笔者想感谢威德福国际提供金融支持。

1。接枝共聚物的合成18-19 <ol><li>合成接枝共聚物（POEM克PDMS和POEA克PDMS以70:30的重量比），用自由基聚合方法，通过混合26毫升（或POEA）POEM单体（ 图3），12毫升PDMS大分子单体，和12毫克的2,2&#39; - 偶氮二（2 - 甲基丙腈）（AIBN）（单体：引发剂[825:1]）在160毫升的EA。 </li><li>密封用橡胶隔膜和有超高纯度氩气吹扫45分钟清澈的溶液的烧瓶中。 </li><li>加热该溶液至72℃（AIBN的分解率为3.2×10 -5秒-1）在不断搅拌下在油浴中24小时。 </li><li>最初明确的解决方案，通常2小时内变得明显乳白色。沉淀出最终的解决方案，在不混溶的溶剂，PE。聚合物在80℃下干燥5天，以除去残留的水分小于5毫乇真空下。 </li><li>结果发现，如果聚合物为nOT适当的干燥，水分过多会导致裂纹的形成，当聚合物被浇铸成薄膜。 </li><li>最后的接枝共聚物（ 如图4所示）的分子量为500,000 g / mol的使用凝胶渗透色谱法用聚苯乙烯校准的标准。 </li><li>复杂的接枝共聚物的LiTFSI在李：EO比为1:20（1克诗G-PDMS（70:30）170毫克的LiTFSI）在一个共同的溶剂THF形成电解质。 </li></ol> 2。复合阴极材料的制备<ol><li>合成的阴极通过将球磨后的LiFePO 4粉末（临沂Gelon新电池材料）和炭黑（超级P），并且将混合物溶解在GCE溶液的5:1:1的重量比。 </li><li>淤浆加热至80℃（打开盖），在搅拌的同时。下一步超声浆料通过磁力搅拌，以确保适当的混合。在负载因数为10毫克/厘米2到铝箔上的刮片铝箔，以确保更好地层压到铝。 </li><li>复合阴极在真空烘箱中干燥，在80℃的CO / N，以去除残留的十二烷基硫酸钠和水分。 </li></ol> 3。纽扣电池的制备和测试<ol><li>复合阴极到充满氩气的手套箱中，冲头运送到使用一个高精度的电极切割机EL-CUT（EL-CELL）的小圆片（面积= 1.4厘米2）。 DROP蒙上纯GCE溶液（POEM-G-PDMS的LiTFSI，都溶解在THF）在电极上盘形成电解质层。 </li><li>在手套箱内的热板上加热最终的阴极电解液光盘露点为-80℃至蒸发，十二烷基硫酸钠，和组装为CR2032纽扣细胞沿大小相等的GCE涂层金属锂片（Sigma-Aldrich公司的0.75毫米厚），使用手动关闭工具（Hohsen）的。细胞的原理图在图5中示出，其中的灰色颗粒代表的LiFePO 4，黑粒子代表怨恨碳，蓝色的“意大利面条”代表的GCE，阳极的锂金属。 </li><li>细胞组成的第二组相同的LiFePO 4的粉末和锂金属阳极组装，而是使用粘合剂树脂（聚偏氟乙烯的Kynar），聚偏氟乙烯隔板（膜Celgard），和液体电解液的1M的LiPF 6，在EC：DMC以1:1的比（LP30，默克）的性能进行比较。 </li><li>所有组件是在露点为-80℃的手套箱一个32通道MACCOR 4000电池测试仪是用于在室温下的循环测试。 </li></ol> 4。聚合物传导机制<ol><li>该PEO段的运动通常与周围的扭转CC和CO键。半随机的链段运动，有助于形成和断裂的溶剂化离子的配位点，提供的自由体积的离子扩散的电场的影响下，由离子传导。出现节段性运动在vicinit发生y的的玻璃化转变温度Tg，并且变得更简便的，随着温度的进一步增加超出的Tg。在较高的温度下，本地的空隙所产生的聚合物膨胀，移动到自由体积19中的聚合物链段。 </li><li>由于链段运动更快速的在无定形相中比在晶相的 Tg以上，聚合物的离子迁移主要发生在无定形相中。然而，最近锂离子传导结晶乙烯（PEO）6：LiAsF 6表明，虽然导电率超过两个数量级低于在无定形的PEO。 PEO /盐配合物的结晶或无定形的相的组成，温度，及其制备方法20-22。 </li><li>不同的液体，离子移动与溶剂护套完好和运输有关的宏观粘度溶剂中，在固体高分子型，越来越多的聚合物链缠结和不能移动长距离，离子迁移有关的微观粘度的聚合物链段。离子沿聚合物链的运输，需要克服两个活化障碍，均示于图6和7。一是由协调EO单元的离子的溶剂化。这一过程涉及的化学键的形成和断裂，阿累尼乌斯的依赖，和导电性由下式给出 σA（E / kT的） 式中，σ是电导率，A是一个常数，E A与债券是活化能。由于离子解离协调点，以推动在固体聚合物，如果债券是太强大了，阳离子变得动弹不得。阳离子聚合物债券盐溶解需要足够强大，但够弱吨o允许阳离子的流动性。 </li><li>离子的传输是从一个配位到另一个。这个过程是有关该聚合物的链段运动，具有沃格尔塔姆曼弗切尔（VTF）22-25的依赖性，和导电性是其中T 0为参考温度一般选择在50 K低于T 克 。这个公式表明，T 0以上的热运动有助于运输过程中，更快的议案，预计聚合物的 Tg低。 VTF过程有关的 Tg，从而在低温下的速率限制。在高温下，节段性运动变得足够轻便，阿列纽斯过程成为速率限制。 </li></ol>

