基于非线性动力学的锂沉积形貌模拟与预测

金属锂具有极高的理论能量密度,是新一代锂电池中最有潜力的负极材料之一。金属锂沉积时容易形成枝晶,极大影响了锂金属电池的安全性与使用寿命。但由于金属锂性质活泼,缺乏锂电极/电解液界面原位表征方法,锂枝晶生长机制尚不明确。通过有限元方法,基于非线性电极过程动力学,以三次电流模型定量研究了电极/电解液界面行为,并分析不同过程参数对表面电流的影响。结果表明,电极/电解质界面的浓度、电场差异是枝晶生长的主要原因,更大的扩散系数有利于提高界面浓度均匀性,更小的交换电流密度有利于减弱界面反应的敏感性。存在电化学极化区间是均匀沉积的必要条件,电化学极化区间越宽,均匀沉积操作窗口越宽。通过极化曲线可以判断体系是否具有均匀沉积的倾向。加深了对锂电极/电解液界面的电沉积过程的理解,对锂负极保护研究具有指导性意义。     

二次电池中金属锂负极沉脱机理研究进展

金属锂负极是下一代高比能二次电池备受关注的负极材料,以金属锂为负极的锂金属电池具备极高的理论能量密度,但其仍存在充放电循环效率低、电池寿命短等问题。要实现高能量密度高安全性的锂金属电池的合理设计和优化,需要对金属锂负极中锂金属沉积脱出过程的离子输运、电子输运、界面反应等机制机理有清晰的认识。本文针对金属锂负极中存在的枝晶生长、死锂形成、固体电解质界面膜作用等机理问题,综述了研究者们在其沉脱机理的模型与理论计算、实验研究等方面做出的诸多研究进展,为锂金属电池的合理设计提供了更全面的机理认识。     

新能源汽车固态电池中的锂枝晶抑制研究

相比于商业化的锂离子电池,固态电池具有更高的能量密度和更好的安全性。然而,固体电解质依旧面临锂枝晶生长的问题。以目前已大规模工业化的聚氧化乙烯(PEO)基电解质作为研究对象,通过将PEO与高杨氏模量的石榴石型电解质复合,抑制了锂枝晶在PEO基复合电解质中的生长,不仅使电解质膜的离子电导率从9.8×10-6S/cm增加到了3.8×10-4S/cm,还使锂/锂对称电池的临界电流密度从0.4 m A/cm²提高到1.6 mA/cm²。与此同时,组装的基于金属锂负极与传统石墨负极的软包电池可分别获得334.5 W·h/kg与218.2 W·h/kg的能量密度。其中,钴酸锂/复合电解质/石墨软包全电池循环1 000次后的容量保持率可达92.3%,能够满足新能源汽车的需求。     

原位构建富氟SEI的凝胶电解质用于金属锂二次电池

以六氟磷酸锂（LiPF₆）为四氢呋喃的聚合引发剂制备凝胶电解质,同时作为氟源在金属锂负极表面原位构建富含LiF的固态电解质界面层（solid electrolyte interface,SEI）来抑制锂枝晶的生长以及金属锂/电解液之间的副反应。所制备的凝胶电解质具有较高的室温离子电导率（1.33 mS·cm^-1）和较宽的电化学稳定窗口（4.5 V）。原位聚合方式组装金属锂对称电池循环后,锂负极表面没有明显的锂枝晶和被损毁的形貌出现;XPS结果表明锂负极表面生成了富含LiF的SEI。组装的LiFePO₄全电池在1 C的电流密度下,稳定循环400周后仍保持118.7 mAh·g^-1的放电比容量。得益于四氢呋喃在开环聚合反应过程中,促进了LiPF₆分解反应平衡的正向移动,在锂负极表面形成稳定的富含LiF的SEI,能够抑制锂枝晶的生长并防止其被持续性的腐蚀破坏。     

