CN114479017A - 一种有机硼-噻吩共轭聚合物及其制备方法和应用 - Google Patents
一种有机硼-噻吩共轭聚合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种有机硼‑噻吩共轭聚合物及其制备方法和应用，该聚合物的分子结构式为：
其中，m＝16‑20。该聚合物具有优异循环稳定性，可作为锂离子电池负极材料，有较好的电子传导特性，表现出优异的循环稳定性及倍率性能，在高倍率储能器件方面具有广阔的应用前景。
Description
技术领域
本发明涉及有机聚合物锂离子电池技术领域，具体涉及一种可作为锂离子电池负极材料的有机硼-噻吩共轭聚合物及其制备方法和应用。
背景技术
目前，锂离子电池的应用领域越发多元化，许多特殊的使用场景对锂离子电池性能提出了更多的要求，例如大功率、长寿命等。
相比正极材料而言，负极材料的性能对整个电池来说起到了至关重要的作用。传统无机材料作为锂离子电池负极材料时，容易出现容量衰退快，循环稳定性差，首次不可逆容量大，实际比容量低等问题。
因此，需要开发一种倍率性能好、循环稳定性优异的具备商业化前景的锂离子电池负极材料。
发明内容
针对现有技术中的问题，本发明提供了一种有机硼-噻吩共轭聚合物及其制备方法和应用，其中，该有机含硼聚合物具有高电子迁移率的优点，具备成为优良的电极材料的潜力，能够解决现有电极材料中的容量不稳定问题，通过有机硼单元的引入，表现出了稳定的长循环性能。
为实现本发明的目的，本发明采用以下技术方案：
一种有机硼-噻吩共轭聚合物(PBT1),其分子结构式为：
其中，m＝16-20。
一种有机硼-噻吩共轭聚合物的制备方法，包括：
在无水无氧条件下，将单体M1、单体M2、催化剂四(三苯基膦)钯、碘化亚铜溶于脱气的四氢呋喃和二异丙胺的混合溶剂中，加热搅拌，反应结束后，冷却至室温；反应混合物减压抽滤，除去部分不溶物和催化剂，滤液浓缩，在沉淀剂甲醇、正己烷中依次反复溶解析出，直到上清液基本为无色，离心干燥，得到黄色聚合物固体；
其中，M1的分子结构式为：
M2的分子结构式为：
优选的，所述M1的制备方法包括：
将中间体A溶于四氢呋喃中，将四丁基氟化铵加入上述溶液中，搅拌反应结束后，旋去部分溶剂，之后加入水稀释，用二氯甲烷萃取，结合有机相，无水硫酸镁干燥，旋干溶剂，通过柱层析纯化得到白色固体；
其中，中间体A的制备方法包括：
在无水无氧条件下，将1,4-二溴-2,5-双三甲基硅基乙炔苯溶于干燥的四氢呋喃中，-78℃下，逐滴加入正丁基锂，在此温度下反应2h，然后将Mes2BF溶于四氢呋喃中，并在此温度下逐滴滴入上述反应液中，之后反应缓慢升至室温，继续反应过夜；结束后，加入100mL水猝灭反应，用二氯甲烷(3×50mL)萃取，合并有机相，无水硫酸镁干燥，旋干溶剂，加入正己烷，减压过滤得到白色固体。
优选的，所述M2的制备方法包括：
将噻吩、N-碘代琥珀酰亚胺溶于二氯甲烷和冰醋酸的混合溶剂中，室温搅拌4h，反应结束后，加入硫代硫酸钠水溶液猝灭，用二氯甲烷进行萃取，有机相用无水硫酸镁干燥，过滤，旋干溶剂，得到纯的淡黄色固体。
一种有机硼-噻吩共轭聚合物的应用，该聚合物可作为锂离子电池的负极材料；
一种有机硼-噻吩共轭聚合物的应用，该聚合物作为钠离子电池、钾离子电池、锌离子电池、镁离子电池、铝离子电池和钙离子电池中的一种离子电池的负极材料。
本发明与现有技术相比，具有以下有益效果：
该聚合物具有优异循环稳定性，作为锂离子电池负极工作时，有较好的电子传导特性，表现出优异的循环稳定性及倍率性能，1A/g大电流万次循环充放电后容量保持122.4％；该材料中的有机硼单元能有效降低电子传输阻力，在高倍率储能器件方面具有广阔的应用前景。
附图说明
图1为本发明一种有机硼-噻吩共轭聚合物(PBT1)的SEM显微镜照片。
图2为本发明一种有机硼-噻吩共轭聚合物(PBT1)与锂片组装半电池的循环伏安曲线，扫速为0.2m V/s。
图3为本发明一种有机硼-噻吩共轭聚合物(PBT1)与锂片组装半电池的充放电曲线，电流密度为45mA/g，循环10次。
图4为本发明一种有机硼-噻吩共轭聚合物(PBT1)与锂片组装半电池的循环稳定性测试，电流密度为500mA/g，循环5000次。
图5为本发明一种有机硼-噻吩共轭聚合物(PBT1)与锂片组装半电池的循环稳定性测试，电流密度为1A/g，循环10000次。
