混合固液锂离子电池的热失控行为研究

混合固液电解质锂离子电池是一种具有高能量密度、高安全性的储能器件,有望短期内实现产业化。本工作选择混合固液电解质(LATP和电解液)匹配高比容量活性材料(正极NCM811和负极C@SiO)为研究体系,采用绝热加速量热仪和气相色谱仪对全SOC及不同全寿命周期下混合固液电解质锂离子电池进行热失控模拟和产气组分分析,并通过超声检测仪分析不同寿命周期下电解液含量的变化情况。研究结果显示:该体系新鲜电池随荷电态的增加而热安全性降低,产气量增大,且可燃气体的占比会增加。随着循环容量的衰减,电池样品的热失控起始温度、最高产热速率以及产气量变化有所差异,在容量保持率为70%时热稳定性有所改善,结合超声分析结果推测与电解液转化成固态电解质有关。该工作初步探究了该体系电池的热失控行为,为后期内部机理解析和电池设计提供了支撑。

Accurate estimation of Li/Ni mixing degree of lithium nickel oxide cathode materials

Li/Ni mixing negatively influences the discharge capacity of lithium nickel oxide and high-nickel ternary cathode materials.However,accurately measuring the Li/Ni mixing degree is difficult due to the preferred orientation of labbased XRD measurements using Bragg–Brentano geometry.Here,we find that employing spherical harmonics in Rietveld refinement to eliminate the preferred orientation can significantly decrease the measurement error of the Li/Ni mixing ratio.The Li/Ni mixing ratio obtained from Rietveld refinement with spherical harmonics shows a strong correlation with discharge capacity,which means the electrochemical capacity of lithium nickel oxide and high-nickel ternary cathode can be estimated by the Li/Ni mixing degree.Our findings provide a simple and accurate method to estimate the Li/Ni mixing degree,which is valuable to the structural analysis and screening of the synthesis conditions of lithium nickel oxide and high-nickel ternary cathode materials.

电池安全——从锂离子电池到固态电池

1.Introduction To date,the application of lithium-ion batteries(LIBs)has been expanded from traditional consumer electronics to electric vehicles(EVs),energy storage,special fields,and other application scenarios.The production capacity of LIBs is increasing rapidly,from 26 GW·h in 2011 to 747 GW·h in 2020,76% of which comes from China[1].

锂电池失效分析与研究进展

锂电池在使用或储存过程中会出现一定概率的失效,包括容量衰减(跳水)、循环寿命短、内阻增大、电压异常、析锂、产气、漏液、短路、变形、热失控等,严重降低了锂电池的使用性能、一致性、可靠性、安全性.对锂电池失效进行准确诊断并探究其失效机理是锂电池失效分析的主要任务,对锂电池性能提升和技术发展具有深远意义.为了全面且深入地介绍锂电池失效分析,本文从锂电池失效分析的定义、失效表现、失效原因、分析内容、分析流程、困难点等方面进行了简述,希望能为推动中国锂电池失效分析技术的发展起到积极作用.

锂离子电池失效分析概述

商业化的锂离子电池在使用或储存过程中常出现某些失效现象,包括容量衰减、内阻增大、倍率性能降低、产气、漏液、短路、变形、热失控、析锂等,严重降低了锂离子电池的使用性能、一致性、可靠性、安全性。这些失效现象是由电池内部一系列复杂的化学和物理机制相互作用引起的。对失效现象的正确分析和理解对锂离子电池性能的提升和技术改进有着重要作用。锂离子电池失效分析是以电池的失效现象为起点,针对该现象选择适当的测试分析手段,设计合理、有效的失效分析流程,挖掘电池在材料制备和制造工艺层面上的失效主要原因,并能提供相关可靠有效的优化建议。本文综述了锂离子电池的失效现象及其失效机理、失效分析常见的测试分析方法、失效分析流程的设计,并列举了容量衰减、热失控和产气等方面相关分析案例进行说明。

