理论比容量(3860 mAh·g ^-1)和最低的电化学电位(-3.04 V (vs SHE))被誉为电池界的“圣杯”。但是锂金属电池的缺点也尤为明显: 充放电过程中锂金属电池容易在负极不均匀沉积从而产生锂枝晶, 锂枝晶的产生会造成固体电解质介面(SEI)膜的持续破裂, 不稳定的SEI膜又会加剧锂枝晶的形成, 进而刺穿隔膜, 导致电池的循环性能下降, 产生安全隐患, 所以采取相应的措施在负极均匀沉积金属锂尤为重要。本研究使用商业化的铜网, 通过碱性溶剂的氧化和空气气氛煅烧, 在铜网表面形成均一的亲锂氧化铜纳米片阵列。铜网的3D结构可以有效减小电流密度, 亲锂的纳米片阵列可以降低锂的沉积过电势, 均匀沉积锂, 有效抑制锂枝晶的产生。在电流密度为3 mA·cm ^-2的半电池测试中, 稳定循环230圈后库伦效率稳定维持在99%以上; 搭配磷酸铁锂(LFP)全电池测试, 在1C(0.17 mA·mg ^-1)条件下可稳定循环300圈, 容量保持率为95%。本研究为锂金属负极3D集流体的设计提供了新思路。     

金属锂负极的关键技术与研究进展

综述了近几年科研工作者基于金属锂负极本身的改性的最新研究进展。金属锂的理论质量比容量达3860 mAh/g,密度为0.534 g/cm^3,标准还原电位为-3.045 V,这些优势使得金属锂成为下一代理想的锂二次电池(如锂硫、锂空气电池等)的负极材料。然而,锂离子的不均匀沉积导致的锂枝晶生长、体积膨胀及其随之带来的电池安全隐患和循环寿命的降低等缺陷严重困扰着金属锂电池的发展。本文从机械地增加锂负极的表面积、锂合金负极及混合锂负极、锂负极表面层以及二维三维基底四个方面对金属锂负极的改性进行分析。最后提出要实现金属锂电池的产业化,应从解决锂枝晶和体积膨胀两个方面,通过结合不同改性方法进行研究探索。     

金属铋纳米颗粒原位修饰碳纳米管促进锂均匀沉积

锂金属具有高理论比容量和低电化学电位,是发展高能量密度电池最有吸引力的负极材料之一。然而,锂金属负极在反复的沉积/剥离过程中,不可避免地会出现不规则的锂枝晶生长,这将严重影响锂金属电池的循环寿命和使用安全性。本研究发展了一种简单温和的策略,在碳纳米管上原位修饰铋纳米颗粒,并涂覆在商业铜箔表面用作锂金属负极的集流体。研究表明,原位修饰的铋纳米颗粒可显著促进锂均匀沉积,抑制锂枝晶生长,从而提高锂金属电池的电化学性能。在电流密度为1 mA·cm^–2的条件下,基于Bi@CNT/Cu集流体的锂铜电池循环300圈后库仑效率可稳定在98%。基于Li@Bi@CNT/Cu负极的对称电池可稳定循环1000 h。基于Bi@CNT/Cu集流体的磷酸铁锂(LFP)全电池也获得了优异的电化学性能,在1C(170m A·g^–1)倍率下可稳定循环700圈。本研究为抑制锂金属负极枝晶生长提供了新的思路。     

全固态锂电池中金属锂负极及其界面设计的研究进展

锂金属具有低的氧化还原电位(-3.04 V vs标准氢电极)和高比容量(3860 mAh/g),是理想的锂二次电池负极材料.由金属锂负极/固态电解质/嵌锂正极组装的固态锂电池,有望成为未来航空航天、机器人、高端电子和电动汽车等相关技术产业的动力源.然而,在充放电过程中,由于锂的不均匀沉积-溶解造成锂与电解质接触面产生大量树枝状枝晶,并沿着电解质方向不断生长,最终造成电池内部短路而失效.使用较高杨氏模量的固态电解质,可以很大程度上阻挡锂枝晶的生长,但仍不能满足电池长循环和安全性的要求.此外,金属锂与固态电解质表面是固固接触,造成了界面电阻大以及金属锂与固态电解质的界面反应等问题,这严重阻碍了固态锂金属电池的发展与使用.本文综述了近年来基于固态电解质的金属锂电池抑制锂枝晶生长和提高固固界面相容性的相关策略,并对金属锂/固态电解质界面设计的发展趋势进行展望.     

人造固态电解质界面在锂金属负极保护中的应用研究EI北大核心CSCD

锂金属具有最低的氧化还原电位(-3.04V vs标准氢电极)和极高的比容量(3860mAh·g^-1),是理想的锂二次电池负极材料.然而电化学循环过程中,由于锂的不均匀成核生长,其表面产生锂枝晶,锂枝晶持续生长会刺穿隔膜,造成电池短路甚至引发火灾.因此需要对锂金属负极进行保护,抑制负面问题,发挥高性能.人造固态电解质界面技术是一种有效的锂金属负极保护策略,本质是预先在锂金属表面涂覆上保护层,保护层具有较高的离子传导性和电化学稳定性、较好的阻隔性和机械强度,可得到高效率、长寿命和无枝晶的锂金属负极.本文将近年来人造固态电解质界面在锂金属负极保护中的研究进展进行综述,对其制备方法、结构特点、锂金属负极循环性能、全电池电化学性能等方面作了详细介绍,分析当前存在问题并指出锂金属负极研究不仅需要加深机理研究还得与实际应用相结合.     