图6为本发明一种有机硼-噻吩共轭聚合物(PBT1)与锂片组装半电池的倍率性能曲线，电流密度分别为0.5、1、2、5、10A/g。
具体实施方式
下面将结合本发明实施例中的附图；对本发明实施例中的技术方案进行清楚、完整地描述：
如图1所示，一种有机硼-噻吩共轭聚合物(PBT1)，其分子结构如式为：
分子的结构特点是：(1)由于组成聚合物的以2,5-二碘噻吩作为电子给体单元，三甲基苯硼-2,5-双乙炔苯作为电子受体单元，电子可以在聚合物中迁移，形成离域的传导电子。(2)有机硼单元的加入，降低了电子传输阻力。
该聚合物通过中间体M1和中间体M2(2,5-二碘噻吩)合成得到，合成路线如下：
在无水无氧条件下，称取单体M1(0.622g,1.0mmol)、2,5-二碘噻吩(0.34g,1.0mmol)、催化剂四(三苯基膦)钯(0.58g,0.05mmol)、碘化亚铜(0.02g,0.1mmol)溶于脱气的30mL四氢呋喃和10mL二异丙胺的混合溶剂中，加热至70℃，搅拌48h，反应结束后，冷却至室温。反应混合物减压抽滤，除去部分不溶物和催化剂，滤液浓缩，在沉淀剂甲醇、正己烷中依次反复溶解析出，直到上清液基本为无色，离心后在60℃真空干燥箱中干燥24h，得到黄色聚合物固体(产率:520mg,74％)。
其中，中间体M1，合成路线如下：
第一步，Mes2BF的合成：
在无水无氧条件下，称取Mg屑(7.29g,300mmol)置于500mL的三口烧瓶中，连接冷凝管，恒压漏斗，用热枪活化镁屑2h，冷却至室温，向三口烧瓶中转入少许无水四氢呋喃并加入一粒碘单质作为引发剂，然后向恒压漏斗中加入2-溴-1,3,5-三甲基苯(39.82g,200mmol)，并转入70mL四氢呋喃，逐滴滴入，当引发后，立马放入冰浴中，再次将100mL四氢呋喃转入恒压漏斗，逐滴滴完后，在70℃下回流3-4h，冷却至室温，此时格氏试剂制备成功。将溶于100mL四氢呋喃的三氟化硼乙醚溶液(12.6mL)转入恒压漏斗，在0℃下逐滴滴入，之后缓慢升至室温，反应过夜。反应结束后，利用负压将上清液转出，并减压除去溶剂，之后用400mL干燥正己烷进行洗涤，过滤得到澄清溶液，并减压抽干溶剂，得到浅黄色固体(产率:79％,21.25g)。
第二步，1,4-二溴-2,5-二碘苯的合成：
称取1,4-二溴苯(23.59g,100mmol)置于500mL的三口烧瓶中，加入300mL浓硫酸，将碘单质(55.84g,220mmol)缓慢加入上述反应液中，混合液加热至130℃回流搅拌3d，在反应过程中，每隔2-3h手动摇晃反应液使升华的碘单质溶解。反应结束后，冷却至室温。将混合液少量多次缓慢倒入350mL冰水混合物中稀释，之后用二氯甲烷(3×150mL)萃取，有机相用300mL氢氧化钠水溶液洗涤，分离有机相，氢氧化钠层再次用二氯甲烷(3×50mL)进行萃取，合并有机层，用无水硫酸镁干燥，过滤，有机相用旋转蒸发仪除去溶剂，再用二氯甲烷/甲醇混合溶剂进行重结晶，得到白色固体(产率:85％,41.45g)。
第三步，1,4-二溴-2,5-双三甲基硅基乙炔苯的合成：
在无水无氧条件下，称取1,4-二溴-2,5-二碘苯(19.51g,40mmol)，催化剂双(三苯基膦)二氯化钯(1.40g,2.0mmol)，碘化亚铜(0.76g,4.0mmol)溶于200mL甲苯和100mL二异丙胺混合溶液中，将三甲基硅基乙炔(8.25g,84mmol)加入上述反应液中，室温下，搅拌24h。反应结束后，加入150mL水猝灭，用二氯甲烷(3×50mL)萃取，合并有机相，无水硫酸镁干燥，过滤，旋转蒸发仪旋干溶剂，用正己烷做淋洗剂柱层析纯化得到淡黄色固体(产率:11.26g,66％)。
第四步，一溴-2,5-双三甲基硅基乙炔苯的合成：
在无水无氧条件下，称取1,4-二溴-2,5-双三甲基硅基乙炔苯(12.85g,30mmol)溶于240mL干燥的四氢呋喃中，-78℃下，逐滴加入正丁基锂(1.6M,30mmol,18.8mL)，在此温度下反应2h，然后逐滴加入5mL水，之后反应体系缓慢升至室温，继续反应过夜。结束后，加入100mL水猝灭反应，用二氯甲烷(3×50mL)萃取，合并有机相，无水硫酸镁干燥，旋干溶剂，加入正己烷，减压过滤得到白色固体(产率:7.56g,72％)。
第五步，中间体A的合成：
