Increasing the conductivity of crystalline polymer electrolytes

Polymer electrolytes consist of salts dissolved in polymers (for example, polyethylene oxide, PEO), and represent a unique class of solid coordination compounds. They have potential applications in a diverse range of all-solid-state devices, such as rechargeable lithium batteries, flexible electrochromic displays and smart windows. For 30 years, attention was focused on amorphous polymer electrolytes in the belief that crystalline polymer:salt complexes were insulators. This view has been overturned recently by demonstrating ionic conductivity in the crystalline complexes PEO6:LiXF6 (X = P, As, Sb); however, the conductivities were relatively low. Here we demonstrate an increase of 1.5 orders of magnitude in the conductivity of these materials by replacing a small proportion of the XF6- anions in the crystal structure with isovalent N(SO2CF3)2- ions. We suggest that the larger and more irregularly shaped anions disrupt the potential around the Li+ ions, thus enhancing the ionic conductivity in a manner somewhat analogous to the AgBr(1-x)I(x) ionic conductors. The demonstration that doping strategies can enhance the conductivity of crystalline polymer electrolytes represents a significant advance towards the technological exploitation of such materials.     

Relaxation in polymer electrolytes on the nanosecond timescale

The relation between mechanical and electrical relaxation in polymer/lithium-salt complexes is a fascinating and still unresolved problem in condensed-matter physics, yet has an important bearing on the viability of such materials for use as electrolytes in lithium batteries. At room temperature, these materials are biphasic: they consist of both fluid amorphous regions and salt-enriched crystalline regions. Ionic conduction is known to occur predominantly in the amorphous fluid regions. Although the conduction mechanisms are not yet fully understood, it is widely accepted that lithium ions, coordinated with groups of ether oxygen atoms on single or perhaps double polymer chains, move through re-coordination with other oxygen-bearing groups. The formation and disruption of these coordination bonds must be accompanied by strong relaxation of the local chain structure. Here we probe the relaxation on a nanosecond timescale using quasielastic neutron scattering, and we show that at least two processes are involved: a slow process with a translational character and one or two fast processes with a rotational character. Whereas the former reflects the slowing-down of the translational relaxation commonly observed in polyethylene oxide and other polymer melts, the latter appears to be unique to the polymer electrolytes and has not (to our knowledge) been observed before. A clear picture emerges of the lithium cations forming crosslinks between chain segments and thereby profoundly altering the dynamics of the polymer network.     

端羟基超支化聚酯的改性及性能研究

以三羟甲基丙烷和二羟甲基丙酸为原料,在对甲苯磺酸催化下合成了端羟基超支化聚酯,8-[4′-丙氧基（1,1-联苯）-氧]-辛酸为封端剂对超支化聚酯进行改性,采用羟值滴定确定封端率。通过红外光谱（FT-IR）和核磁共振谱(NMR)对改性前后超支化聚酯的化学结构进行了表征,并采用差示扫描量热法（DSC）和广角X射线衍射（WAXD）对所合成超支化聚合物的热性能进行了研究。结果表明,封端剂的最佳用量为聚合物中羟基物质的量的1.05倍,在此条件下,超支化聚合物封端率达到92.02%;改性前后聚合物化学结构与理论结构一致,改性后聚合物玻璃化温度显著升高,且聚合物物相由无定形态转变为晶态与非晶态共存。     

Migration of Cations and Anions in Amorphous Polymer Electrolytes

1 Results Polymer electrolytes are used as ion conductors in batteries and fuel cells.Simple systems consist of a polymer matrix complexing an inorganic salt and are fully amorphous at the temperatures of interest.Both cations and anions are mobile and contribute to charge transport.Most studies on polymer electrolytes use the electrical conductivity to characterize the ion mobility.However,conductivity measurements cannot discriminate between cations and anions.This paper reports some recent results fr...     

新型核-多臂星形聚合物电解质

采用傅里叶转换红外光谱法(FT-IR)、微分扫描量热分析(DSC)、离子阻抗谱等测试手段对以超支化聚缩水甘油(HPG)为核，线型聚氨酯(PEU)为臂的核-多臂星形聚合物进行了表征，对其分子结构与电导性能之间的关系进行了初步探索．结果表明，星形聚合物比线型聚合物有更强的溶盐能力和离子传输能力．氧锂比(氧化乙烯单元与锂离子的摩尔比)为4，共混比(质量)为30％时，体系的最高电导率可达0．2mS／cm．当星形聚合物的臂数为5时，体系的电导率高于相同条件下的其他臂数的聚合物体系．体系的电导率随温度的升高而升高，其变化规律符合Arrhcnius方程．     

凝胶型聚合物电解质电化学性质的研究

研究了以ＰＶＣ和ＰＭＭＡ为基的锂盐复合物凝胶电解质的电化学性质,结果表明,这些电解质具有高的离子电导率和宽的电化学稳定区,但用于二次锂电池时,会因锂电极界面被逐渐腐蚀而影响电池寿命。     