人造固态电解质界面在锂金属负极保护中的应用研究

锂金属具有最低的氧化还原电位(-3.04 V vs标准氢电极)和极高的比容量(3860 mAh·g~(-1)),是理想的锂二次电池负极材料。然而电化学循环过程中,由于锂的不均匀成核生长,其表面产生锂枝晶,锂枝晶持续生长会刺穿隔膜,造成电池短路甚至引发火灾。因此需要对锂金属负极进行保护,抑制负面问题,发挥高性能。人造固态电解质界面技术是一种有效的锂金属负极保护策略,本质是预先在锂金属表面涂覆上保护层,保护层具有较高的离子传导性和电化学稳定性、较好的阻隔性和机械强度,可得到高效率、长寿命和无枝晶的锂金属负极。本文将近年来人造固态电解质界面在锂金属负极保护中的研究进展进行综述,对其制备方法、结构特点、锂金属负极循环性能、全电池电化学性能等方面作了详细介绍,分析当前存在问题并指出锂金属负极研究不仅需要加深机理研究还得与实际应用相结合。     

石墨烯基材料在高性能锂金属电池中的研究进展（英文）

由于相对较低的能量密度,商用锂离子电池(LIB)难以满足便携式电子和电动汽车对储能设备能量密度日益增长的需求。锂(Li)金属具有高理论比容量(3 860 mAh g~(-1))和低的密度(0.59 g cm~(-3)),被认为是下一代高能密度锂电池最具前途的负极之一,如Li-S和Li-O_2电池。然而,由于固态电解质界面层的不稳定,导致锂枝晶生长不可控和库伦效率低等问题,限制了锂金属电池的实际应用。石墨烯基材料(GBMs)具有高比表面积、可调节的孔结构和表面化学特性,已被证明可以显著解决上述问题。本文综述了利用石墨烯基材料来保护锂金属负极的各种策略,并详细讨论了在锂金属保护中具有不同功能和作用的石墨烯基纳米材料的合理设计。文中还讨论了石墨烯基纳米材料用于锂金属负极中未来发展面临的挑战和可能的解决方案。     

用于锂金属负极的轻质、高掺氮量碳纳米纤维基三维集流体

锂金属是未来二次电池实现高能量密度化的关键负极材料,然而,如何实现锂金属的均匀和无枝晶沉积是目前制约其实际应用的关键问题.本论文采用静电纺丝技术及高温碳化方法制备了一种轻质、高掺氮量(9.5at%)的三维碳纳米纤维集流体.该集流体较低的密度能提升基于整个电池的能量密度,而且高掺氮量使其具备亲锂的特性,从而有效降低锂离子...     

Progress on Lithium Dendrite Suppression Strategies from the Interior to Exterior by Hierarchical Structure Designs

Lithium (Li) metal is promising for high energy density batteries due to its low electrochemical potential (?3.04 V) and high specific capacity (3860 mAh g^?1). However, the safety issues impede the commercialization of Li anode batteries. In this work, research of hierarchical structure designs for Li anodes to suppress Li dendrite growth and alleviate volume expansion from the interior (by the 3D current collector and host matrix) to the exterior (by the artificial solid electrolyte interphase (SEI), protective layer, separator, and solid state electrolyte) is concluded. The basic principles for achieving Li dendrite and volume expansion free Li anode are summarized. Following these principles, 3D porous current collector and host matrix are designed to suppress the Li dendrite growth from the interior. Second, artificial SEI, the protective layer, and separator as well as solid‐state electrolyte are constructed to regulate the distribution of current and control the Li nucleation and deposition homogeneously for suppressing the Li dendrite growth from exterior of Li anode. Ultimately, this work puts forward that it is significant to combine the Li dendrite suppression strategies from the interior to exterior by 3D hierarchical structure designs and Li metal modification to achieve excellent cycling and safety performance of Li metal batteries.     

A Highly Reversible,Dendrite-Free Lithium Metal Anode Enabled by a Lithium-Fluoride-Enriched Interphase

Metallic lithium is the most competitive anode material for next-generation lithium (Li)-ion batteries. However, one of its major issues is Li dendrite growth and detachment, which not only causes safety issues, but also continuously consumes electrolyte and Li, leading to low coulombic efficiency (CE) and short cycle life for Li metal batteries. Herein, the Li dendrite growth of metallic lithium anode is suppressed by forming a lithium fluoride (LiF)-enriched solid electrolyte interphase (SEI) through the lithiation of surface-fluorinated mesocarbon microbeads (MCMB-F) anodes. The robust LiF-enriched SEI with high interfacial energy to Li metal effectively promotes planar growth of Li metal on the Li surface and meanwhile prevents its vertical penetration into the LiF-enriched SEI from forming Li dendrites. At a discharge capacity of 1.2 mAh cm⁻², a high CE of >99.2% for Li plating/stripping in FEC-based electrolyte is achieved within 25 cycles. Coupling the pre-lithiated MCMB-F (Li@MCMB-F) anode with a commercial LiFePO₄ cathode at the positive/negative (P/N) capacity ratio of 1:1, the LiFePO₄//Li@MCMB-F cells can be charged/discharged at a high areal capacity of 2.4 mAh cm⁻² for 110 times at a negligible capacity decay of 0.01% per cycle.     