原位构建富氟SEI的凝胶电解质用于金属锂二次电池

以六氟磷酸锂（LiPF₆）为四氢呋喃的聚合引发剂制备凝胶电解质,同时作为氟源在金属锂负极表面原位构建富含LiF的固态电解质界面层（solid electrolyte interface,SEI）来抑制锂枝晶的生长以及金属锂/电解液之间的副反应。所制备的凝胶电解质具有较高的室温离子电导率（1.33 mS·cm^-1）和较宽的电化学稳定窗口（4.5 V）。原位聚合方式组装金属锂对称电池循环后,锂负极表面没有明显的锂枝晶和被损毁的形貌出现;XPS结果表明锂负极表面生成了富含LiF的SEI。组装的LiFePO₄全电池在1 C的电流密度下,稳定循环400周后仍保持118.7 mAh·g^-1的放电比容量。得益于四氢呋喃在开环聚合反应过程中,促进了LiPF₆分解反应平衡的正向移动,在锂负极表面形成稳定的富含LiF的SEI,能够抑制锂枝晶的生长并防止其被持续性的腐蚀破坏。     

LiAlO2-coated LiNi0.8Co0.1Mn0.1O2 and chlorine-rich argyrodite enabling high-performance all-solid-state lithium batteries at suitable stack pressure

All-solid-state lithium batteries (ASSLBs), which are consisted of Li_5.5PS_4.5Cl_1.5 electrolyte, metal lithium anode and LiNi_0.8Mn_0.1Co_0.1O₂ (NCM811) cathode, are speculated as a promising next generation energy storage system. However, the unstable oxide cathode/sulfide-based electrolyte interface and the dendrite formation in sulfide electrolyte using the lithium metal anode hinder severely commercialization of the ASSLBs. In this work, the dendrite formation in sulfide electrolyte is investigated in lithium symmetric cell by varying the stack pressure (3, 6, 12, 24 MPa) during uniaxial pressing, and uniformly nanosized LiAlO₂ buffer layer was carefully coated on NCM811 electrode (LiAlO₂@NCM811) to improve the cathode/electrolyte interface stability. The result shows that lithium symmetrical cell has a steady voltage evolution over 400 h under 6 MPa stacking pressure, and the assembled LiAlO₂@NCM811/Li_5.5PS_4.5Cl_1.5/Li battery under the stack pressure of 6 MPa exhibits large initial discharge specific capacity and excellent cycling stability at 0.05 C and 25 °C. The feasibility of using the lithium metal anode in all-solid-state batteries (ASSBs) under suitable stack pressure combined with uniformly nanosized LiAlO₂ buffer layer coated on NCM811 electrode supply a facile and effective measures for constructing ASSLBs with high energy density and high safety.     

全固态锂电池热安全性研究进展

随着液态锂电池的广泛应用,热失控现象时有发生,其热安全性成为亟待解决的问题。全固态锂电池以其优异的安全性显示出巨大的应用潜力。该文简要介绍了全固态锂电池的基本概念及组成结构,重点阐述了氧化物、硫化物以及聚合物固体电解质的最新研究进展,并对这3类全固态锂电池的热安全性差异进行了总结,包括固体电解质材料级别、固体电解质与活性材料或锂金属负极混合时界面级别以及全电池级别的热安全性。此外,锂枝晶现象对全固态锂电池安全性的影响仍不可忽视。目前,针对材料和界面级别的热安全性研究众多,但全电池级别的研究较少,且多集中在小容量电池,针对全电池级别的热安全性仍需进一步探究。最后,指出了未来高安全性全固态锂电池的商业化应用应着力于解决全固态锂电池中的关键界面问题以及锂枝晶问题。     

Comparative study on surface behaviors of copper current collector in electrolyte for lithium-ion batteries

