CN107759726B - 一种温度敏感型聚合物电解质及其制备方法和应用 - Google Patents
一种温度敏感型聚合物电解质及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种温度敏感型聚合物电解质及其制备方法和应用,所述温度敏感型聚合物电解质的制备方法如下:在剧烈搅拌条件下,将含有电解质的水相组分稳定分散于油相组分中形成乳浊液,然后在持续强搅拌和充惰性气体的条件下升温进行反相悬浮聚合反应即得所述温度敏感型聚合物电解质;所述水相组分和油相组分的体积比为0.1~1.0:1。本发明通过反相悬浮聚合法反应得到了一种温度敏感型聚合物电解质,该电解质绿色环保且能够可逆循环;将其应用于电化学储能器件中可有效解决一直阻碍高比能量密度和高功率储能器件商业化广泛应用的安全性问题。
Description
技术领域
本发明涉及电化学储能器件能源领域,尤其涉及一种温度敏感型聚合物电解质及其制备方法和应用。
背景技术
在互联网信息技术迅猛发展推动下,便携式各类电子产品如智能手机、平板电脑、笔记本电脑和数码相机等不断更新换代,随着生产技术和制造工艺的不断突破和改进,未来这些电子产品必将朝着更加微型化、轻质化、柔性化方向发展。与此同时,这些多实用功能特性便携式电子产品的能源输出核心——电化学储能器件也必将逐渐向着实现轻薄且柔性、高比能量、高比功率、绿色可再生、长循环寿命的目标方向继续研究与开发,也以便使其适用于更多的应用领域,满足高品质生活的应用需求,如电动汽车、混合染料汽车、脉冲电源设备、电站变流以及铁路系统等。
然而,电化学储能器件应用领域的快速扩展,尤其是在能量储存性能方面向更高比能量输出和更高比功率转化的能源动力发展,对储能器件提出了越来越高的技术挑战,特别值得关注的是储能器件的安全性。在日常生产和生活使用中,由于人为的不合理方式电化学储能器件难免会处在不安全的状态下,如过充电、过放电、短路、机械磨损、高温储存与运输。在这些人为形式的滥用条件下,电化学储能器件内部活泼电极和电解液物质之间容易继续发生复杂的化学放热反应以致在狭小器件腔体内温度升高,反过来又继续加速反应进行,迅速形成“雪崩”式的热失控,从而导致储能器件结构损坏,如电解液分解和金属电极熔化,甚至可能出现储能器件冒烟、着火、爆炸、乃至人员受伤等情况。据查阅资料,目前有关于储能器件引起的安全性事故报道仍屡见不鲜,如手机充电爆炸、电脑电池烧损和电动汽车着火,这也就是现有的大容量储能器件在安全性方面尚无法满足储能领域的应用要求的关键问题所在,从而严重阻碍了储能器件的商业化生产与应用。
因此,为了电化学储能器件适用于更广泛的应用领域,在不断追求更高比能量密度和高比功率输出的储能要求时,目前亟待解决的问题是发展新型的安全性保护技术,提高储能器件的使用安全性。目前,针对如何解决电化学储能器件的安全性问题,有不少研究学者分别从电极材料、电解质物质、器件结构与制造等不同方面着手探索与研究,同时也在一定程度上有效克服了储能器件的不安全性问题,使研制的新型电化学储能器件得以在不同能量密度需求领域广泛应用。但由于以往应用的解决方案常以降低电解质离子电导率或室温外电路电导率作为妥协,而且还存在一定的漏电现象和循环寿命短问题,储能器件未能做到绿色环保和快速可逆的安全使用。
随着技术与产业化的发展,研发一种既能达到绿色环保又能可逆循环的电解质,对于指导提高电化学储能器件的使用安全性,进一步继续开发轻薄且柔性、高比能量、高比功率、绿色可再生、长循环寿命的新型储能器件具有极大的现实意义。
发明内容
本发明的目的在于克服现有技术的不足,提供一种温度敏感型聚合物电解质。
本发明通过反相悬浮聚合法反应得到了一种温度敏感型聚合物电解质,该电解质绿色环保且能够可逆循环;将其应用于电化学储能器件中可有效解决一直阻碍高比能量密度和高功率储能器件商业化广泛应用的安全性问题。
本发明的另一目的在于提供上述温度敏感型聚合物电解质在电化学储能器件中的应用。
