摘要： A novel solid-state polymer electrolyte (SPE) based on ionic liquid (IL) and surface functionalized PMMA nanoparticles is reported. It exhibits a much improved ionic conductivity of 5.12 x 10(-4) S cm(-1) at 30 degrees C, an enhanced lithium ion transference number, and a wide electrochemical window of up to similar to 5.1 V. The enhanced ionic conductivity is attributed to the unique self-assembly of PMMA nanoparticles with surface-tethered IL groups. It is also found that further incorporation of the IL-based phase can significantly increase the ion mobility by providing a microscopic fluidic environment. More interestingly, this SPE exhibits excellent elasticity with an exceptionally high elongation-at-break value of up to 1600%. These attributes enable it to be a high-performance membrane electrolyte and a separator that is suitable for flexible and wearable lithium batteries.

关键词： 聚合物固态电解质   锂电池   专利分析  

摘要： 本文以聚合物固态锂电池技术的专利为研究对象,运用专利文献计量学方法,使用Thomson Data Analyzer(TDA)和Microsoft Excel等分析工具,对德温特专利数据库中收录的聚合物固态锂电池技术相关专利的时序分布、国家/地区布局、技术主题、重点申请人等方面进行了分析,并对中国科学院专利在线分析系统中收录的在中国申请的相关专利进行了重点分析,以期为该领域的研发提供参考.

关键词： Anthraquinone   Solid polymer electrolyte   All-solid-state battery  

摘要： An all-solid-state battery was fabricated by using a PEO-base solid polymer as electrolyte and an organic material anthraquinone (AQ) as cathode. The anthraquinone delivers a specific discharge capacity of 183 mAh g(-1) at first cycle at current density of 20 mA g(-1), at 65 degrees C. The use of solid polymer electrolyte reduces the dissolution of organic active material greatly, improving the cycle performance of the battery. Therefore, the all-solid-state battery delivers a better cycling property. It can still retain a capacity of 136 mAh g(-1), after 50 cycles, corresponding to a capacity retention of 74%, while capacity retention of the cell using liquid electrolyte was only 28% after 20 cycles. The all-solid-state battery shows more stable interfacial resistance during charge-discharge process. It displays good rate ability and a better thermal stability. (C) 2016 Elsevier B.V. All rights reserved.

关键词： 全固态锂电池   固体聚合物电解质   活性填料   活化过程   交联反应   一锅法  

摘要： 传统液态锂离子电池经常会发生电解液泄漏和自燃等安全事故,所以全固态聚合物电解质（SPE）以其独有的安全性获得了良好的发展机遇。为了提高SPE的室温锂离子电导率,进一步促进全固态聚合物锂离子电池的发展,本文从对聚环氧乙烷（PEO）基电解质进行改性和开发新材料两个方面出发,设计和制备出了低成本、高安全性、强机械性能和优电化学稳定性等特点的新一代固态聚合物电解质。具体研究结果如下:（1）向PEO基电解质中引入三元硫化物Li10GeP2S12（LGPS）和固体增塑剂丁二腈（SN）,并系统的考察了各组分配比,得到PEO-LiTFSI-1%LGPS-10%SN电解质展现出最高的室温电导率9.10×10-55 Scm-1（约为PEO-LiTFSI的15倍）,且具有较宽的电化学稳定窗口（0～5.5 V）,和良好的对锂稳定性。此外,在40°C下,用其组装的全固态锂离子电池也表现出优越的循环倍率性能,0.1 C和0.5 C时的首次放电比容量分别为160.6 mAhg-1和138.4 mAhg-1,且60周后容量保持率都在90%以上;同时也给出了活化过程产生的相关原因。（2）采用一锅法,通过使三羟甲基三缩水甘油醚（TMPEG）和聚乙二醇二胺（NPEG）发生开环交联反应,制备了一种全新的TMPEG-NPEG固态网状聚合物电解质（SNPE）材料。当TMPEG与NPEG摩尔比为2:1,NPEG的分子量为4000,EO/Li+=16时,TMPEG-NPEG[2:1]-16:1电解质在30°C下电导率最高,达到1.10×10-44 Scm-1（约为PEO-LiTFSI的18倍）。同时,它还具有较宽的电化学窗口（0～5.4 V）,良好的对锂稳定性和杰出的机械性能。其组装的LiFePO4/Li电池在60°C下具有优异的循环倍率性能,0.2 C和1 C的初始放电比容量分别为161.7 mAhg-1和132.7 mAhg-1,且循环100周后的容量保持率分别为90.6%和90.5%。