The chemical and electrochemical stability of Cu current collectors in electrolyte for lithium-ion batteries is investigated. During long-term storage, the surface section of Cu foil is oxidized to copper compounds along with the reduction reaction of electrolyte. A continuous surface film can be formed on the Cu current collector after the foil is immersed in electrolyte for lithium ion batteries at room temperature for 30 days. This surface film is composed of inorganic compounds located in the inner layer and organic/inorganic mixed components stayed outside. It comes from the spontaneous reaction at the interface between Cu foil and electrolyte for the existence of trace water in electrolyte. Different from SEI film spontaneous formation during storage, surface film generated on Cu foil during electrochemical process shows different characteristic and mechanism. By using metal lithium as counter electrode, SEI film on Cu foil in Cu foil/metal Li battery is formed from surface chemical species floating from lithium counter electrode and electrochemical oxidation/reduction process. In contrast, thinner SEI film can be generated merely from electrochemical electrolyte decomposition and precipitation. All the evidences reveal that the structure of SEI film from different conditions is similar, which shows inorganic fluorides located in the inner layer and organic/inorganic mixed lied in the outer layer.     

Poly(ethylene oxide)‐based block copolymer electrolytes for lithium metal batteries

Nanostructured block copolymer electrolytes (BCEs) based on poly(ethylene oxide) (PEO) are considered as promising candidates for solid‐state electrolytes in high energy density lithium metal batteries (LMBs). Because of their self‐assembly properties, they confer on electrolytes both high mechanical strength and sufficient ionic conductivity, which linear PEO cannot provide. Two types of PEO‐based BCEs are commonly known. There are the traditional ones, also called dual‐ion conducting BCEs, which are a mixture of block copolymer chains and lithium salts. In these systems, the cations and anions participate in the conduction, inducing a concentration polarization in the electrolyte, thus leading to poor performances of LMBs. The second family of BCEs are single‐lithium‐ion conducting BCEs (SIC‐BCEs), which consist of anions being covalently grafted to the polymer backbone, therefore involving conduction by lithium ions only. SIC‐BCEs have marked advantages over dual‐ion conducting BCEs due to a high lithium ion transference number, absence of anion concentration gradients as well as low rate of lithium dendrite growth. This review focuses on the recent developments in BCEs for applications in LMBs with particular emphasis on the physicochemical and electrochemical properties of these materials. © 2018 Society of Chemical Industry     

Preparation of transparent LLZTO electrolyte and its application in the observation of Li dendrite

The application of solid-state electrolytes endows the distinctive features of high safety and high energy density for lithium (Li) metal batteries. Among all kinds of solid-state electrolytes, garnet-type Li₇La₃Zr₂O₁₂ (LLZO) with high Young's modulus is a promising candidate. Nevertheless, Li metal can still grow inside LLZO and lead to short circuit. But it is difficult to determine the failure mechanism caused by Li dendrite due to the opacity of the common LLZO. Herein, a transparent Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) electrolyte is fabricated for the observation of Li growth inside the electrolyte directly. The factor that influences the transparency of LLZTO is investigated thoroughly, which is crucial for studying the behavior of Li metal during the plating process inside LLZTO. Results demonstrate that the amount of residual Li-containing compound at grain boundaries is the dominant factor influencing the transparency of LLZTO. The formation of Li filament and its growth process inside transparent LLZTO are also observed directly.     

石榴石型固态电解质Li7La3Zr2O12的改性研究现状

固态电解质是高安全性、高能量密度的全固态锂电池的核心部件,其典型代表Li₇La₃Zr₂O₁₂(LLZO)具有高离子电导率、高机械强度、高电化学稳定性、低界面阻抗以及对锂金属负极良好的稳定性等优势,是科研人员重点关注的对象之一,但与液态电解质相比,目前LLZO仍存在低离子电导率和与电极固-固界面接触等问题。本文主要简介了LLZO的晶体结构、改性方式等对其离子电导率及界面阻抗的影响,同时对LLZO现存的问题进行了总结,对LLZO的未来发展方向进行了展望,为探索全固态锂电池的实际生产应用提供理论指导。     

三维锂金属负极的研究进展

金属锂具有高的理论比容量（3 860 mAh·g^-1）,低的电极电位（-3.04 V与标准氢电极相比）和低的密度（0.53 g·cm^-3）,是最有前途的锂二次电池用的负极材料。但仍存在循环过程中枝晶生长及其导致的低库伦效率、短循环寿命等问题。而3D锂金属负极因具有高比表面积和内部空腔能有效缓解上述问题。特别是纳米技术的发展为3D锂金属负极提供了更高效的形貌与结构。基于金属基和碳基3D锂金属负极对三维锂金属负极的设计及研究进展进行了详细的概述。     

