CN112920437A - 一种压电气凝胶膜及其制备方法 - Google Patents
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Abstract
本发明公开了一种压电气凝胶膜,由直径为2~6nm、平均长度为0.5~10μm的表面氧化的纤维素纳米纤维与层状金属二硫化物在水中混合,通过凝胶化、溶剂置换、冷冻干燥、冷压制膜并高压极化制备得到。本发明优选具有特定直径和长度的TEMPO氧化法处理的纤维素纳米纤维与单片层或少片层状MoS2纳米片复合,使得层状MoS2分散后形成的MoS2纳米片均匀分散在TOCN中,处于完全剥离状态,并通过溶剂置换及冻干过程,所得复合材料具有超多孔结构,并通过优选的TOCN和MoS2恰当比例使所得气凝胶压电膜具有很高的压电性能输出。
Description
技术领域
本发明属于材料技术领域,具体涉及一种压电气凝胶膜及其制备方法。
背景技术
当前塑料等白色污染日趋严重,必须开发可再生材料以取代传统石化产品。因此,生物质原料显得越来越重要。纤维素是自然界中储量最为丰富的天然高分子,其在植物中自组装成天然的纤维素纳米纤维,由于这种纤维素纳米纤维可生物降解、可再生、环境友好,还具有优异的力学性能和良好的透光性等特点,近年来吸引了广泛关注,成为生物质纳米材料研究领域的新兴热点。
MoS2(层状金属二硫化物)是一类具有二维片层类石墨烯结构的带金属光泽粉末,单层状及奇数层二硫化钼纳米片具有不对称的晶体结构,优异的压电活性、热稳定性等。将纤维素纳米纤维和MoS2复合能够综合二者的优点,获得强压电活性的复合压电膜。但目前制备的纤维素纳米纤维/层状金属二硫化物复合压电膜压电性能输出低,已报到的面积为4.5cm2复合致密膜器件开路电压输出约在4.1V,短路电流为0.21uA。而且通常所用纤维素纳米纤维是由强酸水解法或机械分离法等方法得到的,存在纤维长度较短、粗细分布不均匀等缺点,导致制备的复合膜综合性能低下。
发明内容
本发明目的在于提供一种表面氧化纤维素纳米纤维/层状金属二硫化物气凝胶压电膜及其制备方法,所得复合材料具有超多孔结构且有很高的压电性能输出,具备轻质、廉价、安全环保等优点,同时工艺简单,操作方便,对环境无污染。
为达到上述目的,采用技术方案如下:
一种压电气凝胶膜,由直径为2~6nm、平均长度为0.5~10μm的表面氧化的纤维素纳米纤维与层状金属二硫化物在水中混合,通过凝胶化、溶剂置换、冷冻干燥、冷压制膜并高压极化制备得到。
按上述方案,所述表面氧化的纤维素纳米纤维按以下方式制备而来:
将TEMPO与NaBr按质量比1:(1~10)加入水中,搅拌至完全溶解;
按质量比TEMPO:天然纤维素=(0.01~0.1):1加入天然纤维素;
然后按质量比TEMPO:NaClO=(0.01~0.1):1加入NaClO;
用NaOH溶液调节体系pH值为7~14,在10~60℃下氧化反应0.5~6h后过滤、洗涤、干燥得到表面氧化的纤维素纳米纤维。
按上述方案,所述层状金属二硫化物为已剥离的单片层或少片奇数层二硫化钼粉末。
上述压电气凝胶膜的制备方法,包括以下步骤:
1)将TEMPO与NaBr按质量比1:(1~10)加入水中,搅拌至完全溶解;按质量比TEMPO:天然纤维素=(0.01~0.1):1加入天然纤维素;然后按质量比TEMPO:NaClO=(0.01~0.1):1加入NaClO;用NaOH溶液调节体系pH值为7~14,在10~60℃下氧化反应0.5~6h后过滤、洗涤、干燥得到表面氧化的纤维素纳米纤维(TOCN);
