Overdischarge-induced evolution of Cu dendrites and degradation of mechanical properties in lithium-ion batteries

The degradation of mechanical properties of overdischarge battery materials manifests as a significant effect on the energy density,safety,and cycle life of the batteries.However,establishing the correlation between depth of overdischarge and mechanical properties is still a significant challenge.Studying the correlation between depth of overdischarge and mechanical properties is of great significance to improving the energy density and the ability to resist abuse of the batteries.In this paper,the mechanical properties of the battery materials during the whole process of overdischarge from discharge to complete failure were studied.The effects of depth of overdischarge on the elastic modulus and hardness of the cathode of the battery,the tensile strength and the thermal shrinkage rate of the separator,and the performance of binder were investigated.The precipitation of Cu dendrites on the separator and cathode after dissolution of anode copper foil is a key factor affecting the performance of battery materials.The Cu dendrites attached to the cathode penetrate the separator,causing irreversible damage to the coating and base film of the separator,which leads to a sharp decline in the tensile strength,thermal shrinkage rate and other properties of the separator.In addition,the Cu dendrites wrapping the cathode active particles reduce the adhesion of the active particles binder.Meanwhile,the active particles are damaged,resulting in a significant decrease in the elastic modulus and hardness of the cathode.

Investigation on step overcharge to self-heating behavior and mechanism analysis of lithium ion batteries

To obtain intrinsic overcharge boundary and investigate overcharge mechanism,here we propose an innovative method,the step overcharge test,to reduce the thermal crossover and distinguish the overcharge thermal behavior,including 5%state of charge(SOC)with small current overcharge and resting until the temperature equilibrium under adiabatic conditions.The intrinsic thermal response and the self-excitation behaviour are analysed through temperature and voltage changes during the step overcharge period.Experimental results show that the deintercalated state of the cathode is highly correlated to self-heating parasitic reactions.Before reaching the upper limit of Negative/Positive(N/P)ratio,the temperature changes little,the heat generation is significantly induced by the reversible heat(endothermic)and ohmic heat,which could balance each other.Following that the lithium metal is gradually deposited on the surface of the anode and reacts with electrolyte upon overcharge,inducing selfheating side reaction.However,this spontaneous thermal reaction could be“self-extinguished”.When the lithium in cathode is completely deintercalated,the boundary point of overcharge is about 4.7 V(~148%SOC,>40℃),and from this point,the self-heating behaviour could be continuously triggered until thermal runaway(TR)without additional overcharge.The whole static and spontaneous process lasts for 115 h and the side reaction heat is beyond 320,000 J.The continuous self-excitation behavior inside the battery is attributed to the interaction between the highly oxidized cathode and the solvent,which leads to the dissolution of metal ions.The dissolved metal ions destroy the SEI(solid electrolyte interphase)film on the surface of the deposited Li of anode,which induces the thermal reaction between lithium metal and the solvent.The interaction between cathode,the deposited Li of anode,and solvent promotes the temperature of the battery to rise slowly.When the temperature of the battery reaches more than 60℃,the reaction between lithium metal and solvent is accelerated.After the temperature rises rapidly to the melting point of the separator,it triggers the thermal runaway of the battery due to the short circuit of the battery.

Overcharge-to-thermal-runaway behavior and safety assessment of commercial lithium-ion cells with different cathode materials:A comparison study

In this paper,overcharge behaviors and thermal runaway(TR)features of large format lithium-ion(Liion)cells with different cathode materials(LiFePO4(LFP),Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_(2)(NCM111),Li[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_(2)(NCM622)and Li[Ni_(0.8)Co_(0.1)Mn_(0.1)]O_(2)(NCM811))were investigated.The results showed that,under the same overcharge condition,the TR of LFP Li-ion cell occurred earlier compared with the NCM Li-ion cells,indicating its poor overcharge tolerance and high TR risk.However,when TR occurred,LFP Li-ion cell exhibited lower maximum temperature and mild TR response.All NCM Liion cells caught fire or exploded during TR,while the LFP Li-ion cell only released a large amount of smoke without fire.According to the overcharge behaviors and TR features,a safety assessment score system was proposed to evaluate the safety of the cells.In short,NCM Li-ion cells have better performance in energy density and overcharge tolerance(or low TR risk),while LFP Li-ion cell showed less severe response to overcharging(or less TR hazards).For NCM Li-ion cells,as the ratio of nickel in cathode material increases,the thermal stability of the cathode materials becomes poorer,and the TR hazards increase.Such a comparison study on large format Li-ion cells with different cathode materials can provide deeper insights into the overcharge behaviors and TR features,and provide guidance for engineers to reasonably choose battery materials in automotive applications.

