CN110938193A - 一种d-a-d结构聚合物膜pefe及其制备方法和应用 - Google Patents
一种d-a-d结构聚合物膜pefe及其制备方法和应用 Download PDFInfo
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Abstract
一种D‑A‑D结构聚合物膜PEFE,按照如下方法进行制备:(1)将2,7‑二溴‑9芴酮与预先制得的三丁基(2,3‑二氢[3,4‑b][1,4]二恶英‑5‑基锡烷及双三苯基磷二氯化钯按比例混合,在氮气环境下溶于有机溶剂中,在回流温度下反应,得到反应混合液,萃取后,过硅胶柱分离得单体EFE;(2)将D‑A‑D单体EFE和电解质溶于支持电解溶剂中得到电解液,将电解液加入到电解池三电极体系中,与电化学工作站相连,在聚合电压下进行电化学CV聚合反应,用有机溶剂色谱级混合溶液清洗薄膜,干燥。以及提供D‑A‑D结构聚合物膜PEFE的制备方法和应用。本发明既有明显颜色变化,还有较高的比容量及稳定性。
Description
技术领域
本发明涉及一种具有高比容量及高稳定性的聚合物膜及其制备方法和应用,可应用于在电致变色型超级电容器方向。
背景技术
近年来,随着电子设备便携化的发展,可以显示工作状态的储能器件也变得越来越重要。电致变色是通过改变工作电压的大小,材料发生氧化还原反应致使其对光的透射或者反射产生可逆变化,在外观上则反映出颜色的可逆变化。通过颜色变化来显示储能器件的储能状态是一种较为可行的办法,但制备能够满足该需求的大比容量、高对比度以及稳定性能好的材料成为一大问题。
在超级电容器中,与金属氧化物材料相比,导电聚合物材料具有更加相对合适的表面形貌、更好的柔韧性以及低成本等优点。D-A结构是一种有效调节分子能带的一种技术手段,可以降低聚合物的氧化电位,拥有更高的稳定性。迄今为止,也有多种D-A结构的物质在文献中报导过,如苯并噻二唑、喹喔啉及其衍生物等。D-A-D结构不但拥有D-A的优势,而且由于其内消旋作用,有更低的能带隙,还有电子给受体双重基团性质。因此我们设计合成了D-A类似的D-A-D结构的EDOT-芴酮-EDOT,在合适的电压条件下进行电聚合,制备聚合物薄膜。在满足电致变色的应用条件下,同时兼具超级电容器的较高的比容量的特点。
发明内容
为解决在超级电容器储能过程中如何显示工作状态的问题,本发明的目的是提供一种在其工作电压范围下有明显颜色变化的超级电容器聚合物膜电极材料的D-A-D结构聚合物膜PEFE及其制备方法和应用。
为实现上述目的,本发明采用如下技术方案:
一种D-A-D结构聚合物膜PEFE,按照如下方法进行制备:
(1)将式I中的2,7-二溴-9芴酮与预先制得的三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基锡烷及双三苯基磷二氯化钯按(1:1~2:0.002~0.01)比例混合,在氮气环境下溶于有机溶剂A中,在回流温度下反应24~36小时,得到反应混合液B,用去离子水和二氯甲烷萃取后,过硅胶柱分离可得单体EFE,如式II所示;
(2)将步骤(1)所得式2所示的D-A-D单体EFE和电解质溶于支持电解溶剂中得到电解液,单体EFE的浓度为0.1~10mmol/L,支持电解质的初始终浓度为0.01~1mol/L电解溶剂.将电解液加入到电解池三电极体系中,与电化学工作站相连,在聚合电压-0.5~1.4Vvs Ag/AgCl下,聚合圈数在5~20圈下,进行电化学CV聚合反应,得到D-A-D结构聚合物膜PEFE,如式III所示;用有机溶剂色谱级二氯甲烷:乙腈体积比(0.1~10:1)的混合溶液清洗薄膜,干燥即可;
进一步,所述步骤(2)中,电解溶剂为色谱级二氯甲烷:乙腈体积比(0.1~10:1)的混合溶液。
一种D-A-D结构聚合物膜PEFE制备方法,包括以下步骤:
