Research progress on safety of lithium ion battery electrolyte

锂离子电池的能量密度及其安全问题是限制其在电动汽车应用中的主要障碍。随着能量密度的不断提升,当务之急是有效解决锂离子电池的安全性问题。锂离子电池安全问题本质上与当前电解液中使用的高挥发性、易燃的有机溶剂有关。因此,本文主要从电解液的燃烧性角度,介绍了电解液在锂离子电池材料安全性方面的研究现状,包括阻燃添加剂、不燃性氟代有机溶剂、高浓度电解液及固液混合电解质的应用等,分析其对安全性能提升的机理,并对电解液的发展方向进行了展望。     

High safety electrolyte for lithium-ion battery

锂离子电池安全性问题的本质是电池内部发生了热失控,热量不断的累积,造成电池内部温度持续上升,其外在的表现是燃烧、爆炸等。因此,锂离子电池的安全性与比能量、使用温度和倍率性能等存在一定的矛盾。电池能量密度越高、倍率性能越快和使用环境越恶劣,其能量剧烈释放时对电池体系的影响就越大,安全问题也越突出。当前锂离子电池电解液一般由低闪点的碳酸酯、对痕量水和温度敏感的LiPF₆和其它添加剂组成,本身具有高度可燃性。同时,电解液与正负极材料之间形成界面膜被认为是电池热失控的起点。因此,电解液改性是提升电池安全性的重要措施。本文分析了离子液体和氟代溶剂等溶剂对电解液安全性的提升效果,对比了多种锂盐对电解液安全性的影响,介绍了阻燃剂、过充保护剂、锂枝晶抑制剂和成膜稳定剂等电解液添加剂对锂电池安全性的改善。最后,从电池整体应用性能的角度出发,讨论了今后高安全性锂离子电池电解液的研发方向。     

Studies on the standard of lithium ion battery electrolyte

电解液是锂离子电池关键技术之一,在正负极之间起着输送和传导电流的作用,是连接正负极材料的桥梁。它影响着电池的工作电压、能量密度和安全性能等。近年来随着正负极材料的技术进步,电解液为了实现与新材料的匹配,在组分上出现了很大变化,现有的锂电池电解液标准及相应的测试方法也需要进一步更新,才能实现产品的检验规范化和质量标准化。本文介绍了电解液的现状及发展趋势,分析了我国现有电解液相关标准的情况,并对新的电解液国标提出了建议。     

A novel structure of ceramics electrolyte for future lithium battery

In order to fabricate large scale all-solid-state Li battery, we suggested a novel structure of solid electrolyte, which is composed of porous electrolyte supported by honeycomb-type electrolyte. A possibility of fabrication of the honeycomb-supported porous electrolyte and a compatibility of this structure with all-solid-state battery were examined using LLT (Li_0.35La_0.55TiO₃) solid electrolyte which is one of the anticipated solid electrolytes due to its high Li ion conductivity. A porous layer membrane with 3 dimensionally ordered (3DOM) macroporous structure was prepared by a colloidal crystal templating method. The porous honeycomb was fabricated by pushing the membrane into holes of honycomb using a needle followed by calcination. The 3DOM membrane and honeycmb electrolyte were sintered well each other. After filling the 3DOM pores with LiMn₂O₄ cathode material, the compatibility of this novel porous honeycomb electrolyte with all-solid-state battery was examined. The LiMn₂O₄/porous honeycomb cell clearly demonstrated charge and discharge behaviors, indicating the porous honeycomb structure can be applied to the all-solid-state battery. The discharge capacity was 71 mA h g⁻¹ (1.3 mA h cm⁻²) at 30 °C.     