Overcharge performance of LiMn_2O_4/graphite battery with large capacity

The LiMn2O4/grapbite battery was fabricated and its 3 C/10 V overcharge performance was studied. Spinel LiMn2O4 was synthesized by solid-state method and 325680-type size full battery was fabricated. The structure and morphology of the powders were characterized by XRD and SEM technique, respectively. The battery explodes after 3 C/10 V overcharged test, and surface temperature of the battery case arrives at 290 ℃ in 12 s after exploding. Black air is given out with blast. Carbon, MnO, and Li2CO3 are observed in the exploded powders. The cathode electrode remains spinel structure with 5.0 V charged. Cracks in the cathode electrode particles are detected with the increase of voltage by SEM technique. The 5.0 V charged electrode can decompose into Mn3O4 at 400 ℃. It is demonstrated that the decomposition of 5.0 V charged electrode can be promoted and Mn^4＋ can be deoxidized to Mn^2＋ by carbon and electrolyte through the simulation of blast process.

Evolution of the morphology,structural and thermal stability of LiCoO_(2) during overcharge

The overcharge behaviors of 1000 m Ah LiCoO_(2)/graphite pouch cells are systematically investigated through the analysis of morphology,structural and thermal stability of LiCoO_(2) under different state of charge(SOC)of 120%,150%,174%,190%and 220%.The LiCoO_(2) experiences the phase transition from O3 to H1-3 and then O1 together with the grain breakage and boundary slip as evidenced by XRD and SEM analysis respectively,which results in the pronounced Co dissolution after the SOC of 174%.The impedance analysis of the pouch cells and coin cells demonstrates that the main contribution of impedance increase originates from the LiCoO_(2) electrode.Under the combined effect of structural collapse,Co dissolution,and electrolyte oxidization,the thermal stability of Li CoO_(2) cathode materials reduces with the progressing of overcharge as revealed by differential scanning calorimetry(DSC)results.We hope that this comprehensive understanding can provide meaningful guidance for advancing the overcharge performance of LiCoO_(2)/graphite pouch cells.

Effect of Overcharge on Electrochemical Performance of Sealed-Type Nickel/Metal Hydride Batteries

The effects of overcharge on electrochemical performance of AA size sealed-type nickel/metal hydride（Ni/MH） batteries and its degradation mechanism were investigated. The results indicated that the relationship between the effects of different overcharge currents on the increasing velocity of inner pressure and the degradation velocity of cycle life and discharge voltage remains in almost direct proportion. After overcharge cycles, the positive electrode materials remain the original structure, but there occur some breaks because of the irreversible expand of crystal lattice. And the negative electrode alloy particles have inconspicuous pulverization, but are covered with lots of corrosive products and its main component is rare earth hydroxide or oxide. These are all the main reasons leading to the degradation behavior of the discharge capacity and cycle life of Ni/MH batteries.

基于电化学阻抗谱的锂电池过充电阻抗特性与检测方法研究

目前以锂电池为主的电化学储能单元及系统应用日益广泛,而锂电池在实际使用中频发因过充电滥用引发电池故障的情况,因此实际电池的过充电状态准确检测一直是该领域的难点和瓶颈问题。针对此,该文采用电化学阻抗谱技术对单体电池过充电行为及过程开展检测研究,在实验室设计并制定电池过充电模拟循环实验,利用弛豫时间分布法对锂电池阻抗特性进行分析;在获得电池阻抗特性的基础上,对电池弛豫时间分布曲线进行解析;最后筛选阻抗特征参量为模型输入量,构建支持向量机模型进行电池过充电检测。结果表明,弛豫时间分布曲线中的极化峰P1对应锂离子在固态电解质界面(solid electrolyte interphase,SEI)膜中的扩散过程、极化峰P2对应电子在正极材料中的扩散过程、极化峰P3对应锂离子在电极界面的氧化还原反应。过充电会导致电池欧姆内阻、SEI膜内阻与电荷转移电阻的增长速率最大为正常循环的266%、360%和182%,其中固态电解质界面SEI膜内阻为主要因素。电化学阻抗谱的阻抗特征参量以及支持向量机模型可以用于锂电池过充电检测,估计精度达93.24%。不仅可掌握电池的运行状态,还可对过充电进行有效辨识。

