Ionic conductivity in crystalline polymer electrolytes

Polymer electrolytes are the subject of intensive study, in part because of their potential use as the electrolyte in all-solid-state rechargeable lithium batteries. These materials are formed by dissolving a salt (for example LiI) in a solid host polymer such as poly(ethylene oxide) (refs 2, 3, 4, 5, 6), and may be prepared as both crystalline and amorphous phases. Conductivity in polymer electrolytes has long been viewed as confined to the amorphous phase above the glass transition temperature, Tg, where polymer chain motion creates a dynamic, disordered environment that plays a critical role in facilitating ion transport. Here we show that, in contrast to this prevailing view, ionic conductivity in the static, ordered environment of the crystalline phase can be greater than that in the equivalent amorphous material above Tg. Moreover, we demonstrate that ion transport in crystalline polymer electrolytes can be dominated by the cations, whereas both ions are generally mobile in the amorphous phase. Restriction of mobility to the lithium cation is advantageous for battery applications. The realization that order can promote ion transport in polymers is interesting in the context of electronically conducting polymers, where crystallinity favours electron transport.     

Separators for Lithium Ion Batteries

1 Results A separator for rechargeable batteries is a microporous membrane placed between electrodes of opposite polarity, keeping them apart to prevent electrical short circuits and at the same time allowing rapid transport of lithium ions that are needed to complete the circuit during the passage of current in an electrochemical cell, and thus plays a key role in determining the performance of the lithium ion battery. Here provides a comprehensive overview of various types of separators for lithium io...     

Effect of organic-inorganic hybrid P123-em-SBA15 on lithium transport properties of composite polymer electrolyte

A novel PEO-based composite polymer electrolyte by using organic-inorganic hybrid EO20PO70EO20-em-mesoporous silica (P123-em-SBA15) as the filler has been developed. The experiment results show that P123-em-SBA15 can enhance the lithium-ion transference number of the composite polymer electrolyte, which is induced by the special topology structure of P123 in PI23-em-SBAI5 hybrid. In addition, room temperature ionic conductivity of the composite polymer electrolyte can also be increased by about two orders of magnitude. The excellent lithium transport properties suggest that PEO-LiCIO4-P123-em-SBA15 composite polymer electrolyte can be used as electrolyte materials for all solid-state rechargeable lithium polymer batteries.     

纳米添加剂铁路轴承润滑脂摩擦试验数据分析

目前铁路轴承的损坏主要是由于润滑脂的失效引起轴承各部件间的急剧摩擦,这直接导致抱轴的发生,严重影响铁路的安全运输。在4号锂基润滑脂中加入不同纳米材料,配制成不同比例的样品,通过摩擦试验记录试验数据,运用乏信息理论估计每组试验数据的真值,发现不同材料和不同比例的纳米材料作为添加剂对钢球的减摩效果是不同的,纳米氧化锆材料加入到润滑脂中的减摩效果是很明显的,纳米铜材料反而会增大摩擦,不适合作为润滑脂的减摩添加剂。     

气相交换平衡技术在获得近化学计量比LiNbO3晶体中的应用

本文详细介绍了利用气相交换平衡（vapor transport equilibration:VTE)技术获得近化学计量比铌酸锂晶体薄片及其处理工艺。通过测量其OH^-红外吸收谱线宽及吸收边的位置，分析确定晶体薄片中的Li2O含量为49．9％，即[Li]/[Nb]=0.996，接近其化学计量比。     

Lithium intercalation mechanism for β-SnSb in Sn-Sb thin films

Based on the first-principles plane wave pseudo-potential method, the electronic structure and electrochemical performance of LixSn4Sb4 (x=2, 4, 6, and 8) and LixSn12-xSb4 (x=9, 10, 11, and 12) phases were calculated. A Sn-Sb thin film on a Cu foil was also prepared by radio frequency magnetron sputtering. The surface morphology, composition, and lithium intercalation/extraction behavior of the fabricated film were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV). Lithium atoms can easily insert into and extract out of the β-SnSb cell due to the low lithium intercalation formation energy. It is found that lithium atoms first occupy the interstitial sites, and then Sn atoms at the lattice positions are replaced by excessive lithium. The dissociative Sn atoms continue to produce different Li-Sn phases, which will affect the electrode stability and lead to the undesirable effect due to their large volume expansion ratio. The calculated lithium intercalation potential is stable at about 0.7 V, which is consistent with the experimental result.     

锂离子在LiMn2O4正极材料中的界面过程

采用交流阻抗法研究了锂离子在LiMn₂O₄正极材料中的界面过程.结果表明：LiMn₂O₄电极的交流阻抗复平面图中高频区的半圆，是由电解液中的锂离子在LiMn₂O₄表面吸附形成表面层的电阻和电容引起的，中频区的半圆是由电极LiMn₂O₄内的电荷转移反应电阻和双电层电容引起的，而低频区的直线则是由锂离子在LiMn₂O₄中的扩散引起的.     