<ol>
	<li>Tarascon, J. M., Armand, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Issues+and+challenges+facing+rechargeable+lithium+batteries.">Issues and challenges facing rechargeable lithium batteries.</a> Nature. 414 (6861), 359-367 (2001).</li><li>Scrosati, B., Hassoun, J., Sun, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Lithium-ion+batteries.+A+look+into+the+future.">Lithium-ion batteries. A look into the future.</a> Energy Environ. Sci. 4 (9), 3287-3295 (2011).</li><li>Goodenough, J. B., Kim, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Challenges+for+rechargeable+batteries.">Challenges for rechargeable batteries.</a> J. Power Sources. 196 (16), 6688-6694 (2011).</li><li>Wang, Y., He, P., Zhou, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Olivine+LiFePO4:+development+and+future.">Olivine LiFePO4: development and future.</a> Energy Environ. Sci. 4 (3), 805-817 (2011).</li><li>Bruce, P. G., Scrosati, B., Tarason, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Nanomaterials+for+rechargeable+lithium+batteries.">Nanomaterials for rechargeable lithium batteries.</a> Angew. Chem. 47 (16), 2930-2946 (2008).</li><li>Choi, N., Yao, Y., Cui, Y., Cho, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=One+dimensional+Si/Sn+-+based+nanowires+and+nanotubes+for+lithium-ion+energy+storage+materials.">One dimensional Si/Sn - based nanowires and nanotubes for lithium-ion energy storage materials.</a> J. Mater. Chem. 21 (27), 9825-9840 (2011).</li><li>Jeong, G., Kim, Y. U., Kim, H., Kim, Y. J., Sohn, H. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Prospective+materials+and+applications+for+Li+secondary+batteries.">Prospective materials and applications for Li secondary batteries.</a> Energy Environ. Sci. 4 (6), 1986-2002 (2011).</li><li>Walker, C. W., Salomon, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Improvement+of+ionic+conductivity+in+plasticized+PEO-Based+solid+polymer+electrolytes.">Improvement of ionic conductivity in plasticized PEO-Based solid polymer electrolytes.</a> J. Electrochem. Soc. 140 (12), 3409-3412 (1993).</li><li>Daniels, C., Besenhard, J. O. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Handbook of battery materials. , (2011).</li><li>Bard, A. J., Faulkner, L. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Electrochemical methods: fundamentals and applications. , 864 (2001).</li><li>Newman, J., Thomas-Alyea, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Electrochemical systems. , 672 (2004).</li><li>Zu, C., Li, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermodynamic+analysis+on+energy+densities+of+batteries.">Thermodynamic analysis on energy densities of batteries.</a> Energy Environ. Sci. 4 (8), 2614-2624 (2011).</li><li>Balbuena, P., Wang, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Lithium-ion Batteries: solid-electrolyte interphase. , (2004).</li><li>Appetecchi, G. B., Scaccia, S., Passerini, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Investigation+on+the+Stability+of+the+Lithium-Polymer+Electrolyte+Interface.">Investigation on the Stability of the Lithium-Polymer Electrolyte Interface.</a> J. Electrochem. Soc. 147 (12), 4448-4452 (2000).</li><li>Bruce, P. G., Krok, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Characterisation+of+the+electrode/electrolyte+interfaces+in+cells+of+the+type+Li/PEO+LiCF3SO3/V6O13+by+ac+impedance+methods.">Characterisation of the electrode/electrolyte interfaces in cells of the type Li/PEO LiCF3SO3/V6O13 by ac impedance methods.</a> Solid State Ionics. 36 (3-4), 171-174 (1989).</li><li>Huggins, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Energy Storage. , 400 (2010).</li><li>Lee, S., Sch&#246;mer, M., Peng, H., Page, K. A., Wilms, D., Frey, H., Soles, C. L., Yoon, D. Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Correlations+between+ion+conductivity+and+polymer+dynamics+in+hyperbranched+poly(ethylene+oxide)+llectrolytes+for+lithium-ion+batteries.">Correlations between ion conductivity and polymer dynamics in hyperbranched poly(ethylene oxide) llectrolytes for lithium-ion batteries.</a> Chem. Mater. 23 (11), 2685-2688 (2011).</li><li>Trapa, P. E., Reyes, A. B., Das Gupta, R. S., Mayes, A. M., Sadoway, D. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Polarization+in+cells+containing+single-ion+graft+copolymer+electrolytes.">Polarization in cells containing single-ion graft copolymer electrolytes.</a> J. Electrochem. Soc. 153 (6), 1098-1101 (2006).</li><li>Trapa, P. E., Won, Y. Y., Mui, S. C., Olivetti, E. A., Huang, B., Sadoway, D. R., Mayes, A. M., Dallek, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rubbery+graft+copolymer+electrolytes+for+solid-state+thin-film+lithium+batteries.">Rubbery graft copolymer electrolytes for solid-state thin-film lithium batteries.</a> J. Electrochem. Soc. 152 (1), A1-A5 (2005).</li><li>Walker, C. W., Salomon, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Improvement+of+ionic+conductivity+in+plasticized+peo-based+solid+polymer+electrolytes.">Improvement of ionic conductivity in plasticized peo-based solid polymer electrolytes.</a> J. Electrochem. Soc. 140 (12), 3409-3412 (1993).</li><li>Bard, A. J., Faulkner, L. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Electrochemical methods: fundamentals and applications. , 864 (2001).</li><li>Michnick, R. B., Rhoads, K. G., Sadoway, D. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Relative+dielectric+constant+measurements+in+the+butyronitrile-chloroethane+system+at+subambient+temperatures.">Relative dielectric constant measurements in the butyronitrile-chloroethane system at subambient temperatures.</a> J. Electrochem. Soc. 144 (7), 2392-2398 (1997).</li><li>Orazem, M. E., Tribollet, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Electrochemical impedance spectroscopy. , (2008).</li><li>Cogger, N. D., Evans, N. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=An+introduction+to+electrochemical+impedance+measurement.">An introduction to electrochemical impedance measurement.</a> Technical Note, Solartron Analytical Technical Report. No. 6, (1999).</li><li>Marzantowiz, M., Dygas, J. R., Krok, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Impedance+of+interface+between+PEO:LiTFSI+polymer+electrolyte+and+blocking+electrodes.">Impedance of interface between PEO:LiTFSI polymer electrolyte and blocking electrodes.</a> Electrochim. Acta. 53 (25), 7417-7425 (2008).</li><li>Clarson, S. J., Semlyen, J. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Studies+of+cyclic+and+linear+poly(dimethyl-siloxanes):+21.+high+temperature+thermal+behavior.">Studies of cyclic and linear poly(dimethyl-siloxanes): 21. high temperature thermal behavior.</a> Polymer. 27 (1), 91-95 (1986).</li></ol>