(1)将式I中的2,7-二溴-9芴酮与预先制得的三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基锡烷及双三苯基磷二氯化钯按(1:1~2:0.002~0.01)比例混合,在氮气环境下溶于有机溶剂A中,在回流温度下反应24~36小时,得到反应混合液B,用去离子水和二氯甲烷萃取后,过硅胶柱分离可得单体EFE,如式II所示;
(2)将步骤(1)所得式2所示的D-A-D单体EFE和电解质溶于支持电解溶剂中得到电解液,单体EFE的浓度为0.1~10mmol/L,支持电解质的初始终浓度为0.01~1mol/L电解溶剂.将电解液加入到电解池三电极体系中,与电化学工作站相连,在聚合电压-0.5~1.4Vvs Ag/AgCl下,聚合圈数在5~20圈下,进行电化学CV聚合反应,得到D-A-D结构聚合物膜PEFE,如式III所示;用有机溶剂色谱级二氯甲烷:乙腈体积比(0.1~10:1)的混合溶液清洗薄膜,干燥即可;
进一步,所述步骤(2)中,电解溶剂为色谱级二氯甲烷:乙腈体积比(0.1~10:1)的混合溶液。
一种D-A-D结构聚合物膜PEFE,所述D-A-D结构聚合物膜PEFE用于电致变色型超级电容器。
本发明的有益效果为:所述的聚合物薄膜PEFE,通过扫描电镜(SEM)对其进行表征,证明通过电化学聚合的方式形成形貌均匀的聚合物薄膜材料;通过使用电化学工作站和紫外-可见分光光度计对其电化学性能及光谱电化学测试进行分析,可以看出该聚合物既有明显颜色变化,还有较高的比容量及稳定性。
附图说明
图1是D-A-D结构单体EFE在扫速100mV下循环伏安聚合曲线图。
图2是D-A-D结构聚合物PEFE膜的SEM图像。
图3是D-A-D结构聚合物PEFE薄膜在电流密度0.1mA/cm2、0.2mA/cm2、0.5mA/cm2下恒电流充放电曲线图。
图4是PEFE聚合物膜在电流密度为0.5mA/cm2时循环500圈的循环稳定性图。
图5是PEFE聚合物膜在不同不同光谱下的对比度及响应时间图。
具体实施方式
下面通过具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
实施例1
参照图1~图5,一种D-A-D结构聚合物膜PEFE,按照如下方法进行制备:
(1)单体EFE的合成
对3,4-乙烯二氧噻吩(EDOT)锡化,将EDOT(6mmol,0.852g)溶解在干燥的四氢呋喃(40mL)中,在-78℃的N2氛围下,缓慢滴加正丁基锂(6.6mmol,4.125mL,1.6M),缓慢升温至-40℃,搅拌1h,再降温至-78℃,缓慢滴加三丁基氯化锡(7.2mmol,2.347g),并在室温下搅拌8h,过中性氧化铝柱过滤去除固体杂质,得到产物三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷,将2,7-二溴-9芴酮(3mmol,1.014g),三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷(6mmol,2.593g)及双三苯基磷二氯化钯(0.025mmol,0.01755g)在N2氛围下溶解于50ml干燥甲苯中,加热至110℃下保持回流24小时。体系冷却后,用去离子水和二氯甲烷萃取,并加入无水硫酸镁搅拌干燥,之后旋转蒸发掉溶剂拌样,选择流动相(PE:DCM=1:2)层析过柱。最终得到目标产物(EWE)。1H NMR(500MHz,CDCl3)δ8.07(d,J=1.6Hz,1H),7.82(dd,J=7.9,1.7Hz,1H),7.78(d,J=1.8Hz,1H),7.61(dd,J=7.9,1.8Hz,1H),7.49(d,J=7.9Hz,1H),7.39(d,J=7.9Hz,1H),6.36(s,1H),4.38-4.34(m,2H),4.30-4.25(m,3H).MALDI-TOF-MS(M)(m/z):461.1[M+H]+.