Study on the Ion Association in PVdF-based Gel Polymer Electrolyte

IntroductionGel polymer electrolytes were originally described byFeuillade and Perche[1]and further characterized byAbraham and Alamgir[2 ,3], and formed by trapping liquidorganic solutions in a polymer matrix. Compared with solidpolymer electrolytes , gel polymer electrolytes can contactwith electrode tightly and have a room temperatureconductivity of above 10-3S·cm-1,so they are of practicalinterest for the development of new-design,advancedlithiumbatteries . A variety of polymers as poly…     

从盐湖卤水中萃取锂

选取磷酸三丁酯(TBP)为萃取剂,200号溶剂汽油为稀释剂,氯化铁(FeCl3.6H2O)为共萃取剂,从青海盐湖含锂卤水中萃取锂,并对TBP质量分数对萃取率的影响,相比对萃取率及分配比的影响进行研究。研究结果表明:共萃剂FeCl3在萃取过程中作用明显,同时,水相氢离子浓度是非常重要的影响因素,适当的酸度既可以保证锂离子进入有机相,减少氢离子与有机溶剂络合的机会,又可以保证铁离子在溶液中不发生水解;最佳萃取工艺条件如下:TBP质量分数为60%,萃取相比(O/A)为1.5,n(Fe3 )/n(Li )为1.3,水相氢离子浓度为0.05 mol/L。在此条件下,锂的萃取率可达到80%,锂、镁分离效果较好,萃取液经洗涤、反萃取和深度除镁后,可制备高纯度碳酸锂。     

Novel Amphiphilic Polymer Gel Electrolytes Based on PEG-b-GMA-co-MMA

1 Results Gel polymer electrolytes for lithium battery have been widely investigated recently because of their high ion conductivity at room temperature. We synthesized and characterized novel gel electrolytes based on amphiphilic copolymethacrylates containing different lengths of ethylene oxide (EO) chain as ionophilic units and methyl methacrylate (MMA) chain as ionophobic units[1]. Their electrochemical properties were also measured.1H NMR and FTIR analysis results elucidated that PEG-b-glycidyl met...     

聚酯及其电解质的热稳定性

以酯交换反应合成了聚丁二酸酯系列,与高氯酸锂制成固体电解质。通过对聚酯及其电解质的热失重分析,将其热分解进行了动力学处理,结果表明这一系列聚酯分解温度相近,与链节单元长度无关;聚酯电解质的热稳定性比聚酯差,且随无机盐含量提高而降低。利用色-质谱联用技术,剖析了聚酯及其固体电解质的分解产物,提出了它们各自的分解机理。     

P(AN-MMA)/TiO_2 Nano-composite Polymer Electrolyte by in-situ Polymerization

1 Introduction With the development of portable electric devices,polymer lithium ion batteries (PLiBs) have been widely used as the power sources because of their high energy density and safe property[1].P(AN-MMA) copolymer is a kind of cheap macromolecules easily dissolving in the polar solvents such as carbonate,it has been applied as gel polymer electrolyte in PLiBs.Here we prepare a kind of highly conductive nano-composite polymer electrolytes using the P(AN-MMA) copolymer incorporated with TiO2 nan...     

A Bragg glass phase in the vortex lattice of a type II superconductor

Although crystals are usually quite stable, they are sensitive to a disordered environment: even an infinitesimal amount of impurities can lead to the destruction of crystalline order. The resulting state of matter has been a long-standing puzzle. Until recently it was believed to be an amorphous state in which the crystal would break into 'crystallites'. But a different theory predicts the existence of a novel phase of matter: the so-called Bragg glass, which is a glass and yet nearly as ordered as a perfect crystal. The 'lattice' of vortices that contain magnetic flux in type II superconductors provide a good system to investigate these ideas. Here we show that neutron-diffraction data of the vortex lattice provides unambiguous evidence for a weak, power-law decay of the crystalline order characteristic of a Bragg glass. The theory also predicts accurately the electrical transport properties of superconductors; it naturally explains the observed phase transitions and the dramatic jumps in the critical current associated with the melting of the Bragg glass. Moreover, the model explains experiments as diverse as X-ray scattering in disordered liquid crystals and the conductivity of electronic crystals.     

应用EQCM研究含有二苯基联苯胺和二亚酰胺官能团的电活性聚合物的氧化还原过程

运用电化学石英晶体微天平技术(EQCM)联合循环伏安法(CV)和计时安培分析法对3种含有二苯基联苯胺和二亚酰胺的电活性聚合物薄膜进行了研究.这些聚合物薄膜具有多个氧化和还原状态.中性聚合物薄膜可以在二苯基联苯胺连接处被电化学氧化或在二亚酰胺处被电化学还原.在氧化还原转化过程期间,聚合物薄膜的电子转移、离子补偿和溶剂运输的动力学取决于聚合物的类型、其所处的氧化还原状态、电位扫描速率和氧化还原转换的方向.确定了包含二苯基联苯胺聚合物在不同电化学条件的氧化还原转化的机理.动力学控制步骤也许与聚合物薄膜在每个氧化还原状态的特定几何结构有关,并受到不同电解质和溶剂的影响.研究了含有二苯基联苯胺和二亚酰胺的电活性聚合物薄膜电子转移反应的级数、反离子补偿和溶剂传输,并定量地测定了氧化还原过程中离子和溶剂进出电活性膜的流量.     