A panoramic view of Li7P3S11 solid electrolytes synthesis,structural aspects and practical challenges for all-solid-state lithium batteries

The development of an inorganic electrochemical stable solid-state electrolyte is essentially responsible for future state-of-the-art all-solid-state lithium batteries (ASSLBs). Because of their advantages in safety, working temperature, high energy density, and packaging, ASSLBs can develop an ideal energy storage system for modern electric vehicles (EVs). A solid electrolyte (SE) model must have an economical synthesis approach, exhibit electrochemical and chemical stability, high ionic conductivity, and low interfacial resistance. Owing to its highest conductivity of 17 mS·cm^-1, and deformability, the sulfide-based Li₇P₃S₁₁ solid electrolyte is a promising contender for the high-performance bulk type of ASSLBs. Herein, we present a current glimpse of the progress of synthetic procedures, structural aspects, and ionic conductivity improvement strategies. Structural elucidation and mechanistic approaches have been extensively discussed by using various characterization techniques. The chemical stability of Li₇P₃S₁₁ could be enhanced via oxide doping, and hard and soft acid/base (HSAB) concepts are also discussed. The issues to be undertaken for designing the ideal solid electrolytes, interfacial challenges, and high energy density have been discoursed. This review aims to provide a bird's eye view of the recent development of Li₇P₃S₁₁-based solid-state electrolyte applications and explore the strategies for designing new solid electrolytes with a target-oriented approach to enhance the efficiency of high energy density all-solid-state lithium batteries.     

湿化学法制备石榴石型固态电解质Li7La3Zr2O12

锂电池因能量密度高、循环寿命长、绿色清洁等特点被广泛应用,但其液态电解质易泄漏、挥发,且隔膜易被锂枝晶刺穿造成短路,引发危险。固态电解质大多是不具燃烧性的无机材料,室温下离子电导率较高、电化学窗口宽且适用温度范围广。因此,采用固态电解质替代液态电解质具有十分重要的意义。相对于其他类型固态电解质,石榴石型氧化物Li₇La₃Zr₂O₁₂（LLZO）具有离子电导率高、电化学窗口宽（>5V vs. Li/Li⁺）、对锂稳定性好和热稳定性高等特点,是非常具有发展潜力的无机固态电解质。本文采用溶胶-凝胶法和低温燃烧法两种湿化学法合成LLZO粉末,对应的电解质片在40℃时的离子电导率分别为1.22×10^-5S/cm和3.87×10^-6S/cm,活化能分别为0.34eV和0.32eV。从实验结果综合比较,溶胶-凝胶法为最佳制备方法。     

Effect of silica on the interfacial stability of the PEO-based polymer electrolytes

Summary In order to evaluate the effect of silica on stabilizing the interface of lithium metal electrode/solid polymer electrolyte, the cyclic behavior for silica-free and silica-containing polymer electrolyte under electrical stress was investigated using cyclic voltammetry. These electrolytes have an ionic conductivity of the order 10^-4 S/cm at above 60°C and most importantly the introduction of hydrophilic silica in PEO-based polymer electrolyte has brought about the enhanced stability of lithium metal electrode/polymer electrolyte interface especially under electrical stress. This in turn supports the suitability of the composite polymer electrolytes with hydrophilic silica for fabrication of enhanced rechargeable solid lithium polymer batteries. Received: 7 May 2002/ Revised version: 10 July 2002/ Accepted: 12 July 2002     

Electrochemical characteristics of lithium metal anodes with diamond like carbon film coating layer

To overcome the poor electrochemical characteristics of lithium metal anodes due to the dendrite formations, diamond like carbon (DLC) films were deposited onto the surface of lithium metal by radio frequency-plasma enhanced chemical vapor deposition (CVD) technique using acetylene gas as carbon precursor. The substrate temperature was selected as the main experimental parameter to control the bonding characteristic (sp²/sp³ ratio) of the films. The presence of diamond like structures was confirmed by Raman and Fourier transform infra red spectroscopy. The DLC coated lithium metal was then characterized as an anode material for lithium secondary batteries. The results showed that the DLC coated lithium metal anodes exhibited better electrochemical characteristics in terms of higher specific capacity and smaller interfacial impedance. These improved characteristics were attributed to the presence of DLC film coating which might suppress the dendrite's formation by protecting the lithium metal surface from the direct contact with the electrolyte.     