Dead lithium phase investigation of Sn-Zn alloy as anode materials for lithium ion battery

In this work, based on First-principle plane wave pseudo-potential method, we have carried out an in-depth study on the possible dead lithium phase of Sn-Zn alloy as anode materials for lithium ion batteries. Through investigation, we found that the phases Li_xSn₄Zn₄(x = 2, 4, 6, 8) contributed to reversible capacity, while the phases Li_xSn₄Zn_8−(x−4)(x = 4.74, 7.72) led to capacity loss due to high formation energy, namely, they were the dead lithium phases during the charge/discharge process. And we come up with a new idea that stable lithium alloy phase with high lithiation formation energy (dead lithium phase) can also result in high loss of active lithium ion, besides the traditional expression that the formation of solid electrolyte interface film leads to high capacity loss. Supported by the National Natural Science Foundation of China (Grant No. 50771046), Natural Science Foundation of Guangdong Province (Grant No. 05200534), Key Projects of Guangdong Province and Guangzhou City (Grant Nos. 2006A10704003 and 2006Z3-D2031) and China Postdoctoral Science Foundation (Project No. 20080440764)     

Materials for Lithium Batteries Prepared via Mechanochemical Route

1 Results Nanostructured materials are currently of interest for lithium-ion batteries due to relevant demands for high-rate performance batteries and the aspect of structural stability (reversibility) under charge-discharge processes.Decreasing of particle size facilitates the reducing of diffuse paths for lithium ions as compared with micron-sized materials and the increasing of surface contact between electrode and electrolyte leading to acceleration of ionic transport and of charge-discharge process...     

锂离子电池正极材料锰酸锂制备方法的研究进展

LiMn2O4以其价格低、电位高、环境友好、安全性能高等优点,成为最有希望取代LiCoO2的主流材料之一.LiMn2O4的生产制备方法众多, 文中详细介绍了锰酸锂的晶体结构特点,阐述了锰酸锂的各种制备方法,探讨了采用不同的原料、不同的制备方法对提高锰酸锂性能的差异.从电解液方面、尖晶石锰酸锂晶体结构层面分析了其容量衰减的原因,希望能够为锰酸锂材料的研究者提供借鉴,为其生产提供理论依据.     

Synthesis of dandelion-like TiO2 microspheres as anode materials for lithium ion batteries with enhanced rate capacity and cyclic performances

Dandelion-like TiO₂ microspheres consisting of numerous rutile single-crystalline nanorods were synthesized for the first time by a hydrothermal method. Their crystal structure, morphology and electrochemical properties were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and galvanostatic charge and discharge tests. The results show that the synthesized TiO₂ microspheres exhibit good rate and cycle performances as anode materials of lithium ion batteries. It can be found that the dandelion-like structure provides a larger specific surface area and the single-crystalline nanorod provides a stable structure and fast pathways for electron and lithium ion transport, which contribute to the rate and cycle performances of the battery.     

不同锂源和碳源对RAPET法合成LiFePO_4/C的影响

以自制的磷酸铁作为铁源和磷源,用高温自生压力法（即RAPET法）合成了LiFe-PO4/C复合材料,分别比较了以葡萄糖、蔗糖或柠檬酸为碳源和以碳酸锂或氢氧化锂为锂源所得LiFePO4/C复合材料电化学性能的影响。利用X射线衍射（XRD）、循环伏安（CV）、交流阻抗（EIS）和充放电测试等方法,分别对样品的晶型和电化学性能等进行了表征和分析。结果表明：以柠檬酸为碳源、碳酸锂为锂源制备的LiFePO4/C复合材料电化学性能更优异,首次放电比容量达到166.1mAh/g。     

四聚甲基锂Li4(CH3)4的电子结构的量子化学研究

用Gaussian98W程序对四聚甲基锂Li4(CH3)4的电子结构作了量子化学计算,根据分子轨道能级、电子密度集居数分析、原子电荷、化学键键级等对Li4(CH3)4的缺电子多中心键的特点进行了理论解释.计算表明在Li4(CH3)4中每个碳原子与4个锂原子形成化学键,与一个距离较远的锂原子形成化学键的键级高于与3个距离较近的锂原子的键级,生成不对等的5中心2电子键(5c-2e);四聚甲基锂中Li-C键的平均键级是0.3749,平均键能为132.1kJ/mol.     

