过充保护添加剂氰基功能化2, 5-二叔丁基对苯二酚的合成及其在锂离子电池中的应用

设计合成了单氰基功能化的2, 5-二叔丁基-1-（β-氰基乙氧基）-4-甲氧基苯（RS-MCN）和双氰基功能化的2, 5-二叔丁基-1, 4-（β-氰基乙氧基）苯（RS-DCN）,并用作氧化还原过充添加剂开展了其在锂离子电子中的应用研究。通过丙烯氰和2, 5-二叔丁基对苯二酚的迈克尔加成反应可高效合成RS-MCN和RS-DCN,氰乙基取代后的过充保护添加剂分子的可逆氧化还原电位分别为4.02、4.08 V（vs Li/Li⁺）;并且单氰基取代的RS-MCN在商业碳酸酯电解液1 mol·L^-1 LiPF6/EC+DEC+EMC（1：1：1,体积比）中的溶解度可高达0.3 mol·L^-1。RSMCN和RS-DCN对LiFePO₄/Li电池的过充保护性能和电极相容性也进行了深入的研究,实验结果表明：RSMCN具有更好的过充保护性能和电极相容性,其5 V截止电压过充保护时间可超过1200 h,100%过充保护大于90周循环;0.3 mol·L^-1 RS-MCN的添加能使100%过充的LiFePO₄/Li电池在2.5C倍率条件下正常循环,其放电比容量达153.5 mAh·g^-1。此外,RS-MCN的添加对LiFePO₄/Li电池在2.5-3.8 V条件下的循环性能有明显改善,添加有RS-MCN的电池在60周的循环后容量保持率高达94.4%,而商业电解液的电池在60周循环后的容量保持率降至84.3%。因此,氰基功能化RS-MCN是一类具有潜在应用前景的过充保护添加剂。     

阻燃剂对5Ah锂离子软包电池倍率性能和安全性能的影响研究

在电解液中加入不同含量(5 %,10 %,20 %)的阻燃剂,研究了其对LiNi _0.4Co_0.2Mn_0.4 O₂三元材料作为正极材料组装的5 Ah锂离子软包电池的倍率性能、过充性能和短路性能的影响. 实验结果表明,电解液中5 %体积含量的阻燃剂使软包电池在1C和2C放电时,具有最好的倍率性能;当阻燃剂的体积含量提升到20 %,在过充时,电池表面温度升高的最少;在短路实验时,电池不起火、不爆炸.     

过充保护添加剂1,2-二甲氧基-4-硝基苯和1,4-二甲氧基-2-硝基苯在锂离子电池中的应用

在锂离子电池电解液1 mol·L^-1 LiPF₆/(碳酸乙烯酯(EC)+碳酸二乙酯(DEC)+碳酸甲乙酯(EMC) (1:1:1,体积比))中分别添加1,2-二甲氧基-4-硝基苯(DMNB1)和1,4-二甲氧基-2-硝基苯(DMNB2)作为防过充添加剂.采用循环伏安(CV)、恒流充放电、过充测试、电化学阻抗谱(EIS)、扫描电子显微镜(SEM)等手段研究了DMNB1和DMNB2 的防过充效果, 以及添加剂与LiNi_1/3Co_1/3Mn_1/3O₂材料的相容性. 结果表明: DMNB1 和DMNB2 的氧化电位都在4.3 V (vs Li/Li⁺)以上, 且均能显著提高电池的过充保护性能. 100%过充和5 V截止电压过充测试表明, DMNB1 的防过充性能优于DMNB2. 采用基础电解液、添加0.1 mol·L^-1 DMNB1 和添加0.1 mol·L^-1DMNB2 电解液的LiNi_1/3Co_1/3Mn_1/3O₂/Li 电池, 0.2C 倍率下循环100 次, 容量保持率分别为98.4%、95.9%和68.1%. 证明硝基在添加剂苯环上的取代位置和其电化学性能之间有着密切联系.     

功能添加剂对锂离子电池的防过充电化学行为研究

研究了功能添加剂3-氯苯甲醚(3CA)和联苯(BP)联合使用在锂离子电池电解液中的防过充行为。通过采用微电极循环伏安法、动电位扫描分析、扫描电镜法和充放电法等手段研究表明：联苯和3-氯苯甲醚混合添加剂的聚合电位随3-氯苯甲醚含量的增加由4.7V前移至4.6V (vs. Li/Li+);电池在正常工作电压(2.75V~4.2V)下,添加剂不参与电池反应过程;当电压高于4.2V电池发生过充时,3-氯苯甲醚在电极表面首先发生氧化还原飞梭分流限压对电池进行过充保护;电压继续升高时,联苯在电极表面发生电聚合反应,生成的聚合膜表面光滑致密是电子的良导体能有效的阻止Li+的嵌入与脱出,并通过自放电使电池处于安全状态,防止电池过充发生爆炸。两种防过充机制共同作用,对电池实施多重护防,提高了电池的安全性能。     