Noise characterization of surface processes of the Li/organic electrolyte interface

The processes occurring in aprotic electrolyte on a lithium electrode in the steady state conditions and under polarization are studied using the method of electrochemical noise characterization. The evidence of the electro-chemical noise measurements on polarized lithium electrodes indicates that the discharge of lithium ions under cathodic polarization, as well as lithium anodic dissolution, is localized under the passive film rather than on its surface. An increase in the polarizing current results in local breakdown of the film; in this case, the electrochemical process emerges on the electrode surface affecting the character of potential fluctuations. The intensity of electrochemical noise significantly increases in the course of cathodic polarization with high currents. The reason is that lithium metal crystals, which are formed under the passive film, perforate the film, and dendrites grow on its surface. The method shows the dependence of electrochemical noise intensity on the nature of the electrolyte and establishes the correlation between the stability of the lithium electrode in the course of cycling and the intensity of fluctuations. This offers an opportunity of using the method of electrochemical noise for screening organic electrolytes for lithium batteries.     

锂离子电池大电流放电过程模拟研究

随着锂离子电池的广泛应用,电池以更大功率、更高倍率运行的需求日益迫切,探索锂离子电池大电流运行时的电-热行为及内部关键参数演化十分必要。建立了锂离子电池的电化学-热(ECT)模型和电池材料的热滥用模型,模拟了方形单层LiCoO₂/C电芯在不同放电电流下的电-热行为,对比分析了电池分别以1C和14C倍率放电时电池内部关键电化学参数的演化过程。结果表明:随着放电电流增加,电池内部积聚的热量会引发材料的放热反应,有引发电池热失控的可能性;大电流放电过程电解液中锂离子浓度、输运电流密度、过电势、电解质电势和固相颗粒表面的锂离子浓度波动较大,在电池内部相关区域形成了明显的浓度差、密度差和电势差。     

固态无机电解质Li7La3Zr2O12的改性研究进展

作为一种固态无机电解质材料,石榴石型立方相Li₇La₃Zr₂O₁₂具有较高的室温锂离子电导率、较宽的电化学窗口和优良的热稳定性等特点,是高安全性、高能量密度固态锂离子电池实现商业化应用的关键。阐述了Li₇La₃Zr₂O₁₂的晶体结构与锂传导机理,综述了元素掺杂、聚合物电解质复合、烧结助剂引入、表面包覆或修饰等方式对Li₇La₃Zr₂O₁₂的物相结构稳定性、界面阻抗与相容性、烧结活性、离子电导率等进行改性的最新研究进展。最后,针对Li₇La₃Zr₂O₁₂在产业化应用中所面临的障碍与挑战,提出了制备新工艺的开发、离子电导率的多重改性以及柔性复合电解质膜的结构设计与优化等应对策略,为推动高性能固态锂离子电池的发展提供依据。     

锂离子在三维骨架复合锂金属负极中的沉积规律

锂金属具有极高的理论比容量和极低的氧化还原电极电势,成为了新一代高比能二次电池最理想的负极材料。然而,锂金属负极其走向大规模应用仍存在诸多问题与挑战。三维骨架复合负极可以控制金属锂均匀形核,低电流密度下均匀沉积,有望推动锂金属负极的实用化。为了更高效地指导锂金属负极设计和优化,采用相场理论,对三维骨架锂金属负极中比表面积对金属锂沉积过程的作用机制进行了定量分析和探究,发现了比表面积调控金属锂沉积的两阶段作用机理,并提出了基于比表面积参数的三维骨架负极设计与优化方向,从而最大程度发挥三维骨架在调控稳定金属锂负极上的积极作用。