没有利益冲突的声明。

LiFePO 4的 / GCE /李曲线的表现出更大的过电位比磷酸铁锂/ LP30/Li充电和放电曲线。由于在玻碳电极作为电解质和粘合剂，离子传导被提供给所有的阴极颗粒，并且几乎整个实际的比容量（150毫安时/克）是可访问的。还没有实现，因为它是有限的锂扩散于LiFePO 4的颗粒在室温下，这是低的理论比容量为170毫安时/克。右图所示的前50深循环的循环能力。在第5个循环的能量效率?...

锂（Li）是一种高正电性的金属，（-3.04 V相对于标准氢电极），最轻的金属（6.94克/摩尔当量，比重为0.53克/厘米3）。这使得它的吸引力作为便携式能量存储装置中的活性物质的负极和理想的选择。的尺寸和重量的问题。 图1表明，锂基电池（锂离子，的PLiON，Li金属）具有更高的能量密度比铅酸，镍镉，镍金属氢化物电池1。 一个完整的锂离子电池组成的阴极（正极），阳极（负极），一种电解质，和一个分离器（ 图2）。的阴极和阳极的插层化合物，其中锂离子可以嵌入或脱嵌可逆地（如果阳极是碳，黎地嵌入为中性李）。电解质离子传导和绝缘电网卡电极之间的导通。分隔符是可渗透的离子，但机械刚性，以避免在两电极短路。当电池在完全充电的状态下，所有的李已经插在阳极，当细胞在完全放电的状态下，所有的锂离子在阴极间。自发反应期间，通过外部电路的电源的装置，从阳极到阴极的电子流放电，而从阳极到阴极通过电解质的离子流。在阴极的离子和电子的再结合，以保持电中性。在充电时，流是相反的。 大多数锂离子电池发展至今一直专注于正极材料的电池的能量密度，而不是对电解质，仍大多是几十年来的相同，因为它们决定。的电解质这块电池是一个关键，因为它会影响整体的输出功率能力由于impedan的策通过电解质本身，在电极 - 电解质界面。 在锂离子电池中使用的电解液一般由不同的LiX的非水溶剂中的盐的。与其他电化学系统中使用的水电解质，锂离子的电解质的缺点是较低的导电性，成本较高，易燃，和环境问题。优势包括宽阔的温度范围内（其中电解质仍然是液体）从-150℃〜300℃，在较宽的电压窗口（高达5 V与对Li / Li +），更好地与电极的相容性（水电解质锂金属和形式的氢氧化锂和氢）2，3，4-6，发生剧烈反应。 在电池中使用的主要的非水电解质包括碳酸酯类有机液体，聚合物，离子液体，和陶瓷。这些电解质在实用锂离子batteri的要使用需要满足若干标准ES。它们包括的导电率至少为10毫西门子/厘米，一个大的电化学窗口（&gt; 4.5 V的高电压阴极），低蒸气压，良好的热和化学稳定性，低毒性，和低成本。对于某些严格的应用，例如电动汽车，所有这些基准都必须满足在宽的温度范围内，通常是从-20℃至60℃。由于这项工作的重点是有机聚合物电解质，本文的其余部分将集中在这些电解质。 包括基于碳酸酯的电解液的锂盐溶解在有机溶剂中。但是，它是困难的任何一种溶剂，以满足所有的要求。例如，低蒸气压，如碳酸亚乙酯（EC）和碳酸亚丙酯（PC）的溶剂中，往往有更高的粘度，导致降低导电性。也EC是一种室温下为固体，这要求将它与其它溶剂组合。一般来说，电解质是几种溶剂的组合。常用的溶剂和它们的物理性质列于表1。 <table border="1"><tbody><tr><td> 名 </td><td> 熔点温度（°C） </td><td> 沸点温度（℃） </td><td> 粘度（MPA *） </td></tr><tr><td>碳酸二甲酯（DMC） </td><td> 4.6 </td><td> 90 </td><td> 0.5902（25℃） </td></tr><tr><td>碳酸二乙酯（DEC） </td><td> -43 </td><td> 126.8 </td><td> 0.7529（25℃） </td></tr><tr><td>碳酸乙烯酯（EC） </td><td> 36.5 </td><td> 238 </td><td> 1.9（40°C） </td></tr><tr><td>碳酸丙烯酯（PC）的</td><td> -54.53 </td><td> 242 </td><td> 2.512（25℃） </td></tr></tbody></table> 表1中。常见的碳酸酯溶剂 7。 更安全的副奥尔加NIC电解质聚合物为主的电解质。聚合物电解质薄膜，不挥发，不易燃，和它们的灵活性，允许它们被轧制，并印上一个大的商业规模。赖特等人在1973年首次证明聚氧化乙烯（PEO）的离子传导盐复合物（PEO）。后来发现使用PEO基固态聚合物电解质，抑制树突的生长8-17液态电解质锂金属枝晶生长相关的安全问题是可以解决的。有三种主要类型的聚合物电解质：（1）无溶剂的干燥固体聚合物，（2）凝胶电解质，以及（3）增塑的聚合物，在我们的工作中使用的无溶剂干式合成。 本文将讨论（一）无溶剂干聚合物的合成，（b​​）聚合物传导机制，以及（c）提供固体聚合物和有机电解液的温度循环。