(2)聚合物(PEFE)材料的制备
将EFE单体(0.01mmol,0.0048g),四丁基六氟磷酸铵(TBAPF6)(1mmol,0.387g)溶解于9ml色谱级二氯甲烷与1ml色谱级乙腈的混合溶液中,配制成单体浓度0.001mol/L、电解质浓度0.1mol/L的电解液。在室温下,以氧化铟锡导电玻璃(ITO)作为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极,采用循环伏安阳极氧化法制备聚合物薄膜。设定初始电压为-0.5V、终止电压1.4V、扫速100mV/s,聚合圈数设定为20圈(聚合膜厚度为450nm)。观察EFE聚合曲线,可知氧化还原峰对(1.00V/0.62V)。用二氯甲烷与乙腈(体积比9:1)的混和溶液冲洗,洗掉聚合物薄膜上的低聚物。其中,PEWE聚集态易团聚形成较为致密的整体,但该聚合物薄膜形成较小的团聚体,不易清洗干净,可能对其电化学性能产生一定的影响。
(3)聚合物(PEFE)电化学性能测试
将四丁基六氟磷酸铵(TBAPF6)(1mmol,0.387g)溶解于9ml色谱级二氯甲烷与1ml色谱级乙腈混合溶液中,配制成电解质浓度0.1mol/L的电解液。选择三电极体系,涂有聚合物(PEFE)薄膜的氧化铟锡(ITO)导电玻璃为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极。在室温下,测试其循环伏安曲线,即在0~1.4V电压范围下,以100mV/s的扫速循环伏安扫描一圈。观察PEFE聚合物曲线,可知氧化还原峰对(1.00V/0.62V)。聚合膜均具有两种颜色显示,其中PEWE在中性态下显日晒色,氧化态显灰紫色。依旧在此电解液下进行恒电流充放电测试,在0.1mA/cm2的电流密度下,有较大的比容量及较好的循环稳定性。在0.1mol/L的TBAPF6的二氯甲烷(CH2Cl2)和乙腈(ACN)(v/v=9/1)混合溶液(空白溶液)中,对各聚合膜进行全波段(UV–vis–NIR)吸光度的测试,改变电压,并测试不同电压下聚合物掺杂态吸光度的变化。共轭聚合膜PEWE在中性态下的最大吸收峰在370nm,该波长下的吸收峰即为聚合物的本征吸收峰;在可见光谱区,其最大吸收峰为450nm,此时聚合物薄膜呈现日晒色,随着电压的增加,该吸收峰逐渐减弱直至消失;在500-850nm吸收带的吸收强度逐渐增加,表明增加电压使该聚合链的掺杂逐渐加深,形成单极子态,且发生电子跃迁的单极子态逐步增加,聚合膜慢慢变为灰紫色。除此之外,近红外区出现新的吸收带且随着电压的升高逐渐增强,表明了该材料双极子态的形成及其电子跃迁的变化。
实施例2
一种D-A-D结构聚合物膜PEFE,按照如下方法进行制备:
(1)单体EFE的合成
对3,4-乙烯二氧噻吩(EDOT)锡化,将EDOT(6mmol,0.852g)溶解在干燥的四氢呋喃(40mL)中,在-78℃的N2氛围下,缓慢滴加正丁基锂(6.6mmol,4.125mL,1.6M),缓慢升温至-40℃,搅拌1h,再降温至-78℃,缓慢滴加三丁基氯化锡(7.2mmol,2.347g),并在室温下搅拌8h,过中性氧化铝柱过滤去除固体杂质,得到产物三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷。将2,7-二溴-9芴酮(3mmol,1.014g),三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷(6mmol,2.593g)及双三苯基磷二氯化钯(0.025mmol,0.01755g)在N2氛围下溶解于50ml干燥甲苯中,加热至110℃下保持回流36小时。体系冷却后,用去离子水和二氯甲烷萃取,并加入无水硫酸镁搅拌干燥,之后旋转蒸发掉溶剂拌样,选择流动相(PE:DCM=1:2)层析过柱。最终得到目标产物(EWE)。1H NMR(500MHz,CDCl3)δ8.07(d,J=1.6Hz,1H),7.82(dd,J=7.9,1.7Hz,1H),7.78(d,J=1.8Hz,1H),7.61(dd,J=7.9,1.8Hz,1H),7.49(d,J=7.9Hz,1H),7.39(d,J=7.9Hz,1H),6.36(s,1H),4.38-4.34(m,2H),4.30-4.25(m,3H).MALDI-TOF-MS(M)(m/z):461.1[M+H]+.
