【《单离子传导聚合物电解质综述》9600字】

单离子传导聚合物电解质综述目录TOC\o"1-3"\h\u14665单离子传导聚合物电解质综述 156681.1单离子传导凝胶聚合物电解质简介 19911.2单离子传导聚合物合成策略 1253381.3单离子传导聚合物电解质隔膜的成膜方式 9279541.4在锂金属二次电池中的应用 141.1单离子传导凝胶聚合物电解质简介单离子传导聚合物电解质具有聚合物电解质的特性，质量轻、机械强度好、易成膜、种类多样，也顺应了锂离子电池能量密度高，安全性能好，绿色环保的发展趋势ADDINEN.CITEADDINEN.CITE.DATA[25-27]。按照状态可分为单离子传导凝胶聚合物电解质（SIC-GPE）和单离子传导固态聚合物电解质（SIC-SPE）。SIC-GPE和SIC-SPE阴离子固定策略和成膜方式相同，组成成分却不同。SIC-SPE中不需要加入增塑剂，但含有PEG，聚碳酸酯或者硅氧烷等玻璃转化温度低，在室温条件下为高弹态的聚合物。极性官能团醚键、碳酸酯键解离离子对的同时通过链的运动实现锂离子的传导，但其锂离子电导率依旧很低（室温下<10−5Scm−1）ADDINEN.CITEADDINEN.CITE.DATA[27-34]。尽管已经报道了许多SIC-SPE，但低离子电导率导致电池性能较差并且用SIC-SPE组装的电池只能在高温（>60°C）下以低倍率（通常≤0.2C）工作ADDINEN.CITEADDINEN.CITE.DATA[35-39]。而单离子传导凝胶聚合物电解质中加入了增塑剂来促进离子对解离并传导锂离子，在室温条件下，应用于锂电池可实现高倍率（>1C）稳定的循环。因此，在介绍阴离子固定，实现单离子传导的策略和成膜方式时也会引用SIC-SPE的例子，但只介绍SIC-GPE在锂金属二次电池中的应用。1.2单离子传导聚合物合成策略“阴离子固定”是实现单离子传导的关键，通常的策略包括：（1）将阴离子与聚合物主链通过共价键连接；（2）将阴离子通过官能团反应固定在无机材料上；（3）在双离子型电解质中加入阴离子捕捉剂。图1.3示出了三种策略的示意图。在接下来的章节中，将对单离子传导聚合物电解质进行介绍。图1.3单离子传导聚合物的合成策略：(a)聚合物有机主链；(b)无机主链；(c)阴离子受体1.2.1以有机聚合物为骨架的单离子传导聚合物电解质合成具有聚合物骨架的单离子传导聚合物电解质一般有两种方式：（1）功能锂盐单体（LSM）的直接聚合和（2）通过功能锂盐单体对现有聚合物进行化学改性。这两种方式都是通过官能团间的反应使阴离子通过化学键进行固定。功能锂盐单体（LSM）的直接聚合LSM聚合是一种概念简单、直观、广泛被采用的制备单离子传导聚合物电解质的策略。图1.4所示，功能锂盐单体（LSM）包括可聚合基团、间隔臂和阴离子中心。用于单离子传导聚合物电解质的LSMS通常具有阴离子中的可聚合单元，如丙烯、乙烯、苯乙烯基团。间隔臂有助于离子对的解离和锂离子的传导，通常是低聚乙烯和/或环氧乙烷（EO）装置。阴离子中心主要为容易合成的羧酸盐（-CO2-ADDINEN.CITEADDINEN.CITE.DATA[40-46]）、磺酸盐（-SO3-ADDINEN.CITEADDINEN.CITE.DATA[27,29,47-50]）或磺酰亚胺（-SO2N--SO2-ADDINEN.CITEADDINEN.CITE.DATA[35,51-66]）阴离子。图1.4LSM聚合策略制备的梳妆单离子传导聚合物结构示意图：(a)不含柔性侧链；（b）含柔性侧链自由基聚合物是一种简单而常用的聚合方式。MichelArmand教授团队ADDINEN.CITE<EndNote><Cite><Author>Meziane</Author><Year>2011</Year><RecNum>205</RecNum><DisplayText><styleface="superscript">[65]</style></DisplayText><record><rec-number>205</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603674662">205</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Meziane,Rachid</author><author>Bonnet,Jean-Pierre</author><author>Courty,Matthieu</author><author>Djellab,Karim</author><author>Armand,Michel</author></authors></contributors><titles><title>Single-ionpolymerelectrolytesbasedonadelocalizedpolyanionforlithiumbatteries</title><secondary-title>ElectrochimicaActa</secondary-title></titles><periodical><full-title>ElectrochimicaActa</full-title></periodical><pages>14-19</pages><volume>57</volume><dates><year>2011</year></dates><isbn>0013-4686</isbn><urls></urls></record></Cite></EndNote>[65]在2011年以偶氮二异丁腈（AIBN）为引发剂，通过自由基聚合将-SO2-NLi-SO2-CF3连接到聚苯乙烯链上得到聚（4-苯乙烯磺酰基（三氟甲基磺酰基）酰亚胺）锂（PSTFSI）聚单离子传导聚合物（图1.5bADDINEN.CITE<EndNote><Cite><Author>Meziane</Author><Year>2011</Year><RecNum>205</RecNum><DisplayText><styleface="superscript">[65]</style></DisplayText><record><rec-number>205</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603674662">205</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Meziane,Rachid</author><author>Bonnet,Jean-Pierre</author><author>Courty,Matthieu</author><author>Djellab,Karim</author><author>Armand,Michel</author></authors></contributors><titles><title>Single-ionpolymerelectrolytesbasedonadelocalizedpolyanionforlithiumbatteries</title><secondary-title>ElectrochimicaActa</secondary-title></titles><periodical><full-title>ElectrochimicaActa</full-title></periodical><pages>14-19</pages><volume>57</volume><dates><year>2011</year></dates><isbn>0013-4686</isbn><urls></urls></record></Cite></EndNote>[65]）。