关键词： 固态聚合物电解质   原位合成   锂离子电池   锂金属电池   锂化硅-硫电池  

摘要： 使用固态聚合物电解质取代有机电解液被认为是提升锂电池安全性的有效途径。然而,制备出兼具高离子电导率、低电极/电解质界面阻抗、高机械强度的聚合物电解质材料仍是现阶段的技术难题。本论文研究了新型聚合物电解质的设计制备,并对其系统地进行了电化学表征及界面性质分析。首先,研究了腈类聚合物电解质在锂离子电池中应用。探明了腈乙基取代聚乙烯醇（PVA-CN）基凝胶聚合物电解质的凝胶机理,进而通过改进化成工艺构建了低阻抗的石墨电极/凝胶聚合物电解质界面。在此基础上将PVA-CN在丁二腈（SN）基全固态电解质中原位聚合,并填充于聚丙烯腈（PAN）基电纺纤维膜中制得层次结构腈类全固态电解质（SEN）。腈类原材料之间的结构相容性及层次结构设计使得所制备的SEN膜同时具有高离子电导、高锂离子迁移数、良好的抗拉强度、优越的安全性和柔性。原位合成方法则使电极与SEN之间保持良好的粘附性,明显降低了界面阻抗并使得聚合物电池呈现出良好的电化学性能。第二,开发出一种新型SiO2空心纳米球基复合固态电解质（SiSE）,并将其应用于锂金属电池。这一复合电解质通过将二缩三丙二醇二丙烯酸酯（TPGDA）单体溶于碳酸酯基电解液配得前躯体溶液,再将该前躯体溶液吸入SiO2空心纳米球层后原位聚合而制得。由于稳定、低阻抗的电极/固态电解质界面和SiSE对锂枝晶生长的显著抑制作用,使用SiSE的固态锂金属电池与使用传统隔膜/电解液体系的对照电池相比表现出显著提高的循环性能和安全性。第三,针对锂化硅-硫全电池中纳米锂化硅颗粒的高比表面积加剧穿梭效应导致电池性能恶化的问题,将含有氟代碳酸乙烯酯（FEC）的醚类电解液吸入SiO2空心纳米球层制得准固态电解质（OSE）。FEC可有效优化硅颗粒表面固体电解质界面膜（SEI）,而SiO2球表面丰富的介孔结构则可吸附多硫化物限制穿梭效应,使锂化硅-硫全电池的循环性能得到明显改善,并在短路条件下保持结构无损。最后,基于离子液体/聚离子液体不可燃的特性,采用原位方法设计了一种高安全性层次结构聚离子液体基固态电解质（HPILSE）。该电解质同时具备高离子电导率,低电极/电解质界面阻抗和良好的机械强度,在LiFePO4/HPILSE/Li和Na0.9[Cu0.22Fe0.30Mn0.48]O2/HPILSE/Na电池中均表现出优越的电化学性能。

关键词： Thiol-ene polymerization   Poly(ethylene oxide)   Solid polymer electrolytes   Semi-interpenetrating network  