<table border="1">
	<tbody>
		<tr>
			<td>Name of the reagent</td>
			<td>Company</td>
			<td>Catalogue number</td>
			<td>Comments (optional)</td>
		</tr>
		<tr>
			<td>POEM</td>
			<td>Sigma Aldrich</td>
			<td>26915-72-0</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>POEA</td>
			<td>Sigma Aldrich</td>
			<td>32171-39-4</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>LiTFSI</td>
			<td>Sigma Aldrich</td>
			<td>90076-65-6</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>AIBN</td>
			<td>Sigma Aldrich</td>
			<td>78-67-1</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>EA</td>
			<td>Sigma Aldrich</td>
			<td>141-78-6</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>THF</td>
			<td>Sigma Aldrich</td>
			<td>109-99-9</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>PDMS</td>
			<td>Gelest</td>
			<td>146632-07-7</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Argon Gas</td>
			<td>Air Gas</td>
			<td>&nbsp;</td>
			<td>Ultra high purity (Grade 5)</td>
		</tr>
		<tr>
			<td>PE</td>
			<td>Sigma Aldrich</td>
			<td>8032-32-4</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>LiFePO4</td>
			<td>Gelon</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Carbon black</td>
			<td>SuperP</td>
			<td>&nbsp;</td>
			<td>Super P</td>
		</tr>
		<tr>
			<td>Lithium metal</td>
			<td>Alfa Aesar</td>
			<td>7439-93-2</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>PVDF binder resin</td>
			<td>Kynar</td>
			<td>&nbsp;</td>
			<td>Kynar</td>
		</tr>
		<tr>
			<td>PVDF Separator</td>
			<td>Celgard</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>LP30</td>
			<td>Merck</td>
			<td>&nbsp;</td>
			<td>LiPF6 in EC:DMC</td>
		</tr>
		<tr>
			<td>MACCOR battery tester</td>
			<td>MACCOR</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>El-Cut</td>
			<td>EL-CELL</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
		</tr>
	</tbody>
</table>