再将PSTFSI与PEO共混（O/Li=20:1）制得SIC-SPE，在41℃时，离子电导率为7.9410−7Scm−1。接着，周志斌和MichelArmand合作合成阴离子离域更强的结构，并采用相同的聚合方式得到聚[（4-苯乙烯磺酰基）（三氟甲基（S-三氟甲磺酰亚胺）磺酰基）酰亚胺](PSSTFSI)（图1.5dADDINEN.CITE<EndNote><Cite><Author>Ma</Author><Year>2016</Year><RecNum>202</RecNum><DisplayText><styleface="superscript">[64]</style></DisplayText><record><rec-number>202</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603674493">202</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ma,Qiang</author><author>Zhang,Heng</author><author>Zhou,Chongwang</author><author>Zheng,Liping</author><author>Cheng,Pengfei</author><author>Nie,Jin</author><author>Feng,Wenfang</author><author>Hu,Yong‐Sheng</author><author>Li,Hong</author><author>Huang,Xuejie</author></authors></contributors><titles><title>Singlelithium‐ionconductingpolymerelectrolytesbasedonasuper‐delocalizedpolyanion</title><secondary-title>AngewandteChemieInternationalEdition</secondary-title></titles><periodical><full-title>AngewandteChemieInternationalEdition</full-title></periodical><pages>2521-2525</pages><volume>55</volume><number>7</number><dates><year>2016</year></dates><isbn>1433-7851</isbn><urls></urls></record></Cite></EndNote>[64]），其与高分子量的PEO共混制得离子迁移数为0.91，90℃离子电导率提高到了1.3510−4Scm−1。同一年，周志斌和MichelArmand再次一起发表了制备聚[（4-苯乙烯磺酰基）（氟磺酰基）酰亚胺]锂（LiPSFSI）图1.5cADDINEN.CITE<EndNote><Cite><Author>Ma</Author><Year>2016</Year><RecNum>201</RecNum><DisplayText><styleface="superscript">[63]</style></DisplayText><record><rec-number>201</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603674468">201</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ma,Qiang</author><author>Xia,Yu</author><author>Feng,Wenfang</author><author>Nie,Jin</author><author>Hu,Yong-Sheng</author><author>Li,Hong</author><author>Huang,Xuejie</author><author>Chen,Liquan</author><author>Armand,Michel</author><author>Zhou,Zhibin</author></authors></contributors><titles><title>Impactofthefunctionalgroupinthepolyanionofsinglelithium-ionconductingpolymerelectrolytesonthestabilityoflithiummetalelectrodes</title><secondary-title>RSCadvances</secondary-title></titles><periodical><full-title>RSCAdvances</full-title></periodical><pages>32454-32461</pages><volume>6</volume><number>39</number><dates><year>2016</year></dates><urls></urls></record></Cite></EndNote>[63]的方法。由LiPSFSI和高分子量聚环氧乙烷（PEO，Mw=4×106gmol-1）组成新型单锂离子导电聚合物电解质，离子迁移数达到0.90。