为实现上述目的,本发明采用如下技术方案:
一种温度敏感型聚合物电解质,所述温度敏感型聚合物电解质的制备方法如下:
在剧烈搅拌条件下,将含有电解质的水相组分稳定分散于油相组分中形成乳浊液,然后在持续强搅拌和充惰性气体的条件下升温进行反相悬浮聚合反应即得所述温度敏感型聚合物电解质;所述水相组分和油相组分的体积比为0.1~1.0:1;
其中,所述水相组分由如下质量百分比的组分组成:温敏聚合单体20~60%、共聚单体10~30%、交联剂5~10%、引发剂0.5~3%、电解质0~10%、亲水性溶剂50~80%;
所述油相组分由如下质量百分比的组分组成:10~50%分散剂、60~90%疏水性溶剂。
本发明通过将溶解有电解质的反应单体混合物通过搅拌分散、低温加热进行反相悬浮聚合反应制备得到一种温度敏感型聚合物电解质,所述电解质绿色环保且能够可逆循环;将其应用于电化学储能器件中可有效解决一直阻碍高比能量密度和高功率储能器件商业化广泛应用的安全性问题。本发明提供的制备方法反应条件温和、体系粘度低、反应热易扩散,易于推广。
本发明提供的温敏性聚合物电解质可直接填充于储能器件电极之间,用增塑剂溶剂使其充分浸润,最终组装成简单易行的“三明治”结构储能器件。当器件的环境和体系温度升高时,温敏性聚合物由于其内部结构疏水基团的缔合作用而发生体积相收缩,致使电极与电解质之间的接触性能变差和界面阻抗增大,甚至接触面直接脱离,从而电化学储能器件在此状态下停止继续工作,相当于自动断开电路起到自我保护的作用。在温度逐渐降低恢复至室温时,温敏性聚合物的体积相会随之发生膨胀,从而电极与电解质之间重新恢复接触,保持良好运作的预备状态。因此,本发明提供的温度敏感型聚合物电解质能在储能器件由于不慎使用甚至滥用的情况下发生热失控时及时起到一种绿色环保和可逆循环的智能型自我保护机制,克服了以往解决方案的低效性与不可逆性,极大有效地提高了电化学储能器件的安全性,为未来能在安全保障下继续提高器件储能性能提供了新的设计思路和技术引导。
针对于本发明所述的反相悬浮聚合制备温敏性聚合物电解质的实验步骤,将混合均匀的水相溶液加入油相溶液中,在持续强搅拌和充氮气的条件下,升高乳浊液体系温度进行热聚合反应。
优选的,所述的制备温敏性聚合物电解质的实验步骤中,水相须缓慢滴加入处于强烈搅拌和氮气氛围的油相中。
优选地,所述搅拌的速度为200~600r/min;所述惰性气体的流量为20~80mL/min。
优选地,所述反相悬浮聚合反应的反应温度为50~75℃,反应时间为3~8h。更为优选地,所述反应温度为68~75℃。
优选地,将含有电解质的水相组分滴加入油相组分中,在强烈搅拌和惰性气体氛围中先于30~50℃保持15~30min,然后再升温至反应温度。
优选地,将聚合获得的反应产物进行抽滤,并循环使用热有机溶剂充分清洗3~5次,然后置于60°C~80°C烘箱中,烘干时间为12~36h,最后研磨成粉末。
优选地,所述温敏聚合单体为带有不饱和双键的直链或环状伯胺类、仲胺类、叔胺类和酰胺类小分子化合物中的一种或几种。
优选地,所述温敏聚合单体为N-异丙基丙烯酰胺、N,N-二甲基丙烯酰胺、N-丙基丙烯酰胺、N-环丙基丙烯酰胺、N-乙烯基吡咯烷酮、N,N-二乙基丙烯酰胺、N-甲基丙烯酰胺、N-(N,-乙基脲)丙基甲基丙烯酰胺或N-(N,-乙基脲)异丙基甲基丙烯酰胺的一种或几种。
更为优选地,所述温敏聚合单体为N-异丙基丙烯酰胺、N,N-二甲基丙烯酰胺或N-乙烯基吡咯烷酮中的一种或几种。
优选地,所述共聚单体为丙烯酸类、丙烯酸酯类、丙烯酰胺类或带有单不饱和双键的低分子量聚乙二醇丙烯酸酯类的一种或几种。
更为优选地,所述共聚单体为丙烯酸、甲基丙烯酸、丙烯酸-2-羟丙酯、丙烯酸羟丙酯、丙烯酰胺、丙烯腈、甲基丙烯酰胺、聚乙二醇丙烯酸酯、聚乙二醇甲基丙烯酸酯、丙烯酸乙二酯或丙烯酸羟异丙酯中的一种或几种。
最为优选地,所述共聚单体为丙烯酸、丙烯酰胺、丙烯酸-2-羟丙酯、丙烯腈的一种或多种。
