Effects of particle size on the thermal stability of lithiated graphite anode

The thermal behavior of fully lithiated natural graphite flakes with different particle sizes has been investigated using differential scanning calorimetry (DSC). For DSC measurements, a fully lithiated graphite anode was heated in a hermetically sealed high pressure pan with a poly vinylidene diflouride (PVdF) binder and 1 M LiPF₆ solution in ethylene carbonate (EC)-diethyl carbonate (DEC) mixture. It has been founded that the particle size has a strong influence on the thermal stability of the lithiated graphite anode. The heat generation due to the solid electrolyte interface (SEI) decomposition increases with decreasing the particle size. The onset temperatures for exothermic reactions after initial SEI decomposition appear to be lower for graphite electrodes with smaller particle sizes. This is attributed to a thermal induced delithiation facilitated by reduced diffusion path and higher surface area in smaller graphites. The structural changes in graphites during DSC scan have been investigated by ex situ X-ray diffraction (XRD) and Raman spectrometer.     

Synthesis of passively prelithiated SiOx nanoparticles for Li-ion battery anode

A new concept of passive prelithiation to SiO_x nanoparticles is introduced and evaluated by investigating their nanostructures and electrochemical properties. Specifically, Li is incorporated into SiO_x nanoparticles during the nanoparticle synthesis. We obtain Si-Li-O-based nanoparticles, which we call SILIO; these are much larger than SiO_x particles and have totally different nanostructures. Due to nanostructures with various phase distributions, SILIO nanoparticles show enhanced electrochemical properties. The initial reversible capacity (IRC) and initial columbic efficiency (ICE) of SILIO nanoparticles are 946 to 1107 mAh/g and 72% to 77%, respectively, while SiO_x exhibits 1,064 mAh/g of IRC only with 41.5% of ICE. In addition, the stability of SILIO in the air is evaluated to guarantee no unstable phases such as Li₂O_x (x = 0–2) are present in SILIO. Through our findings, we suggest a new nanostructure model composed of crystalline Si, amorphous SiO_x, and lithium silicate.     

Electrolyte additive trimethyl phosphite for improving electrochemical performance and thermal stability of LiCoO2 cathode

The purpose of this paper is to investigate compositions on the interface between LiCoO₂ and electrolyte when trimethyl phosphite TMP(i) is used as an additive in 1 M LiPF₆/EC + DEC electrolyte system and the thermal stability of the electrolyte as well as Li_0.5CoO₂ mixed with the electrolyte. The electrochemical performance of LiCoO₂ electrode in the two electrolyte systems was also studied. It is found that the electrochemical performance, including capacity, cycle performance and 3.6 V plateau efficiency, has been improved in the electrolyte with TMP(i) additive. FTIR analysis indicates that Li_xPO_y is an important surface film composition on the cathode in TMP(i) containing system. A thicker and more passivating surface layer is formed when using TMP(i) additive as an additive. The thermal stability of the cathode is substantially improved in the electrolyte containing TMP(i) additive in the system, especially the exothermic peak around 190 °C, which is associated with the reaction between active surface of cathode and solvents, is obviously restrained.     

硬碳负极材料的热稳定性及其钠离子电池安全性能评测

钠离子电池作为一种有应用前景的能量储存系统,技术发展日趋完善。钠离子电池由于钠资源丰富,在大规模储能及低速电动车应用等领域具有成本优势,引起学术及产业界的广泛关注。随着钠离子电池产业的推进,电池安全性是亟待研究及数据积累的重点问题之一。近年来,随着电动汽车数量的增加和动力电池能量密度的提高,汽车安全事故时有发生,究其原因多为电池单体热量耗散造成。本工作从负极硬碳材料热稳定性、电芯过放电、极端破坏(挤压针刺等)和热失控等方面对钠离子电池进行安全性评测。结果表明,电解液的存在会降低嵌钠态硬碳的稳定性,且随负极嵌钠量增加,放热峰的位置也随之前移且更明显;与无过放电芯比较,软包电芯过放电至0 V对电芯的长循环稳定性基本无影响,循环500周后的容量保持率基本一致,且电流密度大小(0.1和1 C)对电芯容量恢复和循环性能亦无明显影响;挤压针刺测试结果表明钠离子电池安全性能良好,绝热加速量热仪(ARC)测试发现电芯安全性能并未随着荷电状态(SOC)增加趋于不稳定,实验结果表明30% SOC状态下电芯安全性最好。     

The influence of lithium salt on the interfacial reactions controlling the thermal stability of graphite anodes