另外，LiX/PEO（X=PSFSI，PSTFSI，EO/Li+=20）比LiPSS（图1.5aADDINEN.CITE<EndNote><Cite><Author>Ma</Author><Year>2016</Year><RecNum>201</RecNum><DisplayText><styleface="superscript">[63]</style></DisplayText><record><rec-number>201</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603674468">201</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ma,Qiang</author><author>Xia,Yu</author><author>Feng,Wenfang</author><author>Nie,Jin</author><author>Hu,Yong-Sheng</author><author>Li,Hong</author><author>Huang,Xuejie</author><author>Chen,Liquan</author><author>Armand,Michel</author><author>Zhou,Zhibin</author></authors></contributors><titles><title>Impactofthefunctionalgroupinthepolyanionofsinglelithium-ionconductingpolymerelectrolytesonthestabilityoflithiummetalelectrodes</title><secondary-title>RSCadvances</secondary-title></titles><periodical><full-title>RSCAdvances</full-title></periodical><pages>32454-32461</pages><volume>6</volume><number>39</number><dates><year>2016</year></dates><urls></urls></record></Cite></EndNote>[63]）/PEO（EO/Li+=20）电解质的离子电导率高约1-2个数量级。原因是PSFSI-和PSTFSI-阴离子中的−SO2-N--SO2-结构比PSS-阴离子中的−SO3-结构具有更强的离域。而且LiPSFSI聚阴离子中的FSO2−基团使其比LiPSS/PEO和LiPSTFSI/PEO电解质对Li金属电极具有良好的界面相容性。由上可知，相同的主链结构，增强阴离子的离域促进了锂离子的解离，提高了离子迁移速率。图1.5通过自由基聚合制备梳妆单离子传导聚合物结构功能锂盐单体也能够通过与具有一定功能的分子或片段进行聚合，以达到提高离子电导率或者改善力学性能的目的。MichelArmand教授团队将4-苯乙烯磺酰（三氟甲基磺酰）亚胺锂(STFSILi)与PEO采用氮氧化物介导聚合法合成了具有不同的P（STFSILi）/PEO比率（10-40wt%P（STFSILi）的P（STFSILi）-PEO-P（STFSILi）嵌段共聚物（图1.5g）ADDINEN.CITE<EndNote><Cite><Author>Bouchet</Author><Year>2013</Year><RecNum>115</RecNum><DisplayText><styleface="superscript">[35]</style></DisplayText><record><rec-number>115</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603629333">115</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bouchet,Renaud</author><author>Maria,Sébastien</author><author>Meziane,Rachid</author><author>Aboulaich,Abdelmaula</author><author>Lienafa,Livie</author><author>Bonnet,Jean-Pierre</author><author>Phan,TrangNT</author><author>Bertin,Denis</author><author>Gigmes,Didier</author><author>Devaux,Didier</author></authors></contributors><titles><title>Single-ionBABtriblockcopolymersashighlyefficientelectrolytesforlithium-metalbatteries</title><secondary-title>Naturematerials</secondary-title></titles><periodical><full-title>Naturematerials</full-title></periodical><pages>452-457</pages><volume>12</volume><number>5</number><dates><year>2013</year></dates><isbn>1476-4660</isbn><urls></urls></record></Cite></EndNote>[35]。将其与聚丙烯隔膜制备复合型单离子传导聚合物电解质。PEO短链的引入，降低了聚合物的玻璃转化温度。在最佳比例时，离子迁移数达到0.85，在60℃时离子电导率达到了1.310−5Scm−1，并且装配的磷酸铁锂电池能够在60℃以上温度、低倍率条件下正常工作。封伟教授通过简单的自由基共聚反应，以4-苯乙烯磺酰（苯基磺酰）亚胺锂和马来酸酐为原料，合成了交替结构的离聚物P(SSPSILi-alt-MA)(图1.5f)ADDINEN.CITE<EndNote><Cite><Author>Cao</Author><Year>2017</Year><RecNum>56</RecNum><DisplayText><styleface="superscript">[60]</style></DisplayText><record><rec-number>56</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603625717">56</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Cao,Chen</author><author>Li,Yu</author><author>Feng,Yiyu</author><author>Long,Peng</author><author>An,Haoran</author><author>Qin,Chengqun</author><author>Han,Junkai</author><author>Li,Shuangwen</author><author>Feng,Wei</author></authors></contributors><titles><title>Asulfonimide-basedalternatingcopolymerasasingle-ionpolymerelectrolyteforhigh-performancelithium-ionbatteries</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><pages>22519-22526</pages><volume>5</volume><number>43</number><dates><year>2017</year></dates><urls></urls></record></Cite></EndNote>[60]。