An optimal electrolyte addition strategy for improving performance of a vanadium redox flow battery

In this paper, the influences of multistep electrolyte addition strategy on discharge capacity decay of an all vanadium redox flow battery during long cycles were investigated by utilizing a 2-D, transient mathematical model involving diffusion, convection, and migration mechanisms across the membrane as well as the contact resistance in the battery. Results show that with various multistep electrolyte addition strategies, the discharge capacity decay of the battery can be diminished. An optimal multistep electrolyte addition strategy is presented, which is corresponding to adding 1.04 mol L⁻¹ V³⁺ electrolyte to a negative tank while adding 1.04 mol L⁻¹ VO₂⁺ electrolyte to a positive tank. Results show that capacity decay of the battery can be debased by 10.8%, which is due to increased vanadium ions in the negative side and the decreased state-of-charge (SOC) imbalance between two half-cells. This study will propose a practical method for mitigating the discharge capacity decay of the battery during operation.     

A novel organic/inorganic composite solid electrolyte with functionalized layers for improved room‐temperature rate performance of solid‐state lithium battery

High ionic conductivity at room temperature (RT) and good ion transport capability at electrode/electrolyte interface are fundamental requirements for high‐rate solid‐state lithium batteries (SSBs). In this work, we designed a poly (propylene carbonate) (PPC)‐based organic/inorganic composite solid electrolyte (CSE) membrane with high filling of tantalum‐doped lithium lanthanum zirconium oxide (LLZTO) and functionalized layers for enhancing the RT rate performance of SSB. The synergistic effect of LLZTO and interfacial functionalized layers endows the NCM622/CSE/Li battery with high‐rate and cycling performances at RT. The SSB with 20% LLZTO‐filled solid electrolyte shows the initial capacities of 162.0, 148.5 and 130.1 mAh g^?1 at 1C, 2C, and 3C respectively, with retention capacities of 115.6, 104, and 100.6 mAh g^?1 after 150 cycles. This strategy for an organic/inorganic CSE is of great practical significance for the development of high‐rate SSBs.     

新型PEO/LPOS复合聚合物电解质的制备与性能研究

将具有较高电导率和稳定性的硫化物电解质LPOS引入PEO基聚合物中,制备一种新型PEO/LPOS复合聚合物电解质。研究结果表明,1%LPOS的添加能显著改善PEO基聚合物电解质的电导率、锂离子迁移数和电化学稳定性。与纯PEO基电解质相比,新制备的复合聚合物电解质PEO18-LiTFSI-1%LPOS室温电导率由   6.18×106 S/cm提高至1.60×105 S/cm,提高了158%。80 ℃表现出最佳电导率为1.08×103 S/cm,电化学窗口提高至4.7 V,同时具有非常良好的对锂稳定性。以新型复合电解质组装的LiFePO4/Li全固态锂电池表现出良好的循环稳定性,在60 ℃ 1 C下循环50周后放电比容量仍维持在105 mA•h/g以上。     

Improvement of flexible lithium battery shelf life by pre-discharging

Poly (methyl methacrylate) (PMMA)-based gel electrolyte has been used in flexible lithium batteries. These batteries are flexible and less than 0.5 mm thick, which make them suitable as power sources for smart cards and radio frequency identification (RFID) tags. We investigated the electrochemical properties of flexible lithium batteries using an impedance analyzer and potentiostat/galvanostat to evaluate the electrical capacities. To prevent the formation of gas by decomposition of electrolyte solvent, the batteries had to be pre-discharged about 5% of theoretical MnO₂ capacity. Of the three kinds of pre-discharging methods, especially, battery two-step pre-discharging method was performed showed the best electrical properties after storage at 60 °C for 60 days.     

A novel titania nanorods‐filled composite solid electrolyte with improved room temperature performance for solid‐state Li‐ion battery