The thermal stability of graphite anodes used in Li-ion batteries has been investigated, with the influence of electrolyte salt under special scrutiny, LiPF₆, LiBF₄, LiCF₃SO₃ and LiN(SO₂CF₃)₂ in an ethylene carbonate (EC)/dimethyl carbonate (DMC) solvent mixture. Differential scanning calorimetry (DSC) showed exothermic reactions in the temperature range 60-200 °C for all electrolyte systems. The reactions were coupled to decomposition of the solid electrolyte interphase (SEI) and reactions involving intercalated lithium. The onset temperature of the exothermic reactions increased with type of salt in the order: LiBF₄<LiPF₆<LiCF₃SO₃<LiN(SO₂CF₃)₂. X-ray photoelectron spectroscopy (XPS) was used to identify surface species formed prior to and after the exothermic reactions, to clarify different thermal behaviour for different salts. The decomposed SEI's in LiCF₃SO₃ and LiN(SO₂CF₃)₂ electrolytes were found to be mainly solvent-based, including lithium alkyl carbonate decomposition to stable Li₂CO₃ and the formation of poly(ethylene oxide) (PEO)-type polymers. In the LiBF₄ and LiPF₆ systems, decomposition was governed by salt reactions, which decomposed the salts and resulted in the main product LiF.     

混合石墨负极锂离子电池性能的研究

通过改变负极的配方,制作633048 s锂离子电池,分析了各种配方下,电池内阻随不同放电电压的变化情况;比较了不同负极配方电池容量与平台的保持率。当LCG含量小于10%时电池内阻较小,约小于60 mΩ,然而其循环性能和平台保持率小于20%。随着LCG含量的增加,约为15%时,100次循环容量保持率为91%左右,平台保持率为78%左右,内阻约为58mΩ,电池综合性能达到较好的水平。     

3-Chloroanisole for overcharge protection of a Li-ion cell

We observed that 3-chloroanisole (3CA), as an electrolyte additive was very effective for overcharging protection during a 12 V overcharging reaction. During overcharging, the cell voltage did not increase beyond 5.3 V, as opposed to other aromatic compounds that showed a voltage shoot-up to 12 V. This behavior was due to the 3CA decomposition and the formation of conducting polymer film within separator and at cathode/electrolyte interface, which consumes the surplus current and inhibit the voltage increase through the shunting effect. In addition, the use of 3CA did not lead to any problems with rate capability, cycle life, and long-term storage behavior at 50 and 70 °C. Furthermore, during storage at 90 °C for 4 and 24 h, electrolyte with 3CA in a Li-ion cell showed a similar increase of cell thickness as a cell without 3CA.     

锂离子电池电解液及功能添加剂的研究进展

从电解液的组成和功能添加剂两大方面,综合阐述了锂离子电池电解液的研究进展。在电解液组成方面,找到具有高的介电常数和能在石墨类电极表面形成有效SEI的有机溶剂,并且找到具有良好电导率、稳定电化学性能的电解质。而电解液功能添加剂方面,重点研究是找到改善电池安全性能的添加剂。     

Composite anode material of silicon/graphite/carbon nanotubes for Li-ion batteries

A composite anode material of silicon/graphite/multi-walled carbon nanotubes (MWNTs) for Li-ion batteries was prepared by ball milling. This composite anode material showed a discharge capacity of 2274 mAh/g in the first cycle, and after 20 charge-discharge cycles, a reversible capacity of 584 mAh/g was retained, much higher than 218 mAh/g for silicon/graphite composite. It was observed that silicon particles were homogeneously embedded into the “lamellar structures” of flaked graphite particles, and the silicon/graphite composite particles were further wrapped by a MWNTs network. The improvement in the electrochemical properties of the composite anode material was mainly attributed to the excellent resiliency and good electric conductivity of the MWNTs network.     

Promoting the Li storage performances of Li2ZnTi3O8@Na2WO4 composite anode for Li-ion battery

In this work, a reasonable strategy for the construction of Li₂ZnTi₃O₈@Na₂WO₄ composite was employed to promote the Li storage performances of Li₂ZnTi₃O₈. The Li₂ZnTi₃O₈@Na₂WO₄ composites (5, 10, and 15 wt%) were then prepared by a solution dispersion method. The introduction of Na₂WO₄ does not change the structures of the samples and they show similar morphologies with particle sizes from 100 to 200 nm. Suitable amount of Na₂WO₄ modification effectively improves the electrochemical performance of Li₂ZnTi₃O₈. Li₂ZnTi₃O₈@Na₂WO₄ composites (0, 5, 10, and 15 wt%) deliver the discharge/charge capacities of 137.4/136.4, 164.2/162.3, 189.2/188.1, and 154.5/153.3 mAh g^?1 at 0.5 A g^?1 after 100 cycles, respectively. Li₂ZnTi₃O₈@Na₂WO₄ composites (10 wt%) has the highest reversible capacities among all samples. The Na₂WO₄ shell with an excellent electronic conductivity can reduce electrode polarization, decrease the charge transfer resistance, enhance the Li-ion diffusion coefficient of Li₂ZnTi₃O₈, and then improve the electrochemical kinetics of composites. In addition, the formation of Ti–O bonds at the interface can be helpful for the stabilization of the composite, being beneficial for the improvement of their cycling stabilities. These results reveal that Na₂WO₄ coating is a facile and effective strategy to promote the Li storage performance of Li₂ZnTi₃O₈.     