与聚偏氟乙烯-六氟丙烯（PVDF-HFP）共混成膜，以EC/PC为塑化剂，制备SIC-GPE，测得离子迁移数达到0.98，离子电导率2.57×10-3mScm−1。PVDF-HFP为电解质提供了骨架，EC/PC的加入和极性官能团马来酸酐的引入促进了锂离子的溶解，使离子电导率远高于P（STFSILi）/PEO电解质。P(SSPSILi-alt-MA)应用于磷酸铁锂和钛酸锂二次电池，在1C倍率条件先均表现出来优异的循环性能。图1.5中所列通过自由基聚合制备的单离子传导聚合物均为梳妆结构。程寒松教授课题组ADDINEN.CITEADDINEN.CITE.DATA[51-53,56-59]和G.Brunklaus教授课题组ADDINEN.CITE<EndNote><Cite><Author>Borzutzki</Author><Year>2019</Year><RecNum>221</RecNum><DisplayText><styleface="superscript">[55]</style></DisplayText><record><rec-number>221</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603676651">221</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Borzutzki,K</author><author>Thienenkamp,J</author><author>Diehl,M</author><author>Winter,M</author><author>Brunklaus,G</author></authors></contributors><titles><title>Fluorinatedpolysulfonamidebasedsingleionconductingroomtemperatureapplicablegel-typepolymerelectrolytesforlithiumionbatteries</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><pages>188-201</pages><volume>7</volume><number>1</number><dates><year>2019</year></dates><urls></urls></record></Cite></EndNote>[55]则制备了一系列阴离子中心在主链上的直链型单离子传导聚合物电解质。由于阴阳离子间的静电相互作用主导了聚合物主链，造成主链之间的作用力弱，因此，此类单离子传导聚合物均不能单独成膜。一般通过加入聚偏氟乙烯（PVDF）、聚偏氟乙烯-六氟丙烯（PVDF-HFP）或聚乙二醇（PEO）等工程高分子来提供有机骨架，从而形成具有一定机械强度的隔膜。PVDF和PEO为直链型高分子，高分子量的PVDF能够为隔膜提供良好的力学性能，而PEO中的-O-则能够促进锂离子的解离，低玻璃转化温度使链段更容易运动促进锂离子的运输，两者共同作用提高了电解质的离子电导率。PVDF-HFP为无规共聚物，具有交联型的超支化结构，与PVDF相比没有结晶度，能够促进隔膜对塑化剂的浸润，在保持机械强度的同时促进锂离子的传导。图1.6中a、b、c、e和f结构的单离子传导聚合物均是4，4’-二羧基双苯磺酰亚胺和另外一个含两个氨基并具有一定功能性的分子通过羧基与氨基脱水缩合（达到分子设计的目的，给与聚合物不同的性能），再进行锂离子交换制备而成，再将其与PVDF或者PVDF-HFP共混制备得到单离子传导聚合物电解质隔膜。这几种隔膜将阴离子中心固定在主链，具有高离子迁移数达到0.88~0.92。将结构aADDINEN.CITE<EndNote><Cite><Author>Pan</Author><Year>2015</Year><RecNum>177</RecNum><DisplayText><styleface="superscript">[51]</style></DisplayText><record><rec-number>177</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603672652">177</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Pan,Qiyun</author><author>Zhang,Wenchao</author><author>Pan,Meize</author><author>Zhang,Baodan</author><author>Zeng,Danli</author><author>Sun,Yubao</author><author>Cheng,Hansong</author></authors></contributors><titles><title>Constructionofalithiumiontransportnetworkincathodewithlithiatedbis(benzenesulfonyl)imidebasedsingleionpolymerionomers</title><secondary-title>JournalofPowerSources</secondary-title></titles><periodical><full-title>JournalofPowerSources</full-title></periodical><pages>279-288</pages><volume>283</volume><dates><year>2015</year></dates><isbn>0378-7753</isbn><urls></urls></record></Cite></EndNote>[51]中的4，4’-二氨基双苯磺酰亚胺锂替换成2，4-二氨基苯磺酸锂得到含有-SO3-和-SO2-N--SO2-分别在测链和主链的结构bADDINEN.CITE<EndNote><Cite><Author>Sun</Author><Year>2014</Year><RecNum>176</RecNum><DisplayText><styleface="superscript">[57]</style></DisplayText><record><rec-number>176</