在无水无氧条件下，称取1,4-二溴-2,5-双三甲基硅基乙炔苯(10.50g,30mmol)溶于240mL干燥的四氢呋喃中，-78℃下，逐滴加入正丁基锂(1.6M,31mmol,19.4mL)，在此温度下反应2h，然后将Mes2BF(8.45g,63mmol)溶于30mL四氢呋喃中，并在此温度下逐滴滴入上述反应液中，之后反应缓慢升至室温，继续反应过夜。结束后，加入100mL水猝灭反应，用二氯甲烷(3×50mL)萃取，合并有机相，无水硫酸镁干燥，旋干溶剂，加入正己烷，减压过滤得到白色固体(产率:10.11g,65％)。
第六步，中间体M1的合成：
称取A(7.78g,15mmol)溶于150mL四氢呋喃中，将四丁基氟化铵(1.0M,150mmol)加入上述溶液中，室温搅拌6天，反应结束后，旋去部分溶剂，之后加入100mL水稀释，用二氯甲烷(3×50mL)萃取，结合有机相，无水硫酸镁干燥，旋干溶剂，通过柱层析纯化(二氯甲烷:石油醚＝1:20)得到白色固体(产率:3.82g,68％)。
中间体M2(2,5-二碘噻吩)的制备，合成路线如下：
称取噻吩(0.84g,10mmol)、N-碘代琥珀酰亚胺(4.95g,22mmol)溶于20mL二氯甲烷和20mL冰醋酸的混合溶剂中，室温搅拌4h。反应结束后，加入50mL硫代硫酸钠水溶液猝灭，用二氯甲烷(3×20mL)进行萃取，有机相用无水硫酸镁干燥，过滤，旋干溶剂，得到纯的淡黄色固体(产率:3.19g,95％)。
如图2-6中为该有机硼-噻吩共轭聚合物作为锂离子电池负极时，在2.3V出现了微弱的氧化还原峰，属于噻吩单元的可逆循环峰。在1mA g-1的电流密度下，电池具有优异的循环稳定性，经10000次充放电循环后比容量保持率为122.4％，有较好的电子传导特性，有效提升了电极材料的倍率性能，可作为长寿命锂离子电池中的负极材料使用。同样，也可作为钠、钾、锌、镁、铝和钙离子电池中的负极材料。
以上所述仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其改进构思加以等同替换或改变，都应涵盖在本发明的保护范围。
Claims (6)
1.一种有机硼-噻吩共轭聚合物，其特征在于：分子结构式为：
其中，m＝16-20。
2.根据权利要求1所述的一种有机硼-噻吩共轭聚合物的制备方法，其特征在于：包括：
在无水无氧条件下，将单体M1、单体M2、催化剂四(三苯基膦)钯、碘化亚铜溶于脱气的四氢呋喃和二异丙胺的混合溶剂中，加热搅拌，反应结束后，冷却至室温；反应混合物减压抽滤，除去部分不溶物和催化剂，滤液浓缩，在沉淀剂甲醇、正己烷中依次反复溶解析出，直到上清液基本为无色，离心干燥，得到黄色聚合物固体；
其中，M1的分子结构式为：
M2的分子结构式为：
3.根据权利要求2所述的一种有机硼-噻吩共轭聚合物的制备方法，其特征在于：所述的M1的制备方法包括：
将中间体A溶于四氢呋喃中，将四丁基氟化铵加入上述溶液中，搅拌反应结束后，旋去部分溶剂，之后加入水稀释，用二氯甲烷萃取，结合有机相，无水硫酸镁干燥，旋干溶剂，通过柱层析纯化得到白色固体；
其中，中间体A的制备方法包括：
在无水无氧条件下，将1,4-二溴-2,5-双三甲基硅基乙炔苯溶于干燥的四氢呋喃中，-78℃下，逐滴加入正丁基锂，在此温度下反应2h，然后将Mes2BF溶于四氢呋喃中，并在此温度下逐滴滴入上述反应液中，之后反应缓慢升至室温，继续反应过夜；结束后，加入水猝灭反应，用二氯甲烷萃取，合并有机相，无水硫酸镁干燥，旋干溶剂，加入正己烷，减压过滤得到白色固体。
4.根据权利要求2所述的一种有机硼-噻吩共轭聚合物的制备方法，其特征在于：所述M2的制备方法包括：
将噻吩、N-碘代琥珀酰亚胺溶于二氯甲烷和冰醋酸的混合溶剂中，室温搅拌4h，反应结束后，加入硫代硫酸钠水溶液猝灭，用二氯甲烷进行萃取，有机相用无水硫酸镁干燥，过滤，旋干溶剂，得到纯的淡黄色固体。
5.根据权利要求1所述的一种有机硼-噻吩共轭聚合物的应用，其特征在于：该聚合物可作为锂离子电池的负极材料；
6.根据权利要求1所述的一种有机硼-噻吩共轭聚合物的应用，其特征在于：该聚合物可作为钠离子电池、钾离子电池、锌离子电池、镁离子电池、铝离子电池和钙离子电池中的一种离子电池的负极材料。
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