储能技术领域发表文章和专利概览综述

能源危机和环境问题制约着社会发展与人类进步,新型可再生清洁能源的开发利用是解决能源危机和环境问题行之有效的途径,先进储能技术在可再生清洁能源的开发利用过程中具有至关重要的作用。基于储能技术发展的重要性,文章简略介绍了各种先进储能技术,并结合Web of Science搜索引擎,从科技论文发表的年份、国家/地区、机构和专利等角度,对各种先进储能技术进行了文献检索统计,分析其发展趋势。在众多的储能技术中,锂离子电池、超级电容器、钠离子电池、飞轮、超导磁储存、固态电池等基础研究方向比较活跃;锂离子电池、飞轮、超级电容器、压缩空气储能、铅酸电池等则在技术开发方向比较突出。

锂离子扣式电池的组装,充放电测量和数据分析

锂离子电池材料在研发以及初期生产检测阶段,需要通过扣式电池对电化学性能进行测量。测试方法和分析方法的准确规范是精确分析评价电池材料、开发新材料及开发新电池体系的基础。本文总结了以往文献资料,结合实际工作经验,介绍实验室锂离子扣式电池组装流程、充放电性能测量和数据分析方法。

锂电池研究中的循环伏安实验测量和分析方法

循环伏安作为一种重要的电化学测试方法,在电化学领域尤其是锂电池的研究中有着广泛的应用,常用于电极反应可逆性、电极反应机理及电极反应动力学参数的研究。本文介绍了循环伏安的基本原理、测试方法以及常用仪器,并结合实际案例,具体分析了循环伏安在锂电池电极材料反应机理、电极过程动力学以及电解液电化学稳定性方面的应用研究。

锂电池研究中的X射线多晶衍射实验与分析方法综述

X射线多晶衍射技术是研究晶体结构的重要手段,通过对衍射数据的分析,能够得到材料的晶胞参数、原子占位、晶粒大小、晶粒取向、应力分布等信息,对研究材料结构与性能之间的关系具有重要意义。在锂离子电池研究领域,X射线衍射技术广泛应用于材料合成、电芯检测及失效分析中的物相检测,极大地推动了电池材料的进步与发展。本文主要介绍了X射线多晶衍射基本原理与实验方法、测试过程常用参数设置、数据处理与结构精修方法,并结合实例介绍了X射线衍射技术在研究锂离子电池材料结构演化、反应机制、安全性能等方面的应用。

多空间尺度下的金属锂负极表征技术

金属锂因为其优秀的特性被认为是未来锂电池负极的最终之选。然而目前金属锂负极在旧有液态体系中的研究陷入瓶颈,在新兴固态体系中的挑战层出不穷。想要实现金属锂负极的实用化,必须加深对金属锂负极基础科学问题的认识。本文系统论述了多空间尺度下金属锂的电极行为与对应的表征技术。首先综述了多空间尺度下金属锂负极的基础科学和应用技术问题,结合近年来的工作,对全空间尺度下的先进表征手段做了梳理,分析了从原子级到宏观尺度各种表征手段的技术特点,并重点讨论了各类表征技术在研究固态体系中金属锂负极时的特点与可能的发展方向。

A 700 W·h·kg^(-1) Rechargeable Pouch Type Lithium Battery

High-energy-density rechargeable lithium batteries are being pursued by researchers because of their revolutionary potential nature.Current advanced practical lithium-ion batteries have an energy density of around300 W·h·kg^(-1).Continuing to increase the energy density of batteries to a higher level could lead to a major explosion development in some fields,such as electric aviation.Here,we have manufactured practical pouch-type rechargeable lithium batteries with both a gravimetric energy density of 711.3 W·h·kg^(-1)and a volumetric energy density of 1653.65 W·h·L^(-1).This is achieved through the use of high-performance battery materials including high-capacity lithium-rich manganese-based cathode and thin lithium metal anode with high specific energy,combined with extremely advanced process technologies such as high-loading electrode preparation and lean electrolyte injection.In this battery material system,the structural stability of cathode material in a widened charge/discharge voltage range and the deposition/dissolution behavior of interfacial modified thin lithium electrode are studied.