基于阻抗在线测量的锂离子电池过放电诱发内短路识别研究

锂离子电池的过放电行为可诱发内短路进而可能导致热失控。由于单体电池一致性差异和过放电导致的内短路初期电、热特征不明显,使得电压和温度等常规物理参数难以可靠实现故障预警,而阻抗可以反映电池内部信息,对故障状态具有较好的指示能力。该文通过分析锂离子电池过放电诱发内短路引起阻抗变化的机理,基于设计的阻抗在线测量装置,确定用于监测电池内短路故障的特征阻抗频率为70 Hz,获取过放电诱发内短路过程中特征频率下动态阻抗及阻抗变化率,提出一种基于动态阻抗特征的内短路在线识别方法并验证了方法的可靠性。实验结果表明,锂离子电池放电过程中动态阻抗半正弦变化特征可提前约144 s实现过放电预警,动态阻抗针状变化特征可提前约152 s实现内短路故障预警,动态阻抗明显回升特征可作为内短路发生的标志。此外,阻抗变化率特征有助于实现锂离子电池故障识别及预警,该方法在锂离子电池故障在线快速诊断中具有重要的应用潜力。

锂离子电池电解液安全性的影响因素及改进措施

锂离子电池由于能量密度高、高电压和维护成本低等优点而被大家使用.但在使用它们的过程中存在燃烧、爆炸等安全问题.电解液是锂离子电池中最易燃的组分,所以其与锂电池的安全性息息相关.改进电解液是提高锂离子电池安全性的关键方法.首先探讨了影响锂离子电池电解液安全性的因素,然后提出了改善措施,主要包括添加阻燃剂和抗过充添加剂来降低风险.

不同充电条件下三元锂电池过充热失控研究

为了研究充电倍率以及充电倍率的调整方式对过充条件下三元锂电池热失控的影响,分别以0.5C、1.0C、1.5C充电倍率将锂电池过充至热失控。此外,以0.5C充至电池表面温度不再上升时,分别以0.5C和0.07C的幅度逐步调高充电倍率,直至发生热失控。结果表明:以0.5C过充时,在短时间内不会发生热失控;以1.0C和1.5C过充时,均会发生热失控,且1.5C下热失控所需时间更短,热失控的危害更大。相比于采用0.5C幅度提高充电倍率的调节方式,采用0.07C幅度的调节方式会显著提高临界充电倍率,从而降低热失控的风险;以0.07C逐步提高充电倍率的过程中存在一个拐点倍率,当充电倍率小于此拐点倍率时,充电倍率与其对应的峰值温度呈线性关系,而当充电倍率大于拐点倍率后,继续提高充电倍率会导致热失控;先以0.5C过充,而后提高充电倍率导致热失控,其热失控危害远低于1.0C和1.5C过充的危害。因此,应当在符合实际需求的前提下采取较低的充电倍率。如需增加充电倍率,采取缓慢增加的方式有助于降低电池发生热失控的风险。

高镍三元锂离子电池热失控诱发与扩散机制研究

研究了不同加热功率和过充电电流导致高镍三元锂离子电池的热失控失效机制。在不同加热功率和不同过充电倍率下分别触发电池单体和模组中单体的热失控,并结合电压-电流-温度数据分析、计算流体动力学仿真以及其他辅助手段等研究了高镍三元锂离子电池单体和模组热失控的诱发和扩散过程。测试和仿真结果表明:随着加热功率的提高,热失控响应速度逐渐加快,但热失控最高温度呈逐渐下降的趋势;较小的充电倍率可有效抑制热失控和热扩散的发生,而大倍率充电可能引发电池的热失控,由过充电引发的中间电芯的热失控未必造成整个电池模组发生热失控扩散现象。