(2)聚合物(PEFE)材料的制备
将EFE单体(0.01mmol,0.0048g),四丁基六氟磷酸铵(TBAPF6)(1mmol,0.387g)溶解于9ml色谱级二氯甲烷与1ml色谱级乙腈的混合溶液中,配制成单体浓度0.001mol/L、电解质浓度0.1mol/L的电解液。在室温下,以氧化铟锡导电玻璃(ITO)作为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极,采用循环伏安阳极氧化法制备聚合物薄膜。设定初始电压为-0.5V、终止电压1.4V、扫速100mV/s,聚合圈数设定为20圈(聚合膜厚度为450nm)。观察EFE聚合曲线,可知氧化还原峰对(1.00V/0.62V)。用二氯甲烷与乙腈(体积比9:1)的混和溶液冲洗,洗掉聚合物薄膜上的低聚物。其中,PEWE聚集态易团聚形成较为致密的整体,但该聚合物薄膜形成较小的团聚体,不易清洗干净,可能对其电化学性能产生一定的影响。
(3)聚合物(PEFE)电化学性能测试
将四丁基六氟磷酸铵(TBAPF6)(1mmol,0.387g)溶解于9ml色谱级二氯甲烷与1ml色谱级乙腈混合溶液中,配制成电解质浓度0.1mol/L的电解液。选择三电极体系,涂有聚合物(PEFE)薄膜的氧化铟锡(ITO)导电玻璃为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极。在室温下,测试其循环伏安曲线,即在0~1.4V电压范围下,以100mV/s的扫速循环伏安扫描一圈。观察PEFE聚合物曲线,可知氧化还原峰对(1.00V/0.62V)。聚合膜均具有两种颜色显示,其中PEWE在中性态下显日晒色,氧化态显灰紫色。依旧在此电解液下进行恒电流充放电测试,在0.1mA/cm2的电流密度下,有较大的比容量及较好的循环稳定性。在0.1mol/L的TBAPF6的二氯甲烷(CH2Cl2)和乙腈(ACN)(v/v=9/1)混合溶液(空白溶液)中,对各聚合膜进行全波段(UV–vis–NIR)吸光度的测试,改变电压,并测试不同电压下聚合物掺杂态吸光度的变化。共轭聚合膜PEWE在中性态下的最大吸收峰在370nm,该波长下的吸收峰即为聚合物的本征吸收峰;在可见光谱区,其最大吸收峰为450nm,此时聚合物薄膜呈现日晒色,随着电压的增加,该吸收峰逐渐减弱直至消失;在500-850nm吸收带的吸收强度逐渐增加,表明增加电压使该聚合链的掺杂逐渐加深,形成单极子态,且发生电子跃迁的单极子态逐步增加,聚合膜慢慢变为灰紫色。除此之外,近红外区出现新的吸收带且随着电压的升高逐渐增强,表明了该材料双极子态的形成及其电子跃迁的变化。
实施例3
一种D-A-D结构聚合物膜PEFE,按照如下方法进行制备:
(1)单体EFE的合成
对3,4-乙烯二氧噻吩(EDOT)锡化,将EDOT(6mmol,0.852g)溶解在干燥的四氢呋喃(40mL)中,在-78℃的N2氛围下,缓慢滴加正丁基锂(6.6mmol,4.125mL,1.6M),缓慢升温至-40℃,搅拌1h,再降温至-78℃,缓慢滴加三丁基氯化锡(7.2mmol,2.347g),并在室温下搅拌8h,过中性氧化铝柱过滤去除固体杂质,得到产物三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷。将2,7-二溴-9芴酮(3mmol,1.014g),三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷(6mmol,2.593g)及双三苯基磷二氯化钯(0.025mmol,0.01755g)在N2氛围下溶解于50ml干燥甲苯中,加热至110℃下保持回流36小时。体系冷却后,用去离子水和二氯甲烷萃取,并加入无水硫酸镁搅拌干燥,之后旋转蒸发掉溶剂拌样,选择流动相(PE:DCM=1:2)层析过柱。最终得到目标产物(EWE)。1H NMR(500MHz,CDCl3)δ8.07(d,J=1.6Hz,1H),7.82(dd,J=7.9,1.7Hz,1H),7.78(d,J=1.8Hz,1H),7.61(dd,J=7.9,1.8Hz,1H),7.49(d,J=7.9Hz,1H),7.39(d,J=7.9Hz,1H),6.36(s,1H),4.38-4.34(m,2H),4.30-4.25(m,3H).MALDI-TOF-MS(M)(m/z):461.1[M+H]+.