Solid electrolyte–electrode interface based on buffer therapy in solid-state lithium batteries

In the past few years, the all-solid lithium battery has attracted worldwide attentions, the ionic conductivity of some all-solid lithium-ion batteries has reached 10?3–10?2 S/cm, indicating that the transport of lithium ions in solid electrolytes is no longer a major problem. However, some interface issues become research hotspots. Examples of these interfacial issues include the electrochemical decomposition re-action at the electrode–electrolyte interface; the low effective contact area between the solid electrolyte and the electrode etc. In order to solve the issues, researchers have pursued many different approaches. The addition of a buffer layer between the electrode and the solid electrolyte has been at the center of this endeavor. In this review paper, we provide a systematic summarization of the problems on the electrode–solid electrolyte interface and detailed reflection on the latest works of buffer-based therapies, and the review will end with a personal perspective on the improvement of buffer-based therapies.     

Li/LiFePO<Subscript>4</Subscript> battery performance with a guanidinium-based ionic liquid as the electrolyte

A new guanidinium-based ionic liquid (IL) was investigated as a novel electrolyte for a lithium rechargeable battery. The viscosity, conductivity, lithium redox behavior, and charge-discharge characteristics of the lithium rechargeable batteries were investigated for the IL electrolyte with 0.3 mol kg⁻¹ lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. Li/LiFePO₄ cells incorporating the IL electrolyte without additives showed good cycle properties at a charge-discharge current rate of 0.1 C, and exhibited good rate capabilities in the presence of a mass fraction of 10% vinylene carbonate or gamma-butyrolactone.     

Lithium intercalation mechanism for β-SnSb in Sn-Sb thin films

Based on the first-principles plane wave pseudo-potential method, the electronic structure and electrochemical performance of Li_xSn₄Sb₄ (x=2, 4, 6, and 8) and Li_xSn_1-xSb₄ (x=9, 10, 11, and 12) phases were calculated. A Sn-Sb thin film on a Cu foil was also prepared by radio frequency magnetron sputtering. The surface morphology, composition, and lithium intercalation/extraction behavior of the fabricated film were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and cyclic voltammetry (CV). Lithium atoms can easily insert into and extract out of the β-SnSb cell due to the low lithium intercalation formation energy. It is found that lithium atoms first occupy the interstitial sites, and then Sn atoms at the lattice positions are replaced by excessive lithium. The dissociative Sn atoms continue to produce different Li-Sn phases, which will affect the electrode stability and lead to the undesirable effect due to their large volume expansion ratio. The calculated lithium intercalation potential is stable at about 0.7 V, which is consistent with the experimental result.     

锂化分子筛的制备和应用研究

为能够有效、经济且工艺简单地去除锂离子电池非水电解液中的微量水，根据离子交换原理对普通4A分子筛进行锂化处理制备锂化分子筛。经实验验证，这种分子筛既能满足除水的要求，又能大大降低因和Li     

原料对液-固燃烧法合成尖晶石型LiMn_2O_4的影响

以晶体醋酸锂或尿素为反应体系的液相,研究了不同锂和锰为原料,液-固燃烧合成制备尖晶石型LiMn2O4的影响.实验结果表明,不同锂和锰为原料对液-固燃烧合成LiMn2O4的影响较大,其中醋酸锂和二氧化锰为原料,可得到单相的尖晶石型LiMn2O4的产物,但加入尿素不利于合成LiMn2O4;以碳酸锂和二氧化锰或碳酸锂和碳酸锰为原料,产物中都有杂质,但碳酸锂和二氧化锰为原料优于碳酸锂和碳酸锰为反应原料.     

硅钨杂多酸锂作为聚并苯/锂二次电池的新型电解质研究

用聚并苯作正极活性材料,金属锂作负极,以硅钨杂多酸锂Li4SiW12O40代替高氯酸锂作电解质,制成了聚并苯/锂（PAS/Li）二次电池,对该二次电池的性能及影响因素尤其是Li4SiW12O40对电池容量、循环性能和自放电性质进行了系统研究.结果表明:与高氯酸理作电解质的PAS/Li二次电池相比,采用该新型电解质的二次电池不仅克服了高氯酸钾易吸水、易爆炸的不利因素,而且还具有较大的比容量和较小的自放电,循环性也很好,是一种新型、优秀的PAS/Li二次电池的电解质.     

聚氨酯／超支化聚醚／碱金属复合体系及其离子导电性

为了进一步提高聚氨酯/盐复合体系的离子电导率,合成了聚氧化乙烯聚氨酯（PEU）和超支化聚缩水甘油（HPG）,并与高氯酸锂掺杂得到聚氨酯固体电解质,样品成膜后利用红外光谱、DSC和复阻抗谱分析进行了表征,红外分析发现,随氧锂原子比[EO]/[Li]的减小,醚氧键的吸收峰发生红移、高氯酸根谱带则向高频方向移动、DSC和复阻抗谱分析表明该体系是非晶相材料,HPG的加入提高了聚氨酯体系的电导率,室温（20℃）下,[EO]/[Li]=4～6时其最佳电导率σ达到8.5μS/cm,该体系温度和电导率的关系既不完全符合Arrhenius方程,也不完全符合VTF方程,而是呈现为复杂的曲线关系,这可能与HPG的加入有关。