solid-state graft copolymer electrolytes for lithium battery applications

在过去的十年中，电池的安全性一直是非常重要的研究领域。市售锂离子电池采用闪点低（&lt;80℃），易燃，挥发性有机电解质。基于这些有机电解质体系在室温下是可行的，但需要一个冷却系统，确保温度不超过80°C这些冷却系统往往以增加电池的成本和故障，这可能会导致电池故障和爆炸，从而危及人类生命。石油价格上涨导致巨大的需求安全，电动混合动力汽车更经济可行的操作油价继续上涨。基于现有的有机电解质的锂离子电池所用并不适用于高温汽车应用。一个更安全的替代有机电解质是固体聚合物电解质。这项工作将突出合成的接枝共聚物电解质（GCE）聚（邻的xyethylene）甲基丙烯酸酯（POEM），具有较低的玻璃化转变温度（Tg）的聚（氧乙烯）丙烯酸酯（POEA）的方框图。传导机制已经讨论过，它已被证明聚合物节段性运动和离子电导率之间的关系确实有沃格尔塔姆曼弗切尔（VTF）的依赖。是含有市售LP30有机（的LiPF 6的碳酸亚乙酯（EC）：碳酸二甲酯（DMC）以1:1的比例）和GCE电池在环境温度下循环。结果发现，在环境温度下，含有伦大的电池相比，LP30电解质时表现出较大的过电位。然而，在温度大于60℃下，的GCE细胞表现出低得多的超电势，由于高分子电解质电导率快速访问几乎完整的理论比容量为170毫安时/克。

室温下电池的循 ​​环性能， 如图8中所示。左边的图显示的充电和放电曲线与传统的液体电解质（LP30）的细胞在15毫安/ g，且：GCE /粘合剂在10毫安/克。 图9显示了在室温下的固体高分子型细胞的放电电压的档案60℃，和120℃下使用0.05 C.一个低电流的放电电压的档案作为具体的能力的函数示于图10中的放电电流为μA和标记旁边的放电曲线， 图10?...

Watch this Scientific Journal Video about Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications at JoVE.com

Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

锂离子电池使用易燃，易挥发的有机电解质，是适用于环境温度下应用。一个更安全的替代有机电解质是固体聚合物电池。固体高分子型电池的安全运行在高温下（&gt; 120℃），从而使它们适用于高温应用，如深石油钻探和混合动力电动汽车。本文将讨论（一）聚合物的合成，（b​​）聚合物传导机制，以及（c）提供固体聚合物和有机电解液的温度循环。

接枝共聚物固态电解质的锂离子电池的应用

Battery safety has been a very important research area over the past decade. Commercially available lithium ion batteries employ low flash point (&lt;80 ...

solid-state-graft-copolymer-electrolytes-for-lithium-battery

Research

JoVE Journal

Engineering

21.5K 次观看.  Massachusetts Institute of Technology. 锂离子电池使用易燃，易挥发的有机电解质，是适用于环境温度下应用。一个更安全的替代有机电解质是固体聚合物电池。固体高分子型电池的安全运行在高温下（> 120℃），从而使它们适用于高温应用，如深石油钻探和混合动力电动汽车。本文将讨论（一）聚合物的合成，（b​​）聚合物传导机制，以及（c）提供固体聚合物和有机电解液的温度循环。