(2)聚合物(PEFE)材料的制备
将EFE单体(0.01mmol,0.0048g),六氟磷酸锂(LiPF6)(1mmol,0.387g)溶解于9ml色谱级二氯甲烷与1ml色谱级乙腈的混合溶液中,配制成单体浓度0.001mol/L、电解质浓度0.1mol/L的电解液。在室温下,以氧化铟锡导电玻璃(ITO)作为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极,采用循环伏安阳极氧化法制备聚合物薄膜。设定初始电压为-0.5V、终止电压1.4V、扫速100mV/s,聚合圈数设定为20圈(聚合膜厚度为450nm)。观察EFE聚合曲线,可知氧化还原峰对(1.00V/0.62V)。用二氯甲烷与乙腈(体积比9:1)的混和溶液冲洗,洗掉聚合物薄膜上的低聚物。其中,PEWE聚集态易团聚形成较为致密的整体,但该聚合物薄膜形成较小的团聚体,不易清洗干净,可能对其电化学性能产生一定的影响。
(3)聚合物(PEFE)电化学性能测试
将六氟磷酸锂(LiPF6)(1mmol,0.387g)溶解于9ml色谱级二氯甲烷与1ml色谱级乙腈混合溶液中,配制成电解质浓度0.1mol/L的电解液。选择三电极体系,涂有聚合物(PEFE)薄膜的氧化铟锡(ITO)导电玻璃为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极。在室温下,测试其循环伏安曲线,即在0~1.4V电压范围下,以100mV/s的扫速循环伏安扫描一圈。观察PEFE聚合物曲线,可知氧化还原峰对(1.00V/0.62V)。聚合膜均具有两种颜色显示,其中PEWE在中性态下显日晒色,氧化态显灰紫色。依旧在此电解液下进行恒电流充放电测试,在0.1mA/cm2的电流密度下,有较大的比容量及较好的循环稳定性。在0.1mol/L的TBAPF6的二氯甲烷(CH2Cl2)和乙腈(ACN)(v/v=9/1)混合溶液(空白溶液)中,对各聚合膜进行全波段(UV–vis–NIR)吸光度的测试,改变电压,并测试不同电压下聚合物掺杂态吸光度的变化。共轭聚合膜PEWE在中性态下的最大吸收峰在370nm,该波长下的吸收峰即为聚合物的本征吸收峰;在可见光谱区,其最大吸收峰为450nm,此时聚合物薄膜呈现日晒色,随着电压的增加,该吸收峰逐渐减弱直至消失;在500-850nm吸收带的吸收强度逐渐增加,表明增加电压使该聚合链的掺杂逐渐加深,形成单极子态,且发生电子跃迁的单极子态逐步增加,聚合膜慢慢变为灰紫色。除此之外,近红外区出现新的吸收带且随着电压的升高逐渐增强,表明了该材料双极子态的形成及其电子跃迁的变化。
实施例4
一种D-A-D结构聚合物膜PEFE,按照如下方法进行制备:
(1)单体EFE的合成
对3,4-乙烯二氧噻吩(EDOT)锡化,将EDOT(6mmol,0.852g)溶解在干燥的四氢呋喃(40mL)中,在-78℃的N2氛围下,缓慢滴加正丁基锂(6.6mmol,4.125mL,1.6M),缓慢升温至-40℃,搅拌1h,再降温至-78℃,缓慢滴加三丁基氯化锡(7.2mmol,2.347g),并在室温下搅拌8h,过中性氧化铝柱过滤去除固体杂质,得到产物三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷,将2,7-二溴-9芴酮(3mmol,1.014g),三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷(6mmol,2.593g)及双三苯基磷二氯化钯(0.025mmol,0.01755g)在N2氛围下溶解于50ml干燥甲苯中,加热至110℃下保持回流24小时。