摘要： We developed highly promising solid polymer electrolytes (SPEs) based on a novel cross-linker containing star-shaped phosphazene with poly(ethylene oxide) (PEO) branches with very high ionic conductivity (7.6 x 10(-4) S cm(-1)), improved mechanical stability, and good electrochemical stability for all solid-state lithium batteries. In particular, allyl groups were introduced at the ends of the cross-linker in order to overcome the easy self-polymerization of existing cross-linking acrylate end groups. A novel semi-interpenetrating network (semi-IPN) SPE was prepared by in-situ radical polymerization of a precursor solution containing lithium salt, poly(ethylene glycol) dimethyl ether as a plasticizer, and a mixture of pentaerythritol tetrakis(3-mercaptopropionate) and a synthesized hexakis(allyloxy)cyclotriphosphazene (thiol-ene PAL) as the cross-linker. Batteries employing LiFePO4 as the cathode, lithium foil as the anode, and the SPE thin film as the electrolyte were assembled and tested. At ambient temperature, the initial discharge capacity was 147 mAh/g at 0.1 degrees C and 132 mAh/g at 0.5 degrees C, and 97% of the capacity was retained at the 100th cycle. All-solid-state pouch-package lithium cells assembled with the SPEs exhibited stable electrochemical performance, even under a severely wrinkled state. These outstanding properties of SPEs based on thiol-ene PAL demonstrate feasibility for practical battery applications with improved reliability and safety. (C) 2016 Elsevier B.V. All rights reserved.

关键词： Solid polymer electrolyte   Lithium-sulphur battery   Cross-linking   Ionic conductivity   Semi-interpenetrated networks  

摘要： Semi-interpenetrated network Solid Polymer Electrolytes (SPEs) were fabricated by UV-induced cross linking of poly(ethyleneglycol) diacrylate (PEGDA) and divinylbenzene (DVB) within a poly(ethyleneoxide) (PEO) matrix (M-w = 5 x 10(6) g mol(-1)), comprising lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI), at a molar ratio of EO:Li similar to 30:1. The influence of the DVB content on the final SPE properties was investigated in detail. An increase of DVB concentration resulted in self-standing polymer electrolytes. The DVB cross-linker incorporation was found to decrease the crystallinity of the PEO matrix from 34% to 23%, with a decrease in the melting temperature (T-m) of the membrane from 50 degrees C to 34 degrees C. Moreover, the influence of the DVB concentration on the ionic conductivity was determined for polymer electrolytes with 0,10, 20 and 45% DVB from room temperature (RT) to 80 degrees C. The resulting SPEs showed a high electrochemical stability of 4.3 V as well as practical conductivity values exceeding 10(-4)S cm(-1) at 70 degrees C. Cycling performance of these semi-interpenetrated SPE's have been shown with a Li metal polymer battery and all solid-state Li sulphur battery. (C) 2016 Elsevier Ltd. All rights reserved.

关键词： poly(ethylene oxide)   LiTNFSI   polymer electrolytes   solid-state batteries   Li batteries  

摘要： Solid polymer electrolytes (SPEs) would be promising candidates for application in high-energy rechargeable lithium (Li) batteries to replace the conventional organic liquid electrolytes, in terms of the enhanced safety and excellent design flexibility. Herein, we first report novel perfluorinated sulfonimide salt-based SPEs, composed of lithium (trifluoromethanesulfonyl)(n-nonafluorobutanesulfonyl)imide (Li[(CF3SO2)(n-C4F9SO2)N], LiTNFSI) and poly(ethylene oxide) (PEO), which exhibit relatively efficient ionic conductivity (e.g., 1.04 x 10(-4) S cm(-1) at 60 degrees C and 3.69 x 10(-4) S cm(-1) at 90 degrees C) and enough thermal stability (>350 degrees C), for rechargeable Li batteries. More importantly, the LiTNFSI-based SPEs could not only deliver the excellent interfacial compatibility with electrodes (e.g., Li-metal anode, LiFePO4 and sulfur composite cathodes), but also afford good cycling performances for the Li|LiFePO4 (>300 cycles at 1C) and Li-S cells (>500 cycles at 0.5C), in comparison with the conventional LiTFSI (Li[(CF3SO2)(2)N])-based SPEs. The interfacial impedance and morphology of the cycled Li-metal electrodes are also comparatively analyzed by electrochemical impedance spectra and scanning electron microscopy, respectively. These indicate that the LiTNFSI-based SPEs would be potential alternatives for application in high-energy solid-state Li batteries.