考虑过充/过放的电化学储能电站建模及故障特性分析

随着电化学储能的广泛应用,其已成为解决可再生能源并网问题的热门方案之一。然而,储能电站的充放电模式转换及不同的运行控制策略等,将导致电网故障特征更为复杂。为全面、深入地分析储能电站的并网故障特征,文中基于实际的储能电站拓扑结构和运行控制策略,建立了电化学储能电站仿真模型,模拟在常规充/放电、故障穿越、过充/过放等不同工况下储能电站的动态响应过程。在此基础上,明确了储能电站在常规充/放电和过充/过放场景下的故障特性差异,分析了产生差异的决定因素。最后,基于PSCAD/EMTDC仿真平台完成了所建模型的功能性验证,研究结果为了解储能电站的工作原理、研究储能电站的并网控制策略及保护方案提供了借鉴。

月球探测储能电池过放电影响分析

月球探测器与卫星等航天器不同,在月面工作时,月夜时间长达14 d,储能电池存在过放电的风险。通过对储能电池进行不同时长的过放电(采用电阻模拟载荷将电池过放电至0 V)试验,探讨了电池过放电对电池的容量、自放电等性能的影响。结果表明:过放电时间越长,电池的自放电性能越差,电池容量有小幅度下降。但经过活化后,自放电性能有明显改善。

锂离子电池微过充循环老化特性与失效机理研究

锂离子电池在实际工作中会因为电池组的不一致性或充电系统故障而出现微过充现象,长期循环会引发安全隐患。为探究微过充循环对锂离子电池老化特性及其失效机理的影响,将电池分别过充至不同截止电压,应用电化学阻抗谱、弛豫时间分布和容量增量分析等技术对其进行老化分析,并结合拆解后电极的扫描电子显微镜(SEM)、能量色散X射线谱(EDS)和X射线光电子能谱(XPS)表征加以验证。实验结果表明,与正常循环相比,微过充循环会显著加速电池老化,导致电池比容量衰减速度加快;随着循环次数的增加,电池内部的可用锂离子和活性材料不断消耗,电池各类阻抗明显增加,其中4.5 V微过充循环电池的电荷转移电阻较初始状态增加了196.15%;微过充循环还会加剧电池极化现象,降低材料的循环稳定性;微过充循环后,电池的活性材料逐渐从集流体上脱落,正极材料的活性颗粒破裂,负极材料表面固体电解质界面(SEI)膜增厚,F、P元素含量显著增加。

锂离子电池过充行为实验研究

过充电是造成锂离子电池系统热失控的主要原因之一,研究锂离子电池过充前后的性能参数变化规律是实现电池热失控及时预警的基础。以方壳磷酸铁锂(LFP/GC)电池为研究对象,研究了电池过充至不同截止电压后的外特性参数变化规律,并定性评估其热失控风险。结果表明,锂离子电池过充后电化学极化内阻变化明显,与电池过充程度紧密关联,过充至4.5 V时急剧增大至初始值6倍,同时电池内部压力也随过充而增加。电池过充后,检测到电池直流内阻分量和膨胀压力的明显变化,可以将其作为判断过充是否严重的重要依据,研究成果可以为电池管理系统(BMS)和能量管理系统(EMS)特征参数的选取提供参考,作为电池系统风险预警和安全监控的重要依据。

锂离子电池石墨负极失效及其先进表征方法

在便携式设备和电动汽车发展日益受到关注的背景下,锂离子电池凭借其能量密度高、循环寿命长、自放电小等优点成为了大规模应用的商业电池。然而,锂离子电池在使用的过程中存在析锂、短路、热故障以及产气等多种失效形式,造成了锂离子电池容量衰减、电池膨胀、热失控等。因此,揭示电池失效原因对高安全长寿命锂离子电池进一步发展有着巨大的推进作用。本文针对锂离子电池中应用较为普遍的石墨负极,阐述了石墨负极在析锂、高低温、过充等条件下的失效机制,并重点介绍了对于不同失效机制下的先进表征方法,其通过石墨的结构、脱嵌锂时的相变、石墨表面的形貌、负极所释放的热量和反应所产生的气体等多种途径进行分析,总结出四种失效原因主要影响了石墨层间距、石墨脱嵌锂时的相变、活性锂的损耗,另外还会有界面膜生成以及一系列副反应等失效机制。最后,本文归纳了针对各种失效原因的表征方法并进行了分类,同时展望了对于电池失效分析的规范化和标准化,对未来的电池失效分析研究有一定的推动作用。