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603672556">176</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sun,Yubao</author><author>Rohan,Rupesh</author><author>Cai,Weiwei</author><author>Wan,Xifei</author><author>Pareek,Kapil</author><author>Lin,An</author><author>Yunfeng,Zhang</author><author>Cheng,Hansong</author></authors></contributors><titles><title>APolyamideSingle‐IonElectrolyteMembraneforApplicationinLithium‐IonBatteries</title><secondary-title>EnergyTechnology</secondary-title></titles><periodical><full-title>EnergyTechnology</full-title></periodical><pages>698-704</pages><volume>2</volume><number>8</number><dates><year>2014</year></dates><isbn>2194-4288</isbn><urls></urls></record></Cite></EndNote>[57]。虽然锂离子离子迁移数有少量下降，从0.92下降到0.88，但提高了结构中的锂离子含量，室温离子电导率从1.4×10-4Scm-1提高到3.8×10-4Scm-1。换成阻燃片段4，4’-二氨基二苯砜得到c结构ADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2018</Year><RecNum>175</RecNum><DisplayText><styleface="superscript">[58]</style></DisplayText><record><rec-number>175</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603672497">175</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Yunfeng</author><author>Chen,Yazhou</author><author>Liu,Yuan</author><author>Qin,Bingsheng</author><author>Yang,Zehui</author><author>Sun,Yubao</author><author>Zeng,Danli</author><author>Passerini,Stefano</author><author>Liu,Zhihong</author><author>Cheng,Hansong</author></authors></contributors><titles><title>Highlyporoussingle-ionconductivecompositepolymerelectrolyteforhighperformanceLi-ionbatteries</title><secondary-title>JournalofPowerSources</secondary-title></titles><periodical><full-title>JournalofPowerSources</full-title></periodical><pages>79-86</pages><volume>397</volume><dates><year>2018</year></dates><isbn>0378-7753</isbn><urls></urls></record></Cite></EndNote>[58]，增加了隔膜的热稳定，明火点燃后火焰自动熄灭。换成含有-C（CF3）基团的4,4’-（六氟异丙基）二苯胺所得结构eADDINEN.CITE<EndNote><Cite><Author>Borzutzki</Author><Year>2019</Year><RecNum>221</RecNum><DisplayText><styleface="superscript">[55]</style></DisplayText><record><rec-number>221</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603676651">221</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Borzutzki,K</author><author>Thienenkamp,J</author><author>Diehl,M</author><author>Winter,M</author><author>Brunklaus,G</author></authors></contributors><titles><title>Fluorinatedpolysulfonamidebasedsingleionconductingroomtemperatureapplicablegel-typepolymerelectrolytesforlithiumionbatteries</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><pages>188-201</pages><volume>7</volume><number>1</number><dates><year>2019</year></dates><urls></urls></record></Cite></EndNote>[55]与结构c相比，提高其溶解性，使锂离子交换更加彻底，离子迁移数提高了0.02。