视频: Solid-state Graft Copolymer Electrolytes for Lithium Battery Applications

Construction and Testing of Coin Cells of Lithium Ion Batteries

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime. Lithium ion batteries have also been considered to be used in electric and hybrid vehicles1 or even electrical grid stabilization systems2. All these applications simulate a dramatic increase in the research and development of battery materials3-7, including new materials3,8, doping9, nanostructuring10-13, coatings or surface modifications14-17 and novel binders18. Consequently, an increasing number of physicists, chemists and materials scientists have recently ventured into this area. Coin cells are widely used in research laboratories to test new battery materials; even for the research and development that target large-scale and high-power applications, small coin cells are often used to test the capacities and rate capabilities of new materials in the initial stage. 
 In 2010, we started a National Science Foundation (NSF) sponsored research project to investigate the surface adsorption and disordering in battery materials (grant no. DMR-1006515). In the initial stage of this project, we have struggled to learn the techniques of assembling and testing coin cells, which cannot be achieved without numerous help of other researchers in other universities (through frequent calls, email exchanges and two site visits). Thus, we feel that it is beneficial to document, by both text and video, a protocol of assembling and testing a coin cell, which will help other new researchers in this field. This effort represents the "Broader Impact" activities of our NSF project, and it will also help to educate and inspire students.
In this video article, we document a protocol to assemble a CR2032 coin cell with a LiCoO2 working electrode, a Li counter electrode, and (the mostly commonly used) polyvinylidene fluoride (PVDF) binder. To ensure new learners to readily repeat the protocol, we keep the protocol as specific and explicit as we can. However, it is important to note that in specific research and development work, many parameters adopted here can be varied. First, one can make coin cells of different sizes and test the working electrode against a counter electrode other than Li. Second, the amounts of C black and binder added into the working electrodes are often varied to suit the particular purpose of research; for example, large amounts of C black or even inert powder were added to the working electrode to test the "intrinsic" performance of cathode materials14. Third, better binders (other than PVDF) have also developed and used18. Finally, other types of electrolytes (instead of LiPF6) can also be used; in fact, certain high-voltage electrode materials will require the uses of special electrolytes7.

A protocol to construct and test coin cells of lithium ion batteries is described. The specific procedures of making a working electrode, preparing a counter electrode, assembling a cell inside a glovebox and testing the cell are presented.

钮扣电池锂离子电池的建设和测试

Rechargeable lithium ion batteries have wide applications in electronics, where customers always demand more capacity and longer lifetime.  Lithium ion ...

科研

工程学

Probing and Mapping Electrode Surfaces in Solid Oxide Fuel Cells

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen 1-7. The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion2. Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation8-12. It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition8, 10, 13, 14 ("coking") and sulfur poisoning11, 15 and the manner in which surface modifications stave off this degradation16. The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM, other properties such as local electronic states, ion diffusion coefficient and surface potential can also be investigated17-22. In this work, electrochemical measurements, Raman spectroscopy, and SPM were used in conjunction with a novel test electrode platform that consists of a Ni mesh electrode embedded in an yttria-stabilized zirconia (YSZ) electrolyte. Cell performance testing and impedance spectroscopy under fuel containing H2S was characterized, and Raman mapping was used to further elucidate the nature of sulfur poisoning. In situ Raman monitoring was used to investigate coking behavior. Finally, atomic force microscopy (AFM) and electrostatic force microscopy (EFM) were used to further visualize carbon deposition on the nanoscale. From this research, we desire to produce a more complete picture of the SOFC anode.

We present a unique platform for characterizing electrode surfaces in solid oxide fuel cells (SOFCs) that allows simultaneous performance of multiple characterization techniques (e.g. in situ Raman spectroscopy and scanning probe microscopy alongside electrochemical measurements). Complementary information from these analyses may help to advance toward a more profound understanding of electrode reaction and degradation mechanisms, providing insights into rational design of better materials for SOFCs.

在固体氧化物燃料电池电极表面的探测和测绘

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen ...

Characterization of Electrode Materials for Lithium Ion and Sodium Ion Batteries Using Synchrotron Radiation Techniques

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. During insertion or removal of alkali metal ions, the redox states of transition metals in the compounds change and structural transformations such as phase transitions and/or lattice parameter increases or decreases occur. These behaviors in turn determine important characteristics of the batteries such as the potential profiles, rate capabilities, and cycle lives. The extremely bright and tunable x-rays produced by synchrotron radiation allow rapid acquisition of high-resolution data that provide information about these processes. Transformations in the bulk materials, such as phase transitions, can be directly observed using X-ray diffraction (XRD), while X-ray absorption spectroscopy (XAS) gives information about the local electronic and geometric structures (e.g.&#160;changes in redox states and bond lengths). In situ experiments carried out on operating cells are particularly useful because they allow direct correlation between the electrochemical and structural properties of the materials. These experiments are time-consuming and can be challenging to design due to the reactivity and air-sensitivity of the alkali metal anodes used in the half-cell configurations, and/or the possibility of signal interference from other cell components and hardware. For these reasons, it is appropriate to carry out ex situ experiments (e.g.&#160;on electrodes harvested from partially charged or cycled cells) in some cases. Here, we present detailed protocols for the preparation of both ex situ and in situ samples for experiments involving synchrotron radiation and demonstrate how these experiments are done.

We describe the use of synchrotron X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) techniques to probe details of intercalation/deintercalation processes in electrode materials for Li-ion and Na-ion batteries. Both in situ and ex situ experiments are used to understand structural behavior relevant to the operation of devices

正极材料的同步辐射技术锂离子和钠离子电池表征

Intercalation compounds such as transition metal oxides or phosphates are the most commonly used electrode materials in Li-ion and Na-ion batteries. ...