锂电池安全性多尺度研究策略:实验与模拟方法

作为新一代电化学储能体系,锂离子电池在消费电子产品、交通动力系统、电网储能等领域具有重要的应用价值。然而,在锂离子电池的商业化进程中,安全性事故时有发生,影响了锂离子电池的大规模应用。本文从电池安全性的三个研究尺度:材料、电芯、系统,综述了与之对应的重要研究方法,其中每个尺度均包括基于物理样品的实验方法和基于计算机数学模型的模拟方法。本文介绍了这些方法的基本原理,通过典型案例展示了这些方法在安全性研究中的适用场景和作用,并探讨了实验和模拟方法之间的联系,着重介绍了材料热分析、材料加热过程中结构分析、电芯加速度量热分析、电芯安全性数值模拟等方法。基于对多尺度研究策略的系统综述,认为安全性研究需要在各个尺度联合同步开展。最后,展望了下一代锂电池,如固态电池、锂金属电池等,可能面临的电池安全性问题。这些新体系的安全性研究仍处于早期,其材料和验证型电芯的安全性研究是当前阶段值得关注的重要课题。

Strategies to curb structural changes of lithium/transition metal oxide cathode materials & the changes' effects on thermal & cycling stability

Structural transformation behaviors of several typical oxide cathode materials during a heating process are reviewed in detail to provide in-depth understanding of the key factors governing the thermal stability of these materials. We also discuss applying the information about beat induced structural evolution in the study of electrochemically induced structural changes. All these discussions are expected to provide valuable insights for designing oxide cathode materials with significantly improved structural stability for safe, long-life lithium ion batteries, as the safety of lithium-ion batteries is a critical issue; it is widely accepted that the thermal instability of the cathodes is one of the most critical factors in thermal runaway and related safety problems.

Improved electrochemical performance of Li(Ni0.6Co0.2Mn0.2)O2 at high charging cut-off voltage with Li1.4Al0.4Ti1.6（PO4）3 surface coating

Ba0.8Sr0.2FeO3-δhas been surface-modified by the lithium-ion conductor Li1.4Al0.4Ti1.6(PO4)3via a facile mechanical fusion method. The annealing temperature during coating process shows a strong impact on the surface morphology and chemical composition of Li(Ni0.6 Co0.2 Mn0.2)O2. The 600-?C annealed material exhibits the best cyclic stability at high charging cut-off voltage of 4.5 V(versus Li+/Li) with the capacity retention of 90.9% after 100 cycles, which is much higher than that of bare material(79%). Moreover, the rate capability and thermal stability are also improved by Li1.4Al0.4Ti1.6(PO4)3coating. The enhanced performance can be attributed to the improved stability of interface between Ba0.8Sr0.2FeO3-δand electrolyte by Li1.4Al0.4Ti1.6(PO4)3modification. The results of this work provide a possible method to design reliable cathode materials to achieve high energy density and long cycle life.

Improved electrochemical performances of high voltage LiCoO_2 with tungsten doping

The effects of tungsten W doping and coating on the electrochemical performance of LiCoO2 cathode are compara- tively studied in this work. The amount of modification component is as low as 0.1 wt% and 0.3 wt% respectively. After 100 cycles between 3.0 V-4.6 V, 0.1 wt% W doping provides an optimized capacity retention of 72.3%. However, W coating deteriorates battery performance with capacity retention of 47.8%, even lower than bare LiCoO2 of 55.7%. These different electrochemical performances can be attributed to the surface aggregation of W between doping and coating methods. W substitution is proved to be a promising method to develop high voltage cathodes. Practical performance relies on detailed synthesis method.

Artificial solid electrolyte interphase based on polyacrylonitrile for homogenous and dendrite-free deposition of lithium metal

High chemical reactivity, large volume changes, and uncontrollable lithium dendrite growth have always been the key problems of lithium metal anodes.Coating has been demonstrated as an effective strategy to protect the lithium metal.In this work, the effects of polyacrylonitrile(PAN)-based coatings on electrodeposited lithium have been studied.Our results show that a PAN coating layer provides uniform and dendrite-free lithium deposition as well as better cycling performance with carbonate electrolyte.Notably, heat treatment of the PAN coating layer promotes the formation of larger deposit particle size and higher coulombic efficiency(85%).The compact coating layer of heat-treated PAN with a large Young modulus(82.7 GPa) may provide stable protection for the active lithium.Improved homogeneity of morphology and mechanical properties of heat-treated PAN contribute to the larger deposit particles.This work provides new feasibility to optimize the polymer coating through rational modification of polymers.