锂离子电池电解液中杂质的影响及其脱除

介绍了有机电解液制备过程中各种杂质的来源、对锂离子电池性能的影响及脱除方法。     

Electrochemical properties of Si/Ni alloy–graphite composite as an anode material for Li-ion batteries

Si/Ni alloy and graphite composites were synthesized using arc-melting followed by high energy mechanical milling (HEMM). Alloy particles comprising of NiSi₂, NiSi and Si phases were distributed finely and uniformly on the surface of graphite in the composites obtained after HEMM. The composite containing 60 wt.% of Si/Ni alloy exhibited a stable capacity of 780 mAh/g. Fourier transform infrared spectroscopy (FTIR) analysis confirmed that some bonds were formed between alloy and graphite after HEMM, which appeared to retain the electrical connection between alloy and graphite during cycling. X-ray diffraction (XRD) analysis indicated that NiSi₂ and NiSi phases, which acted as an inactive alloy matrix remained invariant during charge and discharge. In addition to NiSi₂ and NiSi phases, disordered graphite layers also played the role of media for the accommodation of large volume change of Si during cycling. The large reversible capacity and good cycleability showed that Si/Ni alloy and graphite composite could be an alternative to conventional graphite-based anode materials for lithium-ion secondary batteries.     

Effect of 1-butyl-1-methylpyrrolidinium hexafluorophosphate as a flame-retarding additive on the cycling performance and thermal properties of lithium-ion batteries

1-Butyl-1-methylpyrrolidinium hexafluorophosphate (BMP-PF₆) was used as a flame-retarding additive in the liquid electrolyte, and the influence of BMP-PF₆ content on cycling performance and thermal properties of lithium-ion batteries was investigated. Self-extinguishing time and DSC studies demonstrated that the addition of BMP-PF₆ to the electrolyte provided a significant suppression in the flammability of the electrolyte and an improvement in the thermal stability of the cell. The optimum BMP-PF₆ content in the electrolyte was found to be 10 wt.% for improving safety without degrading cycling performance of the cell.     

A ternary MnO/MnTiO3@C composite anode with greatly enhanced cycle stability for Li-ion batteries

Manganese monoxide (MnO) has been widely studied as a potential anode material of Li-ion batteries because of its high specific capacity and abundant raw materials. However, the poor cycling stability of MnO associating to its large volume change during the repeated conversion reaction with Li⁺ has restricted its practical applications. Herein, ternary MnO/MnTiO₃@C composite anode materials are prepared by in situ capturing TiO₂ nanoparticles into sea urchin-like MnO₂ in a mild hydrothermal reaction, followed by resorcinol-formaldehyde (RF) resin coating and thermal treatment. With the strong stabilization effect of the MnTiO₃ component, the optimized ternary MnO/MnTiO₃@C composite anode exhibits greatly enhanced cycling performance as compared to MnO@C. A reversible capacity of 383 mAh g^?1 is preserved after 500 cycles at 1000 mA g^?1. This improved cycle performance can be originated from the stable TiO crystals and the highly reversible amorphous Li_xMnTiO₃ phase generated in the first lithiation process. The reasonably high specific capacity and robust cycle stability enable the ternary MnO/MnTiO₃@C composites to be promising alternative anode materials to graphite for Li-ion batteries.     

Si基锂离子电池负极材料研究进展

硅具有高的理论比容量、较低的嵌锂电位、来源广泛且环境友好等优点,被认为是下一代锂离子电池负极材料的有力竞争者。然而,在锂离子脱嵌过程中巨大的体积膨胀引起了活性材料的粉化和破裂,这带来了电极循环性能差、容量衰减快甚至电极失效等一系列问题。迄今为止,有大量关于改性硅基材料的报道。本文将重点介绍硅基材料的纳米结构化设计和硅/碳材料的结合。首先,分析了硅的储锂及失效机制,从机理上理解硅的失效对其电化学性能的影响。其次,从理论上阐述了纳米级硅材料对缓解体积效应的机理,从结构设计、材料合成、形态特征和电化学性能等方面论证了纳米硅材料的优势。随后,从缓解体积膨胀、提高电导率和形成稳定的固体电解质（SEI）膜等方面总结了硅碳复合材料的研究进展。此外,还讨论了将导电聚合物和金属引入硅基材料的电化学性能增强机理。最后,从提高首次库仑效率、SEI膜稳定性和质量负载量等方面对硅基材料的产业化应用提出几点建议。     