体系冷却后,用去离子水和二氯甲烷萃取,并加入无水硫酸镁搅拌干燥,之后旋转蒸发掉溶剂拌样,选择流动相(PE:DCM=1:2)层析过柱。最终得到目标产物(EWE)。1H NMR(500MHz,CDCl3)δ8.07(d,J=1.6Hz,1H),7.82(dd,J=7.9,1.7Hz,1H),7.78(d,J=1.8Hz,1H),7.61(dd,J=7.9,1.8Hz,1H),7.49(d,J=7.9Hz,1H),7.39(d,J=7.9Hz,1H),6.36(s,1H),4.38-4.34(m,2H),4.30-4.25(m,3H).MALDI-TOF-MS(M)(m/z):461.1[M+H]+.
(2)聚合物(PEFE)材料的制备
将EFE单体(0.01mmol,0.0048g),四丁基六氟磷酸铵(TBAPF6)(1mmol,0.387g)溶解于10ml色谱级二氯甲烷与1ml色谱级乙腈的混合溶液中,配制成单体浓度0.001mol/L、电解质浓度0.1mol/L的电解液。在室温下,以氧化铟锡导电玻璃(ITO)作为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极,采用循环伏安阳极氧化法制备聚合物薄膜。设定初始电压为-0.5V、终止电压1.4V、扫速100mV/s,聚合圈数设定为20圈(聚合膜厚度为450nm)。观察EFE聚合曲线,可知氧化还原峰对(1.00V/0.62V)。用二氯甲烷与乙腈(体积比10:1)的混和溶液冲洗,洗掉聚合物薄膜上的低聚物。其中,PEWE聚集态易团聚形成较为致密的整体,但该聚合物薄膜形成较小的团聚体,不易清洗干净,可能对其电化学性能产生一定的影响。
(3)聚合物(PEFE)电化学性能测试
将四丁基六氟磷酸铵(TBAPF6)(1mmol,0.387g)溶解于9ml色谱级二氯甲烷与1ml色谱级乙腈混合溶液中,配制成电解质浓度0.1mol/L的电解液。选择三电极体系,涂有聚合物(PEFE)薄膜的氧化铟锡(ITO)导电玻璃为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极。在室温下,测试其循环伏安曲线,即在0~1.4V电压范围下,以100mV/s的扫速循环伏安扫描一圈。观察PEFE聚合物曲线,可知氧化还原峰对(1.00V/0.62V)。聚合膜均具有两种颜色显示,其中PEWE在中性态下显日晒色,氧化态显灰紫色。依旧在此电解液下进行恒电流充放电测试,在0.1mA/cm2的电流密度下,有较大的比容量及较好的循环稳定性。在0.1mol/L的TBAPF6的二氯甲烷(CH2Cl2)和乙腈(ACN)(v/v=10/1)混合溶液(空白溶液)中,对各聚合膜进行全波段(UV–vis–NIR)吸光度的测试,改变电压,并测试不同电压下聚合物掺杂态吸光度的变化。共轭聚合膜PEWE在中性态下的最大吸收峰在370nm,该波长下的吸收峰即为聚合物的本征吸收峰;在可见光谱区,其最大吸收峰为450nm,此时聚合物薄膜呈现日晒色,随着电压的增加,该吸收峰逐渐减弱直至消失;在500-850nm吸收带的吸收强度逐渐增加,表明增加电压使该聚合链的掺杂逐渐加深,形成单极子态,且发生电子跃迁的单极子态逐步增加,聚合膜慢慢变为灰紫色。除此之外,近红外区出现新的吸收带且随着电压的升高逐渐增强,表明了该材料双极子态的形成及其电子跃迁的变化。
实施例5
一种D-A-D结构聚合物膜PEFE,按照如下方法进行制备:
(1)单体EFE的合成