优选地,所述电解质为偏碱性、中性、偏酸性无机电解质或有机离子液体中的一种或几种。
更为优选地,所述电解质为LiNO3、LiClO4、NaCl、KCl、NaNO3、NH4Cl、H2SO4、H3PO4、FeSO4、ZnSO4、Na2S2O6、[Co(NH3)6]Cl3、季铵盐、季鏻盐、咪唑盐、吡咯盐等化合物的一种或几种。
优选地,所述电解质在水相组成中的摩尔浓度为0~6.0mol/L。
优选地,所述亲水性溶剂为含有单或多个羟基、羧基、氨基、酰胺基、酮醛羰基亲水性基团化合物的一种或几种;所述疏水性溶剂为烃类、醚类或酯类中的一种或几种。
更为优选地,所述亲水性溶剂为去离子水、甲醇、乙醇、丙酮、乙酸、丙醇、异丙醇或N,N-二甲基甲酰胺中的一种或几种。所述疏水性溶剂为环己烷、正己烷、苯、甲苯、三氯甲烷、乙酸乙酯、庚烷、辛烷的一种或多种。
优选地,所述交联剂为不饱和双官能团化合物如双丙烯酰胺和双丙烯酸聚乙二醇类,或不饱和多官能团化合物如三烯蔗糖类或三丙烯酸类中的一种或几种。
更为优选地,所述交联剂为N,N-亚甲二丙烯酰胺、季戊四醇三丙烯酸酯、蔗糖三烯丙基醚、季戊四醇三烯丙基醚或聚乙二醇二丙烯酸酯水溶性交联剂中的一种或几种。
优选地,所述引发剂为酰类过氧化物、酮类过氧化物、过硫酸类、偶氮类或氧化还原类的一种或多种。
更为优选地,所述引发剂为过硫酸钾、过硫酸铵或偶氮二异丁腈中的一种或几种。
优选地,所述分散剂为无机分散剂类如硅酸盐、或有机小分子分散剂类如表面活性剂、或高分子分散剂类如聚二甲基硅氧烷PEG-7磷酸酯中的一种或几种。
更为优选地,所述分散剂为高分子分散剂类如失水山梨醇脂肪酸酯系列Span 20、Span 40、Span 60、Span 80,或聚氧乙烯失水山梨醇脂肪酸酯系列Tween 20、Tween 40、Tween 60、Tween 80,或聚二甲基硅氧烷PEG-7磷酸酯中的一种或几种。
本发明同时保护上述温度敏感型聚合物电解质在电化学储能器件中的应用。
本发明提供的温度敏感型聚合物电解质,在组装“三明治”结构的储能器件过程中可直接填充于两电极板之间,滴加增塑剂溶剂使其充分浸润,利用温敏性聚合物在体系和环境的温度升高时,其内部结构疏水基团作用增强而导致本体体积发生收缩,从而使电极与聚合物电解质界面接触阻抗增大甚至断开,实现了储能器件在高温环境中智能停止工作的目的,避免了器件在高温条件下工作容易产生热失控而导致的安全隐患,可见大大提高了电化学储能器件的安全性能和实用效果。
与现有技术相比,本发明具有如下有益效果:
本发明提供的的温度敏感型聚合物电解质是通过反相悬浮聚合方法反应制备而成的,反应具备条件温和、体系粘度低、反应热易扩散等优点。本发明制备得到的温度敏感型聚合物电解质绿色环保且能够可逆循环,可应用于电化学储能器件中,解决一直阻碍高比能量密度和高功率储能器件商业化广泛应用的安全性问题。为下一代追求更高比能量、更高比功率的电化学储能器件提供了安全性保障和安全技术指导。
附图说明
图1为本发明提供的热缩型水凝胶体积相转变过程的示意图。
图2为本发明实施例5提供的超级电容器组装实物图。
图3为本发明实施例5中测试由复合碱性电解质的温敏性P(NVP-co-HPA)共聚物组装而成的超级电容器的电化学阻抗谱。
具体实施方式
基于本发明提出一种温度敏感型聚合物电解质以解决电化学储能器件应用安全性问题的设计目的,而且为了进一步突显本发明设计思路和技术方案的创新性和优越性,下面将对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是说明本发明设计旨意的一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的氛围。在实施例的实验操作及测试过程中,除非特别说明,本发明实施例所采用的试剂、方法和设备为本技术领域的常规试剂、方法和设备。
实施例1 温敏型PAH-g-PNIPAAm共聚物的制备