苯甲醚及其溴取代物用作锂离子电池防过充添加剂的研究

选择苯甲醚、2-溴苯甲醚、3-溴苯甲醚作为锂离子电池有机电解液的防过充添加剂. 采用循环伏安测试、恒流充放电测试、电化学阻抗分析、扫描电镜分析等手段, 研究三种添加剂的防过充作用效果, 以及对LiNi_1/3Co_1/3Mn_1/3O₂ (NCM)正极性能的影响. 结果表明: 三种添加剂均具有合适的氧化电位和良好的氧化还原特性, 能够提高锂离子电池的防过充性能. 其中2-溴苯甲醚的防过充作用效果最优, 电池经0.1 C充电长达近50 h后才达到5 V截止电压, 且可承受过充的次数相对最多, 但该添加剂对NCM正极的循环性能影响较大; 苯甲醚的防过充效果仅次于2-溴苯甲醚, NCM正极在添加有苯甲醚的电解液中循环性能良好, 0.2 C充放电循环80次后容量仍能保持93.8%左右. 含上述三种添加剂的电池经过充后, 均会有一部分氧化还原产物吸附在NCM正极表面, 增加电池的整体阻抗, 其中含2-溴苯甲醚的电池表现最为明显.     

锂离子电池爆炸机理分析

研究L iCoO2(或L1.05Co1/3N i1/3Mn3O2)/L ixC6锂离子电池材料的热分解特性以及锂离子电池在加热、过充、短路等情况下的爆炸机理.实验表明,50~350℃之间负极表面存在SEI膜的分解、L ixC6与电解液乃至L ixC6与PVDF等3种放热反应,电解液于178℃时开始放热,L i1-xCo1/3N i1/3Mn1/3O2的热分解反应起始于230℃.锂离子电池在150℃加热时爆炸,1.5 C过充至15 m in时爆炸,短路情况下不发生爆炸.     

铈盐配合物对锂离子电池的抗过充性能

通过在锂离子电池的电解液中添加五硝酸根合铈(Ⅲ)酸四丁基铵的方法来提高电池的安全性,讨论了氧化还原添加剂的作用原理,并考察了作用效果.实验结果表明,五硝酸合铈(Ⅲ)配合物在锂离子电池电解液中的氧化电位在4.0 V左右,扩散系数为3.82×10-6cm2/s.L iFePO4/L i模拟电池的研究结果表明,当电池发生过充时五硝酸合铈(Ⅲ)配合物可以在电池的正极上氧化,并扩散到电池的负极上还原,通过在电池的正负极之间穿梭将电池的电压稳定在4.0 V.     

纳米钴基氧化物锂离子电池负极材料的研究

采用流变相法合成Co3 O4 ,CoB1.3 6 O2 .8,CoB0 .5Al0 .1O1.5样品 ,并研究其作为锂离子电池负极材料的电化学性能 .当电池在 0 .0 1～ 3.0 0V的电压范围之间循环时 ,Li/Co3 O4 电池表现出最好的充放电性能 :循环 30周后 ,可逆比容量仍能保持为初始比容量 (931mAh/g)的 95 % .掺杂了B ,Al材料 ,其可逆比容量与未掺杂的相比明显降低 ,而且第 1周可逆容量随掺杂的B、Al量的增加而减少 .通过异位XRD方法研究了不同充放电态Co3 O4 电极材料结构的变化 .结果表明 ,Co3 O4 电极在充放电过程中与Li的反应机理不同于传统的过渡金属与Li的反应机理 ,即非Li+ 的嵌入 /脱出或合金的形成 ,而是Co3 O4 的可逆还原氧化以及Li2 O的可逆形成与分解机理     

三氟乙氧基磷酸酯的合成与性能研究

为提高锂离子电池安全性,本文制备了锂离子电池阻燃添加剂-三氟乙氧基磷酸酯(TFP).通过红外(IR)光谱法鉴定了产物结构;讨论了反应时间、反应物浓度比与产率的关系;以及TFP的加入对1mol/LLiPF6EC/EMC/DMC(1:1:1Vol.)电解液的可燃性、分解电压和离子电导率的影响.结果表明:反应时间、反应物浓度比对TFP产率影响较为明显,当催化剂为15mol.%(相对于三氯氧磷),反应时间6h,三氟乙醇与三氯氧磷摩尔比为6:1时,TFP的产率可以达到94.00%;添加TFP对电解液阻燃效果显著,对电解液的分解电压无不利影响,电解液电导率会有所下降,对Li/LiCoO2电池的比容量影响不大.     