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.     

Stable Li Metal Anodes via Regulating Lithium Plating/Stripping in Vertically Aligned Microchannels

Li anodes have been rapidly developed in recent years owing to the rising demand for higher‐energy‐density batteries. However, the safety issues induced by dendrites hinder the practical applications of Li anodes. Here, Li metal anodes stabilized by regulating lithium plating/stripping in vertically aligned microchannels are reported. The current density distribution and morphology evolution of the Li deposits on porous Cu current collectors are systematically analyzed. Based on simulations in COMSOL Multiphysics, the tip effect leads to preferential deposition on the microchannel walls, thus taking full advantage of the lightening rod theory of classical electromagnetism for restraining growth of Li dendrites. The Li anode with a porous Cu current collector achieves an enhanced cycle stability and a higher average Coulombic efficiency of 98.5% within 200 cycles. In addition, the resultant LiFePO₄/Li full battery demonstrates excellent rate capability and stable cycling performance, thus demonstrating promise as a current collector for high‐energy‐density, safe rechargeable Li batteries.     

Recent research progress of alloy-containing lithium anodes in lithium-metal batteries

Lithium metal is regarded as one of the most ideal anode materials for next-generation batteries, due to its high theoretical capacity of 3860 mAh g⁻¹ and low redox potential (−3.04 V vs standard hydrogen electrode). However, practical applications of lithium anodes are impeded by the uncontrollable growth of lithium dendrite and continuous reactions between lithium and electrolyte during cycling processes. According to reports for decades, artificial solid electrolyte interface (SEI), electrolyte additives, and construction of three-dimensional (3D) structures are demonstrated essential strategies. Among numerous approaches, metals that can alloy with lithium have been employed to homogenize lithium deposition and accelerate Li ion transportation, which attract more and more attention. This review aims to summarize the lithium alloying applied in lithium anodes including the fabricating approaches of alloy-containing lithium anodes, and the action mechanism and challenges of fabricated lithium anodes. Based on summarizing the literature, shortcomings and challenges as well as the prospects are also analyzed, to impel further research of lithium anodes and lithium-based batteries.     

A Novel Organic “Polyurea” Thin Film for Ultralong‐Life Lithium‐Metal Anodes via Molecular‐Layer Deposition

Metallic Li is considered as one of the most promising anode materials for next‐generation batteries due to its high theoretical capacity and low electrochemical potential. However, its commercialization has been impeded by the severe safety issues associated with Li‐dendrite growth. Non‐uniform Li‐ion flux on the Li‐metal surface and the formation of unstable solid electrolyte interphase (SEI) during the Li plating/stripping process lead to the growth of dendritic and mossy Li structures that deteriorate the cycling performance and can cause short‐circuits. Herein, an ultrathin polymer film of “polyurea” as an artificial SEI layer for Li‐metal anodes via molecular‐layer deposition (MLD) is reported. Abundant polar groups in polyurea can redistribute the Li‐ion flux and lead to a uniform plating/stripping process. As a result, the dendritic Li growth during cycling is efficiently suppressed and the life span is significantly prolonged (three times longer than bare Li at a current density of 3 mA cm^?2). Moreover, the detailed surface and interfacial chemistry of Li metal are studied comprehensively. This work provides deep insights into the design of artificial SEI coatings for Li metal and progress toward realizing next‐generation Li‐metal batteries.     

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.     

Functional Separator Enabled by Covalent Organic Frameworks for High-Performance Li Metal Batteries

Uncontrolled ion transport and susceptible SEI films are the key factors that induce lithium dendrite growth, which hinders the development of lithium metal batteries (LMBs). Herein, a TpPa-2SO₃H covalent organic framework (COF) nanosheet adhered cellulose nanofibers (CNF) on the polypropylene separator (COF@PP) is successfully designed as a battery separator to respond to the aforementioned issues. The COF@PP displays dual-functional characteristics with the aligned nanochannels and abundant functional groups of COFs, which can simultaneously modulate ion transport and SEI film components to build robust lithium metal anodes. The Li//COF@PP//Li symmetric cell exhibits stable cycling over 800 h with low ion diffusion activation energy and fast lithium ion transport kinetics, which effectively suppresses the dendrite growth and improves the stability of Li+ plating/stripping. Moreover, The LiFePO4//Li cells with COF@PP separator deliver a high discharge capacity of 109.6 mAh g⁻¹ even at a high current density of 3 C. And it exhibits excellent cycle stability and high capacity retention due to the robust LiF-rich SEI film induced by COFs. This COFs-based dual-functional separator promotes the practical application of lithium metal batteries.