在50mL甲醇溶液中,加入单体10gN-异丙基丙烯酰胺与150mg 4,4,-偶氮双(4-氰基戊酸),在66°C和氮气保护下反应3h,再倒入热水中沉淀,过滤洗涤干燥,获得PNIPAAm-COOH产物。取适量干燥处理好的PNIPAAm-COOH配制成5%的水溶液,在低温下与按一定投料比的1-乙基-3-(二甲基胺丙基)碳化二亚胺反应2天,随后加入1.0g聚烯丙基胺(PAH)继续反应2天,最终制备得PAH-g-PNIPAAm共聚物。
为了研究PAH-g-PNIPAAm共聚物在水溶液中的温敏相变行为,采用动态光散射测试其水合半径(Rh)随温度的变化(浓度为0.1mg/mL)。在低于LCST如30°C,聚合物水合半径7.2nm,而在高于LCST如35°C时,溶液浑浊发生相分离,水合半径缩小为4.6nm。而且当温度在LCST附近范围改变时,可以实现完全可逆的收缩-溶胀过程。
实施例2 温敏型P(NIPAM-co-NVP)水凝胶的制备
准确称取单体0.9g N-异丙基丙烯酰胺和0.1g乙烯基吡咯烷酮、0.02g过硫酸铵、0.05g N,N-亚甲基双丙烯酰胺,溶解于10mL DMSO溶剂中,倒入管型反应器内,采用自由基热聚合的方法进行聚合反应。初始产物用蒸馏水浸泡3d去除未反应产物和线型低聚物,再进行切块,真空干燥30h,温度为60°C。
为了研究共聚物的温敏特性,对实验获得的干胶进行测试在不同温度的蒸馏水中的饱和溶胀比。在10°C,共聚物水凝胶的溶胀比达到31.1g/g,而随着温度的升高,在50°C,水凝胶的溶胀比缩小至5g/g,而且具有可逆的收缩溶胀特点。可见,该共聚物在温度升高时,具有明显的溶胀比变化。
实施例3 温敏型聚N-乙烯基已内酰胺的制备
称取N-乙烯基已内酰胺10.0g,偶氮二异丁腈0.157g溶解于70mL二氧六环中,常温通氮气搅拌30min。将反应转入油浴锅中,升温至68°C,继续通氮气反应8h。悬蒸除去二氧六环,加入正己烷进行沉淀处理,抽滤,真空干燥得到聚N-乙烯基已内酰胺。
为了观察聚合物的温敏性特征,将聚N-乙烯基已内酰胺配制成1.0mg/mL的水溶液,并置于烘箱中,逐渐升高腔内温度。可以很明显观察到,聚合物溶液由初始的透明状态,慢慢地变为浑浊乳液,相转变温度约为58°C。由于温度升高,分子间氢键受到破坏,促使疏水缔合作用增强,发生聚集收缩相转变。
实施例4 温敏型P(NVP-co-HPA)共聚物电解质的制备
水相准备:称取0.195g交联剂N,N-亚甲基双丙烯酸酯、0.021g引发剂偶氮二异丁腈,并量取2.5mL浓度为0.1mol/L的电解质,用去离子水作为水相溶剂,混合搅拌、超声,进行充分溶解,再缓慢滴加2.5mL N-乙烯基吡咯烷酮(NVP)和1.25mL 丙烯酸-2-羟丙酯(HPA),配制成稳定均匀的水相溶液。
油相准备:在250mL三颈烧瓶中加入一定量正己烷与环己烷的配比为1:1的混合油相溶剂及0.14g分散剂Span 60,机械搅拌,加热至50°C左右,使其预先溶解配制成油相溶液。
反相悬浮聚合:以水相油相溶液体积比为1:4的配比量,将水相溶液加入到油相溶液中,通入N2除氧,搅拌转速为约300r/min,持续搅拌分散30min,接着将温度升高至70°C反应5h,冷却至室温,真空抽滤,热甲醇反复洗涤至少三次,烘干。
应用例1温敏型P(NVP-co-HPA)共聚物电解质在超级电容器中的应用
图1为本发明提供的热缩型水凝胶体积相转变过程的示意图。在LCST以下,由于溶剂化作用,水凝胶的分子链网络之间形成氢键和范德华力的相互作用,以致高分子呈现出伸展的线团结构。而随着温度升高,部分分子间的氢键被破坏,大分子链疏水部分的溶剂化层也随之破坏,体系的熵增加,疏水基团的缔合作用增强,水分子从溶剂化层排出表现为相变,同时高分子链收缩成紧密的粒状结构。
为了进一步研究该温敏性聚合物材料在电化学储能器件中的应用性,在反相悬浮聚合反应体系的水相组成中加入0.1mol/L KOH溶液,从而获得复合碱性KOH的温敏性P(NVP-co-HPA)共聚物电解质。