结构fADDINEN.CITE<EndNote><Cite><Author>Zhang</Author><Year>2014</Year><RecNum>174</RecNum><DisplayText><styleface="superscript">[59]</style></DisplayText><record><rec-number>174</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603672419">174</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Yunfeng</author><author>Rohan,Rupesh</author><author>Cai,Weiwei</author><author>Xu,Guodong</author><author>Sun,Yubao</author><author>Lin,An</author><author>Cheng,Hansong</author></authors></contributors><titles><title>Influenceofchemicalmicrostructureofsingle-ionpolymericelectrolytemembranesonperformanceoflithium-ionbatteries</title><secondary-title>ACSappliedmaterials&interfaces</secondary-title></titles><periodical><full-title>ACSappliedmaterials&interfaces</full-title></periodical><pages>17534-17542</pages><volume>6</volume><number>20</number><dates><year>2014</year></dates><isbn>1944-8244</isbn><urls></urls></record></Cite></EndNote>[59]中含有短链PEG和4，4’-二氨基二苯砜，对不同比例（x=1.0、0.8、0.6、0.4、0.2、0，x+y=1）结构的聚合物电解质进行测试，发现离子迁移数相差不大（0.9~0.92之间）。当x=1时，与PVDF－HFP共混的隔膜表现出最高的离子电导率，室温时为4×10-4Scm-1，抗拉强度最大为81.9MPa，伸长率为10.8%。以4，4’-二氟双苯磺酰亚胺和含有两个端羟基的聚乙二醇（PEG，Mw=200、400、600、800和1000）片段进行缩聚，再锂化得到AB交替共聚物dADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2018</Year><RecNum>186</RecNum><DisplayText><styleface="superscript">[52]</style></DisplayText><record><rec-number>186</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603673433">186</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,Yazhou</author><author>Tian,Yunsheng</author><author>Li,Zhong</author><author>Zhang,Nan</author><author>Zeng,Danli</author><author>Xu,Guodong</author><author>Zhang,Yunfeng</author><author>Sun,Yubao</author><author>Ke,Hanzhong</author><author>Cheng,Hansong</author></authors></contributors><titles><title>AnABalternatingdiblocksingleionconductingpolymerelectrolytemembraneforall-solid-statelithiummetalsecondarybatteries</title><secondary-title>JournalofMembraneScience</secondary-title></titles><periodical><full-title>JournalofMembraneScience</full-title></periodical><pages>181-189</pages><volume>566</volume><dates><year>2018</year></dates><isbn>0376-7388</isbn><urls></urls></record></Cite></EndNote>[52]。A为4，4’-二氟双苯磺酰亚胺，是提供锂离子的锂源，B为PEO短链，起着溶解和运输锂离子的作用。该自支撑固态电解质在[EO]/[Li+]为23.7:1时，玻璃化转变温度（Tg）最低，离子电导率最高，30℃时为6.61×10-6Scm-1，在100℃时达到2.24×10-4Scm-1。图1.6通过两种官能团间的反应制备的直链型单离子传导聚合物结构通过LSM聚合除了能够得到梳妆和直链型结构的单离子传导聚合物，还能通过多官能团反应制备超支化结构的聚合物。由于交联度高的聚合物通常不溶大多溶剂，所以超支化结构的单离子传导聚合物电解质通常采用原位聚合的方式直接与PVDF、PVDF-HFP等共混或者直接自成膜。通过功能锂盐单体对现有聚合物进行化学改性。将功能锂盐单体的阴离子通过官能团反应将其以化学键固定在现有高分子聚合物的主链上，得到梳妆的单离子传导聚合物如图1.7所示。一般有两种策略，（1）.先合成具有可进行接枝官能团的锂盐，再选择含有反应位点的高分子进行接枝（图1.7a、b和c结构）；（2）直接对现有的高分子进行化学改性（图1.7d和e结构）。孙玉宝教授课题组通过策略1合成了图1.7a、b和c结构的单离子传导聚合物电解质。a结构ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2018</Year><RecNum>92</RecNum><DisplayText><styleface="superscript">[53]</style></DisplayText><record><rec-number>92</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603627310">92</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,Yazhou</author><author>Xu,Guodong</author><author>Liu,Xupo</author><author>Pan,Qiyun</author><author>Zhang,Yunfeng</author><author>Zeng,Danli</author><author>Sun,Yubao</author><author>Ke,Hanzhong</author><author>Cheng,Hansong</author></authors></contributors><titles><title>Agelsingleionconductingpolymerelectrolyteenablesdurableandsafelithiumionbatteriesviagraftpolymerization</title><secondary-title>RSCadvances</secondary-title></titles><periodical><full-title>RSCAdvances</full-title></periodical><pages>39967-39975</pages><volume>8</volume><number>70</number><dates><year>2018</year></dates><urls></urls></record></Cite></EndNote>[53]由3-氯丙烷磺酰基三氟甲磺酰胺锂与聚乙烯醇（EOVH）通过亲和取代制备而成。