Fine-tuning the Size and Minimizing the Noise of Solid-state Nanopores

Solid-state nanopores have emerged as a versatile tool for the characterization of single biomolecules such as nucleic acids and proteins1. However, the creation of a nanopore in a thin insulating membrane remains challenging. Fabrication methods involving specialized focused electron beam systems can produce well-defined nanopores, but yield of reliable and low-noise nanopores in commercially available membranes remains low2,3 and size control is nontrivial4,5. Here, the application of high electric fields to fine-tune the size of the nanopore while ensuring optimal low-noise performance is demonstrated. These short pulses of high electric field are used to produce a pristine electrical signal and allow for enlarging of nanopores with subnanometer precision upon prolonged exposure. This method is performed in situ in an aqueous environment using standard laboratory equipment, improving the yield and reproducibility of solid-state nanopore fabrication.

A methodology for preparing solid-state nanopores in solution for biomolecular translocation experiments is presented. By applying short pulses of high electric fields, the nanopore diameter can be controllably enlarged with subnanometer precision and its electrical noise characteristics significantly improved. This procedure is performed in situ using standard laboratory equipment under experimental conditions.

微调尺寸和最小化固态纳米孔的噪音

Solid-state nanopores have emerged as a versatile tool for the characterization of single biomolecules such as nucleic acids and proteins1. However, the ...

In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric vehicles.1,2 However, many challenges, such as energy density and battery lifetimes, need to be overcome before this particular battery technology can be widely implemented in such applications.3 This research is challenging, and we outline a method to address these challenges using in situ NPD to probe the crystal structure of electrodes undergoing electrochemical cycling (charge/discharge) in a battery. NPD data help determine the underlying structural mechanism responsible for a range of electrode properties, and this information can direct the development of better electrodes and batteries.
We briefly review six types of battery designs custom-made for NPD experiments and detail the method to construct the &#8216;roll-over&#8217; cell that we have successfully used on the high-intensity NPD instrument, WOMBAT, at the Australian Nuclear Science and Technology Organisation (ANSTO). The design considerations and materials used for cell construction are discussed in conjunction with aspects of the actual in situ NPD experiment and initial directions are presented on how to analyze such complex in situ data.

In Situ Neutron Powder Diffraction Using Custom-made Lithium-ion Batteries

We describe the design and construction of an electrochemical cell for the examination of electrode materials using in situ neutron powder diffraction (NPD). We briefly comment on alternate in situ NPD cell designs and discuss methods for the analysis of the corresponding in situ NPD data produced using this cell.

原位中子衍射用特制的锂离子电池

Li-ion batteries are widely used in portable electronic devices and are considered as promising candidates for higher-energy applications such as electric ...

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of lithium-ion (Li-ion) batteries. However, a number of setbacks prevent their integration into commercial devices. The main limiting factor is due to nanoscale phenomena occurring at the electrode/electrolyte interfaces, ultimately leading to degradation of battery operation. These key problems are highly challenging to observe and characterize as these batteries contain multiple buried interfaces. One approach for direct observation of interfacial phenomena in thin film batteries is through the fabrication of electrochemically active nanobatteries by a focused ion beam (FIB). As such, a reliable technique to fabricate nanobatteries was developed and demonstrated in recent work. Herein, a detailed protocol with a step-by-step process is presented to enable the reproduction of this nanobattery fabrication process. In particular, this technique was applied to a thin film battery consisting of LiCoO2/LiPON/a-Si, and has further been previously demonstrated by in situ cycling within a transmission electron microscope.

Focused Ion Beam Fabrication of LiPON-based Solid-state Lithium-ion Nanobatteries for In Situ Testing

A protocol for the fabrication of electrochemically active LiPON-based solid-state lithium-ion nanobatteries using a focused ion beam is presented.

基于 LiPON 的固态锂离子 Nanobatteries 的聚焦离子束制备方法在原位测试中的研究

Solid-state electrolytes are a promising replacement for current organic liquid electrolytes, enabling higher energy densities and improved safety of ...

All-electronic Nanosecond-resolved Scanning Tunneling Microscopy: Facilitating the Investigation of Single Dopant Charge Dynamics

The miniaturization of semiconductor devices to scales where small numbers of dopants can control device properties requires the development of new techniques capable of characterizing their dynamics. Investigating single dopants requires sub-nanometer spatial resolution, which motivates the use of scanning tunneling microscopy (STM). However, conventional STM is limited to millisecond temporal resolution. Several methods have been developed to overcome this shortcoming, including all-electronic time-resolved STM, which is used in this study to examine dopant dynamics in silicon with nanosecond resolution. The methods presented here are widely accessible and allow for local measurement of a wide variety of dynamics at the atomic scale. A novel time-resolved scanning tunneling spectroscopy technique is presented and used to efficiently search for dynamics.