固态电解质中锂离子传输机理研究进展

固态电解质在室温下表现出非凡的离子导电性,使其有潜力应用于全固态锂离子电池.开发新的高性能固态电解质需要对锂离子传输机理及其规律进行深入研究.本文论述了近期研究中锂离子传输机理方面的研究进展,包括离子传输理论基础的概述;总结Li10GeP2S12、Li7La3Zr2O12和Li1+xAlxTi2-x(PO4)3固态电解...     

N-Phenylmaleimide as a new polymerizable additive for overcharge protection of lithium-ion batteries

Electrochemical properties and overcharge behavior of N-phenylmaleimide (NPM) as a new polymerizable electrolyte additive for overcharge protection of lithium-ion batteries are studied by cyclic voltammetry, charge–discharge performance, electrochemical impedance spectroscopy and scanning electron microscopy (SEM). The results show that NPM can electrochemically polymerize at the overcharge potential of 3.8–4.2 V (vs. Li/Li⁺) and form a thin polymer film on the surface of the cathode, thus preventing voltage runaway. On the other hand, the use of NPM as an overcharge protection electrolyte additive does not influence the normal performance of lithium-ion batteries.     

Xylene as a New Polymerizable Additive for Overcharge Protection of Lithium Ion Batteries

The electrochemical properties and overcharge protection mechanism of xylene as a new polymerizable electrolyte additive for overcharge protection of lithium ion batteries were studied by cyclic voltammetry tests, charge- discharge performance and battery power capacity measurements. It was found that when the battery was overcharged, xylene could electrochemically polymerize at the overcharge potential of 4.3—4.7 V (vs. Li/Li＋) to form a thin polymer film on the surface of the cathode, thus preventing voltage runaway. On the other hand, the use of xylene as an overcharge protection electrolyte additive did not influence the normal performance of lithium ion batteries.     

Bifunctional electrolyte additive for lithium-ion batteries

2-(Pentafluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole was reported as a bifunctional electrolyte additive for lithium-ion batteries. It was found that the reported additive had a redox potential of 4.43 V vs. Li⁺/Li with a reversible oxidation/reduction reaction. Therefore, it is a promising redox shuttle for overcharge protection of most positive electrode materials for current lithium-ion-battery technology. At the same time, the boron center of this additive is a strong Lewis acid and can act as an anion receptor to dissolve LiF generated during the operation of lithium-ion batteries. The possibility of using the novel additive as both the redox shuttle and the anion receptor was discussed.     

锂离子电池爆炸机理研究

安全性是高容量及动力型锂离子电池商品化的主要障碍。当在热冲击、过充、过放、短路等滥用状态下,电池内部的活性物质及电解液等组分间将发生化学、电化学反应,产生大量的热量与气体,当积累到一定程度就会引起电池的着火、爆炸。本文综述了电池内部热量的来源和产生的原因,分析了电池在加热、过充、短路等状态下的爆炸机理,并提出了解决电池爆炸问题的具体措施。     

A highly soluble dimethoxybenzene derivative as a redox shuttle for overcharge protection of secondary lithium batteries

A compound 4-tertbutyl-1,2-dimethoxybenzene (TDB) was synthesized and tested as a redox shuttle for overcharge protection of Li–LiFePO₄ batteries. This isomer of tertbutyl-substituted dimethoxybenzene is miscible with the organic polar electrolytes and provides a solution for the poor solubility of ditertbutyl-substituted 1,4-dimethoxybenzenes as a redox shuttle additive. The experimental results demonstrated that the shuttle molecules added in the electrolyte cannot only provide feasible overcharge protection, but also have indiscernible detrimental influences on the charge–discharge behaviors of Li–LiFePO₄ cells, showing a great prospect for practical applications in commercial rechargeable lithium batteries.     

Degradation of lithium-ion batteries and how to fight it: A review

The phenomenology of the decrease in the capacity and energy density of lithium-ion batteries during their cycling and storage is considered together with the basic factors responsible for this phenomenon (overcharge and self-discharge of batteries, dissolution and phase alterations of electrode materials, cathodic reduction and anodic oxidation of electrolyte components, corrosion of materials of current leads) and the mechanism of chemical and electrochemical electrode processes responsible for degradation of batteries. Possible ways and basic techniques of increasing stability of exploitation characteristics of batteries are considered.Translated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 3–19.Original Russian Text Copyright © 2005 by Kanevskii, Dubasova.     