bADDINEN.CITE<EndNote><Cite><Author>Li</Author><Year>2018</Year><RecNum>94</RecNum><DisplayText><styleface="superscript">[67]</style></DisplayText><record><rec-number>94</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603627310">94</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Li,Zhong</author><author>Lu,Wenhao</author><author>Zhang,Nan</author><author>Pan,Qiyun</author><author>Chen,Yazhou</author><author>Xu,Guodong</author><author>Zeng,Danli</author><author>Zhang,Yunfeng</author><author>Cai,Weiwei</author><author>Yang,Ming</author></authors></contributors><titles><title>Singleionconductinglithiumsulfurpolymerbatterieswithimprovedsafetyandstability</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><pages>14330-14338</pages><volume>6</volume><number>29</number><dates><year>2018</year></dates><urls></urls></record></Cite></EndNote>[67]和cADDINEN.CITE<EndNote><Cite><Author>Du</Author><Year>2019</Year><RecNum>458</RecNum><DisplayText><styleface="superscript">[68]</style></DisplayText><record><rec-number>458</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1616134569">458</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Du,Dandan</author><author>Hu,Xiaojing</author><author>Zeng,Danli</author><author>Zhang,Yunfeng</author><author>Sun,Yubao</author><author>Li,Jun</author><author>Cheng,Hansong</author></authors></contributors><titles><title>Water-InsolubleSide-Chain-GraftedSingleIonConductingPolymerElectrolyteforLong-TermStableLithiumMetalSecondaryBatteries</title><secondary-title>ACSAppliedEnergyMaterials</secondary-title></titles><periodical><full-title>ACSAppliedEnergyMaterials</full-title></periodical><pages>1128-1138</pages><volume>3</volume><number>1</number><dates><year>2019</year></dates><isbn>2574-0962</isbn><urls></urls></record></Cite></EndNote>[68]结构均是通过氨基和酸酐间的脱水聚合而成。与LSM聚合所得单离子传导聚合物相同，由于高接枝率而不能自成膜，需要与PVDF、PEO等共混成膜。从结构中可以出，b结构与a结构相比接枝率更高，且主链上含有极性更大的羧酸亚胺结构，促进了隔膜对溶剂的吸收（吸液率从122%上升到250%），离子电导率得到提高（5.7×10-5Scm-1升高到2.16×10-4Scm-1），离子迁移数也随之升高（从0.88到0.94）。然而，高接枝率的b结构含有高极性醋酸胺结构，造成其易溶于水，使离子交换过程变得耗时且不易处理。采用低极性，不溶于水的聚苯乙烯嵌段的聚合物聚苯乙烯马来酸酐为主链，得到不溶与水的结构c。聚苯乙烯部分使聚合物不溶于水，简化锂离子交换过程，同时马来酸酐接枝部分固定阴离子提供锂离子传导。结构c的离子迁移数为0.93，离子电导率达到1.6×10-4Scm-1，虽有少量下降，但干态隔膜的抗拉强度得到提高，从16MPa上升到18.7MPa。