Influence of carbon coating on the electrochemical performance of SiO@C/graphite composite anode materials

Silicon monoxide(SiO) has been considered as one of the most promising anode materials for next generation highenergy-density Li-ion batteries(LiBs) thanks to its high theoretical capacity. However, the poor intrinsic electronic conductivity and large volume change during lithium intercalation/de-intercalation restrict its practical applications. Fabrication of SiO/C composites is an effective way to overcome these problems. Herein, a series of micro-sized SiO@C/graphite(Si0@C/G) composite anode materials, with designed capacity of 600 mAh·g-1, are successfully prepared through a pitch pyrolysis reaction method. The electrochemical performance of SiO@C/G composite anodes with different carbon coating contents of 5 wt%, 10 wt%, 15 wt%, and 35 wt% is investigated. The results show that the SiO@C/G composite with15-wt% carbon coating content exhibits the best cycle performance, with a high capacity retention of 90.7% at 25℃ and90.1% at 45 0 C after 100 cycles in full cells with LiNi0.5Co0.2Mn0.3O2 as cathodes. The scanning electron microscope(SEM) and electrochemistry impedance spectroscopy(EIS) results suggest that a moderate carbon coating layer can promote the formation of stable SEI film, which is favorable for maintaining good interfacial conductivity and thus enhancing the cycling stability of SiO electrode.

Suppressing transition metal dissolution and deposition in lithium-ion batteries using oxide solid electrolyte coated polymer separator

The dissolution of transition metal(TM)cations from oxide cathodes and the subsequent migration and deposition on the anode lead to the deconstruction of cathode materials and uncontrollable growth of solid electrode interphase(SEI).The above issues have been considered as main causes for the performance degradation of lithium-ion batteries(LIBs).In this work,we reported that the solid oxide electrolyte Li1.5Al0.5Ti1.5(PO4)3(LATP)coating on polyethylene(PE)polymer separator can largely block the TM dissolution and deposition in LIBs.Scanning electron microscopy(SEM),second ion mass spectroscopy(SIMS),and Raman spectroscopy characterizations reveal that the granular surface of the LATP coating layer is converted to a dense morphology due to the reduction of LATP at discharge process.The as-formed dense surface layer can effectively hinder the TM deposition on the anode electrode and inhibit the TM dissolution from the cathode electrode.As a result,both the LiCoO2/SiO-graphite and LiMn2O4/SiO-graphite cells using LATP coated PE separator show substantially enhanced cycle performances compared with those cells with Al2O3 coated PE separator.

Neutron-based characterization techniques for lithium-ion battery research

During the past decades,Li-ion batteries have been one of the most important energy storage devices.Large-scale energy storage requires Li-ion batteries which possess high energy density,low cost,and high safety.Other than advanced battery materials,in-depth understanding of the intrinsic mechanism correlated with cell reaction is also essential for the development of high-performance Li-ion battery.Advanced characterization techniques,especially neutron-based techniques,have greatly promoted Li-ion battery researches.In this review,the characteristics or capabilities of various neutron-based characterization techniques,including elastic neutron scattering,quasi-elastic neutron scattering,neutron imaging,and inelastic neutron scattering,for the related Li-ion-battery researches are summarized.The design of in-situ/operando environment is also discussed.The comprehensive survey on neutron-based characterizations for mechanism understanding will provide guidance for the further study of high-performance Li-ion batteries.

Understanding the battery safety improvement enabled by a quasi-solid-state battery design

The rapid development of lithium-ion batteries(LIBs)is faced with challenge of its safety bottleneck,calling for design and chemistry innovations.Among the proposed strategies,the development of solid-state batteries(SSBs)seems the most promising solution,but to date no practical SSB has been in large-scale application.Practical safety performance of SSBs is also challenged.In this article,a brief review on LIB safety issue is made and the safety short boards of LIBs are emphasized.A systematic safety design in quasi-SSB chemistry is proposed to conquer the intrinsic safety weak points of LIBs and the effects are accessed based on existing studies.It is believed that a systematic and targeted solution in SSB chemistry design can effectively improve the battery safety,promoting larger-scale application of LIBs.