Solid‐state batteries (SSBs) with room temperature (RT) performances had been one of the most promising technologies for energy storage. To achieve a chemical stable and high ionic conductive solid electrolyte, herein, a titania (TiO₂) (B) nanorods‐filled poly(propylene carbonate) (PPC)‐based organic/inorganic composite solid electrolyte (CSE) was prepared for the first time. It was found that by using TiO₂(B) nanorods, the ionic conductivity of the CSE membrane could be improved to 1.52 × 10^?4 S/cm, the electrochemical stable window was more than 4.6 V, and the tensile strength reaches 27 MPa with a strain less than 6%. The CSE was applied for SSB and showed excellent room temperature electrochemical performances. At 25°C, the LiFePO₄/CSE/Li SSB with 3%TiO₂‐filled CSE had the first cycle specific discharge capacity of 162 mAh/g with a capacity retention of 93% after 100 cycles at 0.3C. While the NCM622/CSE/Li SSB with 3%TiO₂‐filled CSE had the first specific discharge capacity of 165 mAh/g with a capacity retention of 88% after 100 cycles at 0.3C. The enhancement effect of TiO₂(B) nanorods could be ascribed that the rod‐like fillers provide more continuous Li‐ion transport path compared with nano particles, and the surface porosity and composition of TiO₂(B) nanorods could also improve the interfacial contact and Lewis acid‐base reaction sites between polymer and fillers. The TiO₂(B) nanorods‐filled CSE with high chemical stability, potential window, and ionic conductivity was promising to meet the requirements of SSBs.     

Modeling the electrochemical behaviors of charging Li‐ion batteries with different initial electrolyte salt concentrations

Based on a 1D electrochemical model, a series of galvanostatic charge processes of lithium ion batteries with different initial electrolyte salt concentrations are simulated and investigated. In light of the simulation results, it is found that many electrochemical characters, including charge curve, end‐of‐charge salt concentration, anode potential, and reaction depth distribution, can all be affected by initial electrolyte salt concentration. Meanwhile, the lithium plating phenomenon commonly occurring during charge is studied with batteries of different salt concentrations during overcharge. A corresponding solution, changing the thickness ratio of anode to cathode, is proposed, which can also be used to extend the charging capacity. Overall, this study gives better understanding of the relevance between electrochemical behaviors of charging battery and initial electrolyte salt concentration, thus emphasizes the important role of electrolyte salt concentration in the performance and health of lithium ion battery. Copyright © 2016 John Wiley & Sons, Ltd.     

Optimization of the electrolyte ratio for the vanadium flow battery and its effect on the battery performance

电解液是钒电池能量存储的核心,其组成对电池的能量转化效率、循环稳定性等具有显著影响。本工作针对正负极电解液体积比、电解液价态,较系统地考察了它们对钒电池电化学性能的影响规律。结果表明,保持正极电解液体积不变,单纯增加负极的体积,可提高电池的放电容量,但对电池的能量转换效率影响较小;电解液价态的升高会在一定程度上降低钒电池的放电容量,但其能量转换效率却呈现先升高后降低的抛物线规律;增加负极电解液体积和提高电解液价态均会导致负极活性物质过量,但后者对电池性能的影响更为显著,在后者的基础上前者对能量转换效率的影响也会被放大。     

Discharge characteristic of a non-aqueous electrolyte Li/O2 battery

Discharge characteristic of Li/O₂ cells was studied using galvanostatic discharge, polarization, and ac-impedance techniques. Results show that the discharge performance of Li/O₂ cells is determined mainly by the carbon air electrode, instead by the Li anode. A consecutive polarization experiment shows that impedance of the air electrode is progressively increased with polarization cycle number since the surfaces of the air electrode are gradually covered by discharge products, which prevents oxygen from diffusing to the reaction sites of carbon. Based on this observation, we proposed an electrolyte-catalyst “two-phase reaction zone” model for the catalytic reduction of oxygen in carbon air electrode. According to this model, the best case for electrolyte-filling is that the air electrode is completely wetted while still remaining sufficient pores for fast diffusion of gaseous oxygen. It is shown that an electrolyte-flooded cell suffers low specific capacity and poor power performance due to slow diffusion of the dissolved oxygen in liquid electrolyte. Therefore, the status of electrolyte-filling plays an essential role in determining the specific capacity and power capability of a Li/O₂ cell. In addition, we found that at low discharge currents the Li/O₂ cell showed two discharge voltage plateaus. The second voltage plateau is attributed to a continuous discharge of Li₂O₂ into Li₂O, and this discharge shows high polarization due to the electrically isolating property of Li₂O₂.     