Low temperature performance of graphite electrode in Li-ion cells

We studied low temperature performance of Li/graphite cell. Results show that capacity of the graphite electrode falls significantly in the temperature range of 0 to −20 °C. When lithiation and delithiation are both carried out at −20 °C, graphite only retains 12% of the room temperature capacity. However, delithiation capacity of graphite increases to 92% of the room temperature value if the lithiation is carried out at room temperature. We believe that the poor low temperature performance of the cell is due to slow kinetics of lithium ion diffusion in graphite rather than low ionic conductivity of electrolyte and solid electrolyte interface (SEI) on the graphite surface. During lithiation and delithiation processes, lithium ion has the similar apparent chemical diffusion coefficient of 10⁻⁹-10⁻¹⁰ cm²/s at 20 °C, depending on the state of lithiation of graphite. We observed a dramatic decrease in lithium ion diffusivity in the temperature range of 0 to −20 °C, and that at low temperatures of <−20 °C, lithium ion has higher diffusivity in the delithiated graphite than in the lithiated one. We also observed that temperature dependence of cycling behavior of the Li/graphite cell follows the change of lithium ion diffusivity.     

A comparison of solid electrolyte interphase (SEI) on the artificial graphite anode of the aged and cycled commercial lithium ion cells

The commercial lithium ion cells with LiCoO₂ as cathode, artificial graphite as anode and 1 M LiPF₆/EC-DEC-EMC (ethylene carbonate-diethyl carbonate-dimethyl carbonate) (1:1:1, v/v/v) with additives (1 wt.% vinylene carbonate (VC) + 1 wt.% propylene sulfite (PS)) as electrolyte were aged at 60% and 100% state of charge (SOC) for 6 months at room temperature and the corresponding cycle performance was measured. Charge/discharge results showed that the capacity retentions after 100 cycles were in the order of fresh cell >60% SOC > 100% SOC. The composition of SEI on the anode was analyzed by X-ray photoelectron spectroscopy (XPS) and the sulfur atom in PS was used as a tagged atom in XPS analysis. The results suggested that the transformation of organic species to inorganic species and the species containing sulfur atom from the reduction of PS was dissolved for the cells aged at 60% and 100% SOC. The SEM and XPS surface and depth profile analysis showed that the increase of the thickness of SEI layer and the variation of compositions on storage or cycling, is one of the most important reasons that results in the deterioration of the cycle performance of commercial lithium ion cells aged at 60% and 100% SOC at room temperature for 6 months.     

Improved thermal stability of graphite electrodes in lithium-ion batteries using 4-isopropyl phenyl diphenyl phosphate as an additive

To enhance the thermal stability of graphite electrodes for lithium-ion batteries, 4-isopropyl phenyl diphenyl phosphate (IPPP) was investigated as an additive in the electrolyte of 1.0 M LiPF₆ in ethylene carbonate and diethyl carbonate (1:1 in weight). The electrochemical performance of Li/IPPP-electrolyte/C half cells was evaluated. The thermal behavior of Li _x C₆ and Li _x C₆-IPPP-electrolytes were examined using a C80 micro-calorimeter. Electrolytes with 5 and 10% IPPP improve the thermal stability of the graphite electrode in the tests. The electrochemical performance of Li/IPPP-electrolyte/C cells is not degraded by the addition of this amount of IPPP to the electrolyte.     

锂离子电池电解液负极成膜添加剂的研究进展

解决锂离子电池电极材料和电解液相容性的关键是形成稳定且Li⁺可导的固态电解质界面膜(SEI膜),因此,对优质负极成膜添加剂的研究成为锂离子电池研发中的一个热点。本文综述了锂离子电池电解液成膜添加剂的作用原理,具体介绍了各类负极成膜添加剂的研究现状,从成膜反应机理和理论计算方面详述了近几年来负极成膜添加剂的研究进展。分析了所存在的问题主要是如何快速地挑选出更适宜、更高效的成膜添加剂,并指出了成膜添加剂未来的发展趋势为:①研究各添加剂与电解液的反应机理,着重开发对锂离子电池副反应小的负极成膜添加剂;②通过选择两种或两种以上的添加剂的协同作用,以弥补一种添加剂的不足;③提高无机成膜添加剂在电解液中的溶解度。