Triallyl Isocyanurate as an Efficient Electrolyte Additive for Layered Oxide Cathode Material-Based Lithium-Ion Batteries with Improved Stability under High-Voltage

In this study, a new electrolyte additive 1,3,5-tri-2-propenyl-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-trione (TAIC) for lithium-ion batteries is reported. The additive is introduced as a novel electrolyte additive to enhance electrochemical performances of layered lithium nickel cobalt manganese oxide (NCM) and lithium cobalt oxide (LiCoO₂) cathodes, especially under a higher working voltage. Encouragingly, we found protective films would be formed on the cathode surface by the electrochemical oxidation, and the stability of the cathode material–electrolyte interface was greatly promoted. By adding 0.5 wt.% of TAIC into the electrolyte, the battery exhibited outstanding performances. The thickness swelling decreased to about 6% after storage at 85 °C for 24 h, while the capacity retention of cycle-life performances under high temperature of 45 °C after the 600th cycle increased 10% in comparison with the batteries without TAIC. Due to its specific function, the additive can be used in high energy density and high voltage lithium-ion battery systems.     

多酚类化合物—丹宁酸用作锂金属负极电解液成膜添加剂

As the application of lithium-ion batteries in advanced consumer electronics, energy storage systems, plug-in hybrid electric vehicles, and electric vehicles increases, there has emerged an urgent need for increasing the energy density of such batteries. Lithium metal anode is considered as the "Holy Grail" for high-energy-density electrochemical energy storage systems because of its low reduction potential (-3.04 V vs standard hydrogen electrode) and high theoretical specific capacity (3860 mAh·g^-1). However, the practical application of lithium metal anode in rechargeable batteries is severely limited by irregular lithium dendrite growth and high reactivity with the electrolytes, leading to poor safety performance and low coulombic efficiency. Recent research progress has been well documented to suppress dendrite growth for achieving long-term stability of lithium anode, such as building artificial protection layers, developing novel electrolyte additives, constructing solid electrolytes, using functional separator, designing composite electrode or three-dimensional lithium-hosted material. Among them, the use of electrolyte additives is regarded as one of the most effective and economical methods to improve the performance of lithium-ion batteries. As a natural polyphenol compound, tannic acid (TA) is significantly cheaper and more abundant compared with dopamine, which is widely used for the material preparation and modification in the field of lithium-ion batteries. Herein, TA is first reported as an efficient electrolyte film-forming additive for lithium metal anode. By adding 0.15% (mass fraction, wt.) TA into the base electrolyte of 1 mol·L^-1 LiPF₆-EC/DMC/EMC (1 : 1 : 1, by wt.), the symmetric Li|Li cell exhibited a more stable cyclability of 270 h than that of only 170 h observed for the Li|Li cell without TA under the same current density of 1 mA·cm^-2 and capacity of 1 mAh·cm^-2 (with a cutoff voltage of 0.1 V). Electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, cyclic voltammetry (CV), and energy-dispersive X-ray spectroscopy (EDS) analyses demonstrated that TA participated in the formation of a dense solid electrolyte interface (SEI) layer on the surface of the lithium metal. A possible reaction mechanism is proposed here, wherein the small amount of added polyphenol compound could have facilitated the formation of LiF through the hydrolysis of LiPF₆, following which the resulting phenoxide could react with dimethyl carbonate (DMC) through transesterification to form a cross-linked polymer, thereby forming a unique organic/inorganic composite SEI film that significantly improved the electrochemical performance of the lithium metal anode. These results demonstrate that TA can be used as a promising film-forming additive for the lithium metal anode.     

全氟烷基膦酸锂电解液的制备与性能研究

选取氯代二异丙基膦(C6H14PCl)为原料, 利用电化学氟化方法, 得到全氟烷基膦酸[(C3F7)2PF3], (C3F7)2PF3与氟化锂(LiF)反应得到全氟烷基膦酸锂(Li[(C3F7)2PF4]), 将其溶于碳酸乙烯酯(EC)和碳酸二甲酯(DMC)质量比为1∶1的混合溶剂中得到电解液, 考察电解液的电导率、抗水性及氧化分解电位. 以LiCoO2为正极, 锂片为负极组装两电极模拟电池体系, 测试得到电池的放电平台为3.7 V; 电池的首次放电比容量为107 mA•h•g－1; 当循环放电40次后, 容量衰减较快, 电池循环50周后, 效率仍保持102%. 交流阻抗图谱表明电解液放电时的阻抗约为140 Ω. 研究结果表明, 全氟烷基膦酸锂有望成为新型锂离子二次电池的电解质盐.