Low temperature thermal safety performance of soft packaged lithium iron phosphate battery

本文以剩余容量接近80%的软包磷酸铁锂电池为研究对象,研究其在-10 ℃低温充放电循环后的安全性能.对低温和常温循环后的电池进行热失控实验分析,同时解剖电池并测试电池材料的锂元素含量和热稳定性能.测试结果表明,电池低温循环过程中容量急剧衰减,低温循环后电池热失控温度明显降低,低温循环过程中电池负极析出了锂单质,电池材料的热稳定性也发生了变化.另外,还对低温循环后的电池进行了满电状态下的常温搁置实验,实验过程中电池全部产生胀气现象,通过进一步测试分析发现,气体以CO和H₂为主.与新电池对比发现,剩余容量接近80%的软包磷酸铁锂电池低温下充放电循环更容易产生锂枝晶,造成其电化学性能发生严重的不可逆衰退,热失控温度明显提前,因此剩余容量接近80%的磷酸铁锂电池应避免在低温下运行.     

Compounding preparation of novel solid electrolyte with high lithium ion conductivity

将二元硫化物固体电解质75Li2S·24P2S5·1P2O5（LPOS）的非晶前驱体与三元硫化物电解质Li10GeP2S12（LGPS）前驱体按不同质量比均匀混合后,在270℃下进行烧结制备得到系列新型固体电解质材料 (1ω%)LPOS·ω%(t-LGPS)（ω=3、5、7、10）。当ω=5时,制得的新型固体电解质95%LPOS·5%(t-LGPS) 在室温下具有最佳的离子电导率1.0×103 S/cm。采用XRD、EIS、SEM等手段对该新型电解质材料的结构、形貌及电化学性能等进行了系统表征,并对电导率提高的机理进行了探讨。构建的全固态锂电池LiCoO2/95%LPOS·5%(t-LGPS)/Li表现出良好的电池性能,在25℃、0.1 C下,电池首周放电容量为115.7 mA·h/g,循环20圈后仍有80.38%的容量保持率。     

Progress on high energy density lithium batteries by CAS battery research group

提高动力电池的能量密度将显著延长续航里程,对发展电动汽车具有重要的意义.中国科学院在2013年底部署了中国科学院战略性先导科技专项,通过合作研究,积极探索了第三代锂离子电池,固态锂电池,锂-硫电池和锂-空气电池等电池体系.其中,采用纳米硅碳负极,富锂正极的24 A·h的锂离子电池单体,质量能量密度达到374 W·h/kg,体积能量密度达到577 W·h/L.8 A·h固态聚合物锂电池60 ℃下能量密度达到240 W·h/kg,基于无机陶瓷固态电解质的固态锂电池室温下能量密度达到240 W·h/kg.37 A·h的锂硫电池单体室温能量密度达到566 W·h/kg,50 ℃达到616 W·h/kg.5 A·h锂空气电池单体能量密度达到526 W·h/kg.目前这些样品电池在综合技术指标方面离实际应用还有较大的距离,需要进一步深入细致的进行基础科学与关键技术方面的研究.从长远考虑,电池能量密度的提高必然进一步增加电池安全性风险,因此不同形式的固态锂电池将是未来长续航动力锂电池的发展方向.     

Differential pulse effects of solid electrolyte interface formation for improving performance on high-power lithium ion battery

Solid electrolyte interface (SEI) formation is a key that utilizes to protect the structure of graphite anode and enhances the redox stability of lithium-ion batteries before entering the market. The effect of SEI formation applies a differential pulse (DP) and constant current (CC) charging on charge-discharge performance and cycling behavior into brand new commercial lithium ion batteries is investigated. The morphologies and electrochemical properties on the anode surface are also inspected by employing SEM and EDS. The electrochemical impedance spectra of the anode electrode in both charging protocols shows that the interfacial resistance on graphite anodes whose SEI layer formed by DP charging is smaller than that of CC charging. Moreover, the cycle life result shows that the DP charging SEI formation is more helpful in increasing the long-term stability and maintaining the capacity of batteries even under high power rate charge-discharge cycling. The DP charging method can provide a SEI layer with ameliorated properties to improve the performance of lithium ion batteries.     