固态锂电池聚合物电解质研究进展

聚合物作为一种固态电解质具有优良的力学和机械性能,它的性质很大程度上决定了固态锂电池的电化学性能。对部分近期比较热门的聚合物电解质的研究进展进行简要总结,将不同聚合物电解质的性能和优缺点进行比较和讨论,并且对聚合物电解质的研究发展进行展望。     

Synthesis and Characterization of a New Network Polymer Electrolyte Containing Polyether in the Main Chains and Side Chains

1 Results A new network polymer electrolyte matrix with polyether in the side chains and main chains was synthesized by the azo-macroinitiator method and urethane reaction.The macroinitiator,polymer and network polymer were confirmed by Fourier-transform infrared (FT-IR) spectroscopy and 1H NMR.FT-IR was also used to study the environment of lithium ions doped in these network polymer electrolytes.Three important groups are considered: N-H,carbonyl,and ether groups.The thermal properties of the polymer ...     

具有高临界相转变温度的热敏性高分子材料

介绍了一类具有高临界相转变温度(UCST)的热敏性高分子材料,并对其相转变机理、热敏性影响因素及表征方法做了讨论。UCST类高分子材料的热敏性受到相对分子质量、疏水基团、溶液中的质子受体/给体、电解质等多种因素的影响。当UCST类高分子材料与具有最低临界相转变温度(LCST)的高分子材料共聚后,可得兼具UCST和LCST特点的新型功能材料,拓展了热敏高分子材料的应用领域。     

Preparation and performance of novel LLTO thin film electrolytes for thin film lithium batteries

We prepared a series of lithium lanthanum titanate(LLTO) thin film electrolytes by radio frequency(RF) magnetron sputtering using LLTO targets in a N2 atmosphere.We also deposited the LLTO thin films in an Ar atmosphere under a same condition as references for comparison.The microstructure morphology and the composition of the thin films were investigated by X-ray diffraction(XRD),scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS),respectively.Results show that the thin film has an amorphous structure with a uniform surface and it is free of pinholes and cracks.Impedance measurements reveal that the ionic conductivity of the electrolytes is beneficial for all solid lithium batteries dependent on the lithium content at room temperature.We found that the amorphous LLTO thin film performs well and it has potential application in microbatteries for use in microelectronic devices.     

锂离子电池的关键材料及其发展

锂离子电池的发展与其负极材料、正极材料和电解质材料的发展相关。本文对锂离子电池的关键材料及其发展进行阐述,以便能够更好的研究和改善电池的性能。     

不同酸处理钛酸锂的转型研究

详细研究了酸的种类和处理时间对钛酸锂转型的影响. 结果显示当相同酸度的硫酸和盐酸用来对钛酸锂进行改性时,在盐酸介质中钛酸锂更容易转变为锐钛矿和金红石型二氧化钛. 硫酸浓度越高,钛酸锂更容易转变为锐钛矿和金红石型二氧化钛;处理时间越长,更多的钛酸锂可以转变为锐钛矿和金红石型二氧化钛. 硫酸根通过螯合双齿配位于二氧化钛,有利于稳定锐钛矿型晶相;亲电的H+和高电负性的Cl-影响Ti-O键,导致TiO6八面体中的Ti-O键断裂和锐钛矿型二氧化钛发生结构重排形成金红石型二氧化钛. 钛锂离子筛稳定的结构和晶相组成能够保证高效、循环往复地提取锂,从这一点来看,相比于盐酸,硫酸更适合作为洗脱剂来制备钛锂离子筛,并且低浓度的盐酸是更好的选择.     

苯甲酸锂、对本二酸锂及均苯三甲酸锂的电化学性能

与传统的锂离子电池（LIBs）无机材料相比,有机电极材料因具有理论容量高、可再生、成本低、环境友好等优点已成为LIBs电极材料的热门研究方向. 然而有机材料易溶解在有机电解液中,阻碍有机电极材料的进一步市场化.本文通过含不同数量羧酸的苯甲酸、对苯二甲酸、均苯三甲酸分别与氢氧化锂进行简单中和反应生成相应的苯甲酸锂、对苯二甲酸锂、均苯三甲酸锂,作为有机负极嵌锂材料,并研究不同数量的羧基锂基团对这三种电极材料电化学性能的影响.研究结果显示苯甲酸锂、对苯二甲酸锂、均苯三甲酸锂电极材料在0.1C电流倍率下首次放电容量分别为~250、~340、~268 mAh g-1,50次循环后,其放电容量分别为~75、~100、~60 mAh g-1,表明对苯二甲酸锂电极材料循环前后放电容量最高.通过溶解性实验表明对苯二甲酸锂是最难溶解在有机电解液中.对苯二甲酸锂能够通过O-LiO-键作用形成二维大分子链的结构,能有效抑制溶解.从以上实验结果看出,对苯二甲酸锂电极材料是最有希望的LIBs有机负极材料.