对3,4-乙烯二氧噻吩(EDOT)锡化,将EDOT(6mmol,0.852g)溶解在干燥的四氢呋喃(40mL)中,在-78℃的N2氛围下,缓慢滴加正丁基锂(6.6mmol,4.125mL,1.6M),缓慢升温至-40℃,搅拌1h,再降温至-78℃,缓慢滴加三丁基氯化锡(7.2mmol,2.347g),并在室温下搅拌8h,过中性氧化铝柱过滤去除固体杂质,得到产物三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷。将2,7-二溴-9芴酮(3mmol,1.014g),三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基)锡烷(6mmol,2.593g)及双三苯基磷二氯化钯(0.025mmol,0.01755g)在N2氛围下溶解于50ml干燥甲苯中,加热至110℃下保持回流36小时。体系冷却后,用去离子水和二氯甲烷萃取,并加入无水硫酸镁搅拌干燥,之后旋转蒸发掉溶剂拌样,选择流动相(PE:DCM=1:2)层析过柱。最终得到目标产物(EWE)。1H NMR(500MHz,CDCl3)δ8.07(d,J=1.6Hz,1H),7.82(dd,J=7.9,1.7Hz,1H),7.78(d,J=1.8Hz,1H),7.61(dd,J=7.9,1.8Hz,1H),7.49(d,J=7.9Hz,1H),7.39(d,J=7.9Hz,1H),6.36(s,1H),4.38-4.34(m,2H),4.30-4.25(m,3H).MALDI-TOF-MS(M)(m/z):461.1[M+H]+.
(2)聚合物(PEFE)材料的制备
将EFE单体(0.01mmol,0.0048g),四丁基六氟磷酸铵(TBAPF6)(1mmol,0.387g)溶解于0.01ml色谱级二氯甲烷与9.99ml色谱级乙腈的混合溶液中,配制成单体浓度0.001mol/L、电解质浓度0.1mol/L的电解液。在室温下,以氧化铟锡导电玻璃(ITO)作为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极,采用循环伏安阳极氧化法制备聚合物薄膜。设定初始电压为-0.5V、终止电压1.4V、扫速100mV/s,聚合圈数设定为20圈(聚合膜厚度为450nm)。观察EFE聚合曲线,可知氧化还原峰对(1.00V/0.62V)。用二氯甲烷与乙腈(体积比0.1:1)的混和溶液冲洗,洗掉聚合物薄膜上的低聚物。其中,PEWE聚集态易团聚形成较为致密的整体,但该聚合物薄膜形成较小的团聚体,不易清洗干净,可能对其电化学性能产生一定的影响。
(3)聚合物(PEFE)电化学性能测试
将四丁基六氟磷酸铵(TBAPF6)(1mmol,0.387g)溶解于9ml色谱级二氯甲烷与1ml色谱级乙腈混合溶液中,配制成电解质浓度0.1mol/L的电解液。选择三电极体系,涂有聚合物(PEFE)薄膜的氧化铟锡(ITO)导电玻璃为工作电极,以抛光后的铂丝作为辅助电极(铂丝长度4cm),以双液接型银/氯化银电极作为参比电极。在室温下,测试其循环伏安曲线,即在0~1.4V电压范围下,以100mV/s的扫速循环伏安扫描一圈。观察PEFE聚合物曲线,可知氧化还原峰对(1.00V/0.62V)。聚合膜均具有两种颜色显示,其中PEWE在中性态下显日晒色,氧化态显灰紫色。依旧在此电解液下进行恒电流充放电测试,在0.1mA/cm2的电流密度下,有较大的比容量及较好的循环稳定性。