图1.7通过锂盐单体对工程高分子化学改性合成的单离子传导聚合物DevarajShanmukaraja教授和MichelArmanda教授等ADDINEN.CITE<EndNote><Cite><Author>Youcef</Author><Year>2020</Year><RecNum>207</RecNum><DisplayText><styleface="superscript">[69]</style></DisplayText><record><rec-number>207</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603674853">207</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Youcef,HichamBen</author><author>Orayech,Brahim</author><author>DelAmo,JuanMiguelLopez</author><author>Bonilla,Francisco</author><author>Shanmukaraj,Devaraj</author><author>Armand,Michel</author></authors></contributors><titles><title>Functionalizedcelluloseasquasisingle-ionconductorsinpolymerelectrolyteforall-solid–stateLi/NaandLiSbatteries</title><secondary-title>SolidStateIonics</secondary-title></titles><periodical><full-title>SolidStateIonics</full-title></periodical><pages>115168</pages><volume>345</volume><dates><year>2020</year></dates><isbn>0167-2738</isbn><urls></urls></record></Cite></EndNote>[69]将氟磺酰异氰酸酯通过氨基甲酸酯键连接到乙基纤维素上，合成了图1.7dADDINEN.CITE<EndNote><Cite><Author>Youcef</Author><Year>2020</Year><RecNum>207</RecNum><DisplayText><styleface="superscript">[69]</style></DisplayText><record><rec-number>207</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1603674853">207</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Youcef,HichamBen</author><author>Orayech,Brahim</author><author>DelAmo,JuanMiguelLopez</author><author>Bonilla,Francisco</author><author>Shanmukaraj,Devaraj</author><author>Armand,Michel</author></authors></contributors><titles><title>Functionalizedcelluloseasquasisingle-ionconductorsinpolymerelectrolyteforall-solid–stateLi/NaandLiSbatteries</title><secondary-title>SolidStateIonics</secondary-title></titles><periodical><full-title>SolidStateIonics</full-title></periodical><pages>115168</pages><volume>345</volume><dates><year>2020</year></dates><isbn>0167-2738</isbn><urls></urls></record></Cite></EndNote>[69]结构的聚合物。他们认为此类功能化纤维素基电解质可增加聚合物的刚性和刚度，来抑制锂枝晶刺穿隔膜。此聚合物与PEO共混制备固态电解质，测得其离子电导率在70℃时接近2.16×10-4Scm-1，锂离子迁移数达到0.9。徐生明教授ADDINEN.CITE<EndNote><Cite><Author>Zhen</Author><Year>2018</Year><RecNum>481</RecNum><DisplayText><styleface="superscript">[70]</style></DisplayText><record><rec-number>481</rec-number><foreign-keys><keyapp="EN"db-id="zrvpwprzbvffa2e52zsp00eutpsxzt5ra9w2"timestamp="1616137647">481</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhen,Li</author><author>Qiming,Yao</author><author>Qi,Zhang</author><author>Yangqiang,Zhao</author><author>Dangxun,Gao</author><author>Shuangshou,Li</author><author>Shengming,Xu</author></authors></contributors><titles><title>Creatingionicchannelsinsingle-ionconductingsolidpolymerelectrolytebymanipulatingphaseseparationstructure†</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><dates><year>2018</year><pub-dates><date>2018/11/23</date></pub-dates></dates><urls><related-urls><url>/10.1039/c8ta08967a</url></related-urls></urls><electronic-resource-num>10.1039/c8ta08967a</electronic-resource-num></record></Cite></EndNote>[70]等合成图1.7e结构的步骤如图1.8所示。首先使用浓硫酸将买到的工程高分子聚醚醚酮（PEEK）进行磺化得到SPEEK，接着用氯化亚砜将磺酸基团变成磺酰氯。最后，依据兴斯堡反应原理将三氟甲磺酰胺与磺酰氯基团反应得到图1.7e结构聚合物TFSISPEEK。再采用“刚柔并济”的思想，将TFSISPEEK分散在交联结构的聚乙二醇中制备固态电解质。测得其在80℃时，离子电导率约为10-4Scm-1，离子迁移数为0.9。图1.8结构图1.7e的合成流程图1.2.2基于有机-无机混合材料的单离子传导聚合物电解质无机和有机材料的结合在传统SPE中得到了很好的探索。例如，将无机纳米材料添加到聚合物基体中，以增加离子导电性并改善聚合物电解质的机械性能ADDINEN.CITEADDINEN.CITE.DATA[71-73]。该方法在制备高导电性单离子传导聚合物电解质方面得到很好的应用。在无机材料的表面，通过共价键连接能够提供锂离子的有机部分，