Development of electrolyte thermodynamic studies for vanadium flow battery

钒液流电池作为可以规模化储能的一种二次电池越来越受到人们的重视,和其它类型的化学电池不同,其电解液不仅是离子导体,也是实现能量存储的电活性物质,是钒电池的核心.为了提高钒电池储能系统的性能并使之稳定运行,必须深刻认识钒电解液的热力学性质及变化规律.溶液热力学的研究可以提供如离子的存在形式,离子的活度及活度系数,不同形式离子对的解离常数等信息.这些热力学基础数据在设计电池和提升其性能方面都有着重要意义.本文对钒液流电池电解液热力学性质的研究进行了综述,重点介绍了量热法,密度法,电导法等在钒溶液研究中的应用,还介绍了Pitzer电解质溶液理论应用于钒溶液的研究情况,最后对热力学在钒液流电池电解液研究中的应用前景进行展望.     

Anti-precipitation effects of TiO2 and TiOSO4 on positive electrolyte of vanadium redox battery

In this study, the effects of TiO₂ and TiOSO₄ on the precipitation of the positive electrolyte of vanadium redox battery (VRB) systems were investigated. TiO₂ and TiOSO₄ were used as anti-precipitating agents for V(V) ions at 40 and 60 °C. The optimum amounts and electrochemical properties of additives were determined by electrochemical methods such as cyclic voltammetry and electrochemical impedance spectroscopy. The optimum amount of additives was identified as wt% 0.004 and 0.003 for TiO₂ and TiOSO₄, respectively. The structural features and composition of electrodes were investigated by scanning electron microscopic and energy-dispersive X-ray analysis. A plausible reaction mechanism was also proposed for redox reaction occurring on the positive electrode of a VRB. The concentration of V(V) ions in the additive including electrolyte were higher than that of blank solution at the end of the thermal precipitation tests. According to thermal and electrochemical studies, TiO₂ and TiOSO₄ can be useful additives for the positive electrolyte of a VRB.     

Synthesis of SnO2/C anode for lithium ion battery by a reflux-assisted hydrothermal method

以氯化亚锡(SnCl₂·2H₂O)及聚乙烯吡咯烷酮(polyvinylpyrrolidone,PVP)为原料,通过回流辅助水热法制备了SnO₂/C复合材料并将其用作锂离子电池负极材料.采用X射线衍射仪(XRD),扫描电子显微镜(SEM)和透射电子显微镜(TEM)分析材料的结构和形貌;用恒流充放电,交流阻抗(EIS)和循环伏安(CV)对复合材料作为锂离子电池负极材料的电化学性能进行表征.所制备的复合材料中,纳米SnO₂晶粒(5~10 nm)均匀分散在由PVP热解形成的无定形碳中.电化学性能测试表明,该复合材料100次循环后,可逆容量为591.7 mA·h/g,呈现较好的循环性能.优异的电化学性能主要归因于纳米SnO₂颗粒在无定形碳基体中均匀分散及无定形碳对锡颗粒体积变化的有效缓冲.     

Research progress of novel binders for silicon-based anode in lithium ion battery

硅基材料由于具有超高的理论比容量,安全的嵌锂工作电位和廉价易得等诸多优点,是下一代高比能量电池体系最理想的负极材料。尽管硅基材料的研究已经进行很长时间,但是硅基材料嵌锂时巨大的体积膨胀,循环性能较差等问题一直难以得到有效解决。开发高性能硅基负极黏结剂是解决硅基材料应用问题的重要途径之一,具有“刚柔并济”结构特性的黏结剂分子能够有效抑制硅基材料结构膨胀粉化,保持电极导电网络的完整性,从而有效提升其循环性能。本文综述了硅基负极黏结剂的特性要求,新型硅基负极黏结剂的研究进展,并对该领域未来潜在的研究方向进行了展望：复合体系聚合物黏结剂的开发;特殊空间构型黏结剂的开发;新型导电黏结剂的开发;自支撑无黏结剂硅基负极的开发。