在0.1mol/L的TBAPF6的二氯甲烷(CH2Cl2)和乙腈(ACN)(v/v=9/1)混合溶液(空白溶液)中,对各聚合膜进行全波段(UV–vis–NIR)吸光度的测试,改变电压,并测试不同电压下聚合物掺杂态吸光度的变化。共轭聚合膜PEWE在中性态下的最大吸收峰在370nm,该波长下的吸收峰即为聚合物的本征吸收峰;在可见光谱区,其最大吸收峰为450nm,此时聚合物薄膜呈现日晒色,随着电压的增加,该吸收峰逐渐减弱直至消失;在500-850nm吸收带的吸收强度逐渐增加,表明增加电压使该聚合链的掺杂逐渐加深,形成单极子态,且发生电子跃迁的单极子态逐步增加,聚合膜慢慢变为灰紫色。除此之外,近红外区出现新的吸收带且随着电压的升高逐渐增强,表明了该材料双极子态的形成及其电子跃迁的变化。
实施例6
一种D-A-D结构聚合物膜PEFE,用于电致变色型超级电容器。
Claims (5)
1.一种D-A-D结构聚合物膜PEFE,其特征在于,按照如下方法进行制备:
(1)将式I中的2,7-二溴-9芴酮与预先制得的三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基锡烷及双三苯基磷二氯化钯按(1:1~2:0.002~0.01)比例混合,在氮气环境下溶于有机溶剂A中,在回流温度下反应24~36小时,得到反应混合液B,用去离子水和二氯甲烷萃取后,过硅胶柱分离可得单体EFE,如式II所示;
(2)将步骤(1)所得式2所示的D-A-D单体EFE和电解质溶于支持电解溶剂中得到电解液,单体EFE的浓度为0.1~10mmol/L,支持电解质的初始终浓度为0.01~1mol/L电解溶剂.将电解液加入到电解池三电极体系中,与电化学工作站相连,在聚合电压-0.5~1.4V vsAg/AgCl下,聚合圈数在5~20圈下,进行电化学CV聚合反应,得到D-A-D结构聚合物膜PEFE,如式III所示;用有机溶剂色谱级二氯甲烷:乙腈体积比(0.1~10:1)的混合溶液清洗薄膜,干燥即可;
2.如权利要求1所述的一种D-A-D结构聚合物膜PEFE,其特征在于,所述步骤(2)中,电解溶剂为色谱级二氯甲烷:乙腈体积比(0.1~10:1)的混合溶液。
3.一种如权利要求1所述的D-A-D结构聚合物膜PEFE的制备方法,其特征在于,包括以下步骤:
(1)将式I中的2,7-二溴-9芴酮与预先制得的三丁基(2,3-二氢[3,4-b][1,4]二恶英-5-基锡烷及双三苯基磷二氯化钯按(1:1~2:0.002~0.01)比例混合,在氮气环境下溶于有机溶剂A中,在回流温度下反应24~36小时,得到反应混合液B,用去离子水和二氯甲烷萃取后,过硅胶柱分离可得单体EFE,如式II所示;
(2)将步骤(1)所得式2所示的D-A-D单体EFE和电解质溶于支持电解溶剂中得到电解液,单体EFE的浓度为0.1~10mmol/L,支持电解质的初始浓度为0.01~1mol/L电解溶剂。将电解液加入到电解池三电极体系中,与电化学工作站相连,在聚合电压-0.5~1.4V vs Ag/AgCl下,聚合圈数在5~20圈下,进行电化学CV聚合反应,得到D-A-D结构聚合物膜PEFE,如式III所示;用有机溶剂色谱级二氯甲烷:乙腈体积比(0.1~10:1)的混合溶液清洗薄膜,干燥即可;
4.如权利要求3所述的制备方法,其特征在于,所述步骤(2)中,电解溶剂为色谱级二氯甲烷:乙腈体积比(0.1~10:1)的混合溶液。
5.一种如权利要求1所述的D-A-D结构聚合物膜PEFE,其特征在于,所述D-A-D结构聚合物膜PEFE用于电致变色型超级电容器。
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