关键词： 全固态聚合物电解质   锂电池   离子电导率   趋势  

摘要： 目前大规模商业化的锂二次电池普遍采用有机碳酸酯类的液态电解质,易泄露、易燃烧、易爆炸等安全问题限制了该类电解质的进一步应用。全固态聚合物电解质(all-solid-state polymer electrolytes,ASPEs)电池具有安全性能好、能量密度高、工作温度区间广、循环寿命长等优点,是锂离子电池领域的研究热点之一。ASPEs通常还具有优异的力学性能,可以很好地抑制锂金属电极在充放电过程中的枝晶生长,所以在锂金属电池领域也具有十分重要的应用前景。作者综述了研究较多的几种ASPEs体系,包括聚氧化乙烯(PEO)基体系、聚碳酸酯基体系、聚硅氧烷基体系、聚合物锂单离子导体体系。PEO基ASPEs是研究最早且研究最多的一类ASPEs材料,但其高结晶性造成室温Li+迁移困难、离子电导率低等问题,所以研究人员研发了一系列降低PEO结晶度、提升体系离子电导率的改性手段。聚碳酸酯基ASPEs主链结构中含有强极性碳酸酯基团而且室温无定形态,使得锂盐更容易解离,且室温离子电导率一般较PEO基要高,是比较有潜力的PEO基ASPEs替代材料。除了碳链聚合物,玻璃化转变温度较低的聚硅氧烷基ASPEs体系也因为其较高的离子电导率受到研究人员关注。在锂电池充放电过程中,Li+才是有效载荷子,电解质中阴离子的迁移会增加电解质体系的浓差极化,所以阴离子不发生迁移、Li+迁移数接近于1的聚合物锂单离子导体也是一类具有研究价值的ASPEs材料。最后,本综述讨论了全固态聚合物电解质的应用前景及未来发展方向,指出了PEO基体系的研究重点在于发展有机-无机复合体系、聚碳酸酯基体系的研究重点在于发展与其它聚合物的共混体系、聚硅氧烷基体系的研究重点在于增强体系力学性能、聚合物锂单离子导体体系的研究重点在于设计离子电导率更高的新型聚阴离子锂盐。

关键词： Solid polymer electrolytes   Cardanol   All-solid-state batteries  

摘要： A series of self-crosslinkable polymers composed of different amounts of ionic conducting units (poly(ethylene glycol) methyl ether methacrylate) and crosslinkable units (2-hydroxy-3-cardanylpropyl methacrylate) obtained from a renewable resource, cardanol, were prepared for application to solid polymer electrolytes. Free-standing solid polymer electrolytes were prepared by mixing the polymers with lithium bis(trifluoromethanesulfonyl) imide followed by UV irradiation to induce reaction of the double bonds in the cardanol moiety, forming the cross-linked structures. The ionic conductivity of the solid crosslinked polymer electrolyte prepared from the polymers containing 8 mol% of the crosslinkable cardanol monomeric units was 1.9 x 10(4) S cm(-1) at 60 degrees C, which is close to those of poly(poly( ethylene glycol) methyl ether methacrylate) in the waxy state. The all-solid-state lithium battery prepared using this solid polymer electrolyte without a separator exhibited stable cell operation, showing 81.4% of capacity retention after 100 charge-discharge cycles, and demonstrating that the self-crosslinkable polymer from the renewable resource is suitable for high-temperature and high-voltage lithium secondary battery applications. (C) 2016 Elsevier Ltd. All rights reserved.