过热下磷酸铁锂锂离子电池的过充电耐受性

研究极端条件下的多场耦合相互作用,有助于深入理解锂离子电池的热失控机理。在85℃的过热环境下,将1380200型20 Ah软包装磷酸铁锂动力锂离子电池的过充电压从4.07 V阶梯式增加至5.42 V,电池发生气体泄压但未出现起火或爆炸,表明电池即使在过热条件下也具有较强的耐过充电能力。泄压过程中,首先检测到氢气的信号,随后检测到一氧化碳、烷烃和烯烃等易燃气体。XRD分析表明,过充电后,正极活性物质磷酸铁锂完全去锂化生成了磷酸铁。SEM结果显示,部分过充电后的磷酸铁颗粒出现裂纹,但结构未被进一步破坏,证实了磷酸铁锂的高热稳定性。

微过充下三元镍钴铝锂离子电池的老化机理

电芯的不一致性及电量不均衡,会导致部分锂离子电池单体出现微过充现象,但此情况对于电池容量的影响未被完全揭示。在不同最高截止电压(4.2 V、4.3 V和4.4 V)下对三元镍钴铝(Li_(x)Ni_(0.80)Co_(0.15)Al_(0.05)O_(2))电池进行恒流充电循环老化实验,采用差分电压分析、电化学阻抗谱(EIS)等测试方法,探究高截止电压循环对电池老化的影响。随着最高截止电压的升高,电池老化速度加快,以2.5 A电流循环280次后,4.2 V、4.3 V、4.4 V下的容量保持率分别为90.30%、88.19%和86.19%。差分电压分析表明,容量衰减加速的原因是正极活性物质损失和活性Li+损失。EIS测试表明,微过充导致固体电解质相界面(SEI)膜阻抗略微升高,电荷转移阻抗升高,且程度随截止电压的升高而增大。

基于活性炭‖Na_(0.44)MnO_(2)的低成本、高倍率和长寿命碱性钠离子电池电容器

水系钠离子电池电容器具有成本低、功率大、安全性好等优点,是下一代大规模储能系统的理想选择之一。本文采用Na_(0.44)MnO_(2)正极、活性炭(AC)负极、6mol·L^(-1)NaOH电解液和廉价的不锈钢集流体构建了可充电碱性钠离子电池电容器。由于Na_(0.44)MnO_(2)正极在碱性电解液中具有较高的过充耐受性,通过首次充电时的原位过充预活化过程可以解决半钠化Na_(0.44)MnO_(2)正极和AC负极初始库伦效率低的缺点。因此,AC‖Na_(0.44)MnO_(2)可充电碱性钠离子电池电容器具有优异的电化学性能,在功率密度为85 W·kg^(-1)时,能量密度达26.6 Wh·kg^(-1),循环10000次后容量保持率为89%。同时,在50℃的高温和-20℃的低温也具有良好的电化学性能。这些结果表明AC‖Na_(0.44)MnO_(2)可充电碱性钠离子电池电容器具备应用于大规模储能的潜力。

Self-actuating protection mechanisms for safer lithium-ion batteries

Safety issue is still a problem nowadays for the large-scale application of lithium-ion batteries(LIBs)in electric vehicles and energy storage stations.The unsafe behaviors of LIBs arise from the thermal run-away,which is intrinsically triggered by the overcharging and overheating.To improve the safety of LIBs,various protection strategies based on self-actuating reaction control mechanisms(SRCMs)have been proposed,including redox shuttle,polymerizable monomer additive,potential-sensitive separator,thermal shutdown separator,positive-temperature-coefficient electrode,thermally polymerizable addi-tive,and reversible thermal phase transition electrolyte.As build-in protection mechanisms,these meth-ods can sensitively detect either the temperature change inside battery or the potential change of the electrode,and spontaneously shut down the electrode reaction at risky conditions,thus preventing the battery from going into thermal runaway.Given their advantages in enhancing the intrinsic safety of LIBs,this paper overviews the research progresses of SRCMs after a brief introduction of thermal runaway mechanism and limitations of conventional thermal runaway mitigating measures.More importantly,the current states and issues,key challenges,and future developing trends of SRCTs are also discussed and outlined from the viewpoint of practical application,aiming at providing insights and guidance for developing more effective SRCMs for LIBs.