图2为本应用例提供的超级电容器组装实物图。活性炭电极的制作过程:在加入质量比为85:10:5的活性炭、乙炔黑和PTFE乳液的玛瑙研钵中,滴加适量的乙醇充分搅拌30min,然后将其滚压成薄片并切割成1.0cm×1.0cm规整形状,再与泡沫镍在10MPa的压力下一起压制成活性炭电极。根据图2的超级电容器组装实物图所示,选取两个活性物质质量相等的活性炭电极浸泡于0.1mol/L KOH溶液中15min,然后将厚度约为1.0mm且中间挖空1.0cm×1.0cm方格的隔膜放置于两活性炭电极之间,在隔膜的挖空方格中填充聚合物电解质,滴加增塑剂溶剂使其浸润,将纽扣电池元件进行封装,再施加5MPa的压力压制密封。
密封好的超级电容器放置3h之后,分别测试其在25°C和80°C的环境氛围中的电化学阻抗,此过程升温与降温之间都是快速进行的,30s以内。测试结果见图3。图3为本应用例中测试由复合碱性电解质的温敏性P(NVP-co-HPA)共聚物组装而成的超级电容器的电化学阻抗谱。从局部放大的小坐标中可以读出,本发明组装的碱性电解质超级电容器在室温25℃下,其电解质与电极之间的界面阻抗约为1.5Ω/cm2。而在快速升温至80℃时,恒温迅速测试其阻抗,从大坐标图中可以读取,界面阻抗为500Ω/cm2,可见,温敏性聚合物电解质在升高温度时,发生明显的微观收缩相分离,以致电解质与电极之间的界面脱离,接触破坏,以致阻抗快速增大。
以此同样,水相组成中加入0.1mol/L H2SO4溶液,从而获得复合酸性H2SO4的温敏性P(NVP-co-HPA)共聚物电解质。将该复合酸性H2SO4的P(NVP-co-HPA)共聚物电解质,应用于超级电容器中测试。电容器的组装具体过程同上述描述一致。最终获得酸性条件下超级电容器的电化学阻抗谱,在25°C时界面阻抗极小,只有0.2Ω/cm2,而在温度升至80°C时,界面阻抗已经增大至350kΩ/cm2。可见,该聚合物电解质在酸性环境下温敏效果最为显著,收缩率更大,以致电解质与电极之间完全断开,起到自我保护作用。
同理,继续再在水相组成中加入0.1mol/L NaCl溶液,从而获得复合中性NaCl的温敏性P(NVP-co-HPA)共聚物电解质。同样,直接将此复合中性盐NaCl的温敏性P(NVP-co-HPA)共聚物电解质,应用于超级电容器中测试。电容器的组装具体过程同上述碱性情况组装的描述一致。最终获得中性条件下超级电容器的电化学阻抗谱,在25°C时界面阻抗约为1.0Ω/cm2,在温度升至80°C时,界面阻抗增大至10Ω/cm2。可见,该聚合物电解质在中性环境下温敏效果微弱,相体积收缩率小。
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (2)
1.一种温度敏感型聚合物电解质,其特征在于,所述温度敏感型聚合物电解质的制备方法如下:
水相准备:称取0.195g交联剂N,N-亚甲二丙烯酰胺、0.021g引发剂偶氮二异丁腈,并量取2.5mL浓度为0.1mol/L的电解质,用去离子水作为水相溶剂,混合搅拌、超声,进行充分溶解,再缓慢滴加2.5mL N-乙烯基吡咯烷酮和1.25mL丙烯酸-2-羟丙酯,配制成稳定均匀的水相溶液;
油相准备:在250mL三颈烧瓶中加入一定量正己烷与环己烷的配比为1:1的混合油相溶剂及0.14g分散剂Span 60,机械搅拌,加热至50℃左右,使其预先溶解配制成油相溶液;反相悬浮聚合:以水相油相溶液体积比为1:4的配比量,将水相溶液加入到油相溶液中,通入N2除氧,搅拌转速为约300r/min,持续搅拌分散30min,接着将温度升高至70℃反应5h,冷却至室温,真空抽滤,热甲醇反复洗涤至少三次,烘干。
2.权利要求1所述温度敏感型聚合物电解质在电化学储能器件中的应用。
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