We demonstrate an all-electronic method to observe nanosecond-resolved charge dynamics of dopant atoms in silicon with a scanning tunneling microscope.

全电子纳秒分辨扫描隧道显微镜: 促进单一掺杂剂电荷动力学的研究

The miniaturization of semiconductor devices to scales where small numbers of dopants can control device properties requires the development of new ...

Electric-field Control of Electronic States in WS2 Nanodevices by Electrolyte Gating

A method of carrier number control by electrolyte gating is demonstrated. We have obtained WS2 thin flakes with atomically flat surface via scotch tape method or individual WS2 nanotubes by dispersing the suspension of WS2 nanotubes. The selected samples have been fabricated into devices by the use of the electron beam lithography and electrolyte is put on the devices. We have characterized the electronic properties of the devices under applying the gate voltage. In the small gate voltage region, ions in the electrolyte are accumulated on the surface of the samples which leads to the large electric potential drop and resultant electrostatic carrier doping at the interface. Ambipolar transfer curve has been observed in this electrostatic doping region. When the gate voltage is further increased, we met another drastic increase of source-drain current which implies that ions are intercalated into layers of WS2 and electrochemical carrier doping is realized. In such electrochemical doping region, superconductivity has been observed. The focused technique provides a powerful strategy for achieving the electric-filed-induced quantum phase transition.

Electric-field Control of Electronic States in WS2 Nanodevices by Electrolyte Gating

Here, we present a protocol to control the carrier number in solids by using the electrolyte.

用电解质浇注法对 WS2纳米器件电子态的电场控制

A method of carrier number control by electrolyte gating is demonstrated. We have obtained WS2 thin flakes with atomically flat surface via scotch tape ...

Experimental Methods for Spin- and Angle-Resolved Photoemission Spectroscopy Combined with Polarization-Variable Laser

The goal of this protocol is to present how to perform spin- and angle-resolved photoemission spectroscopy combined with polarization-variable 7-eV laser (laser-SARPES), and demonstrate a power of this technique for studying solid state physics. Laser-SARPES achieves two great capabilities. Firstly, by examining orbital selection rule of linearly polarized lasers, orbital selective excitation can be carried out in SAPRES experiment. Secondly, the technique can show full information of a variation of the spin quantum axis as a function of the light polarization. To demonstrate the power of the collaboration of these capabilities in laser-SARPES, we apply this technique for the investigations of spin-orbit coupled surface states of Bi2Se3. This technique affords to decompose spin and orbital components from the spin-orbit coupled wavefunctions. Moreover, as a representative advantage of using the direct spin detection collaborated with the polarization-variable laser, the technique unambiguously visualizes the light polarization dependence of the spin quantum axis in three-dimension. Laser-SARPES dramatically increases a capability of photoemission technique.

Here, we combine polarization-variable 7-eV laser with spin- and angle-resolved photoemission technique to visualize the spin-orbital coupling effect in solid states.

自旋角分辨光电子光谱与偏振变激光相结合的实验方法

The goal of this protocol is to present how to perform spin- and angle-resolved photoemission spectroscopy combined with polarization-variable 7-eV laser ...

Three-electrode Coin Cell Preparation and Electrodeposition Analytics for Lithium-ion Batteries

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and subsequent safety issues becomes increasingly important. In a Li-ion cell setup, the voltage measurement across the positive and negative terminals inherently includes the effect of the cathode and anode which are coupled and sum to the total cell performance. Accordingly, the ability to monitor the degradation aspects associated with a specific electrode is extremely difficult because the electrodes are fundamentally coupled. A three-electrode setup can overcome this problem. By introducing a third (reference) electrode, the influence of each electrode can be decoupled, and the electrochemical properties can be measured independently. The reference electrode (RE) must have a stable potential that can then be calibrated against a known reference, for example, lithium metal. The three-electrode cell can be used to run electrochemical tests such as cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). Three-electrode cell EIS measurements can elucidate the contribution of individual electrode impedance to the full cell. In addition, monitoring the anode potential allows the detection of electrodeposition due to lithium plating, which can cause safety concerns. This is especially important for the fast charging of Li-ion batteries in electric vehicles. In order to monitor and characterize the safety and degradation aspects of an electrochemical cell, a three-electrode setup can prove invaluable. This paper aims to provide a guide to constructing a three-electrode coin cell setup using the 2032-coin cell architecture, which is easy to produce, reliable, and cost-effective.

Three-electrode cells are useful in studying the electrochemistry of lithium-ion batteries. Such an electrochemical setup allows the phenomena associated with the cathode and anode to be decoupled and examined independently. Here, we present a guide for construction and use of a three-electrode coin cell with emphasis on lithium plating analytics.

锂离子电池三电极硬币电池制备及电沉积分析

As lithium-ion batteries find use in high energy and power applications, such as in electric and hybrid-electric vehicles, monitoring the degradation and ...