2)将所得表面氧化的纤维素纳米纤维加入到水中分散得到TOCN分散液;将已剥离的的单片层或少片奇数层二硫化钼粉末加入到所述TOCN分散液中经分散得到混合分散液;将混合分散液凝胶化,冷冻干燥,冷压及高压极化得到表面氧化纤维素纳米纤维/层状金属二硫化物压电气凝胶膜。
按上述方案,步骤1中所述天然纤维素为棉花纤维素、木浆、苎麻纤维、甘蔗渣、细菌纤维素、海鞘纤维素中的一种或任意混合。
按上述方案,步骤2中所述分散的方式为机械搅拌或超声处理。
按上述方案,步骤2中所述混合分散液中TOCN的浓度为0.1~1wt%;所述混合分散液中MoS2浓度为2~8wt%。
按上述方案,步骤2中凝胶化方法为浓盐酸酸雾交联或离子交联;交联时间为24~48h。所述浓盐酸酸雾交联即将分散液暴露于密闭高浓度38%盐酸雾中;所述离子交联即使用三价铁离子或钙离子的饱和离子溶液雾化后喷涂于分散液表面。
按上述方案,步骤2中冷冻干燥温度为-60~-50℃,干燥时间为24~48h。
按上述方案,步骤2中冷压条件为0.5~5MPa,冷压时间为15~60min。
按上述方案,步骤2中高压极化的条件为室温电场场强20MV/m下极化2h。
本发明中表面氧化的纤维素纳米纤维(TOCN)是由TEMPO催化氧化体系得到的纤维素纳米纤维,TEMPO催化氧化法能有效地、有选择性地将木浆纤维素C6位上的伯醇羟基催化氧化成醛基和羧基。在碱性环境下,纳米纤维素表面的负电位被提高,使得纳米纤维素之间产生了的相互斥力,从而削弱了纳米纤维素之间的相互作用,最终使纤维素纳米纤维从天然纤维素中分离出来。
本发明选用TEMPO氧化纤维素纳米纤维(TOCN)中直径仅为2~6nm、平均长度为0.5~10μm的纤维素纳米纤维,由于TOCN直径小且长径比大,因而已制备出具有多孔结构的气凝胶膜材料,并且与其他方法得到的纤维素纳米纤维相比,TOCN同时具有更易分散的优点TOCN上带有被氧化后的羧基因而带有负电荷,其本身由于负电荷之间的静电斥力能实现很好地纳米分散,而MoS2纳米片表面能较大,与TOCN的复合可以被TOCN降低表面能,并且由氢键作用相互绑定,可以保证MoS2纳米片在TOCN基体中均匀分散不团聚。
相对于现有技术,本发明的有益效果在于:
本发明优选具有特定直径和长度的TEMPO氧化法处理的纤维素纳米纤维与单片层或少片层状MoS2纳米片复合,使得层状MoS2分散后形成的MoS2纳米片均匀分散在TOCN中,处于完全剥离状态,并通过溶剂置换及冻干过程,所得复合材料具有超多孔结构,并通过优选的TOCN和MoS2恰当比例使所得气凝胶压电膜具有很高的压电性能输出;开路电压达到42V,短路电流达到1.1μA,压电功率密度达到9.1μW/cm2,具有非常高的比表面积(94.7m2/g)和丰富的介孔(平均孔径14.3nm),具备轻质廉价安全环保等优点,在能量收集、自供电传感器等电子功能材料领域具有广泛的应用前景;
本发明直接将TOCN分散液与MoS2纳米片分散液共混或直接配制TOCN和MoS2纳米片混合分散液的方法,分散液的配制和共混方式简单,两种分散液的共混都是物理过程,未发生化学反应,并且工艺简单,操作方便,对环境无污染。整个工艺对设备要求不高,有利于工业化生产。
附图说明
图1:实施例3所制备TOCN/MoS2气凝胶压电膜的SEM图;
具体实施方式
以下实施例进一步阐释本发明的技术方案,但不作为对本发明保护范围的限制。
对比例1
1)制备TEMPO氧化纤维素纳米纤维:取0.01g TEMPO、0.1g NaBr,将其共同加入1000mL水中,在10℃、300r/min下磁力搅拌10min使其充分混合均匀至TEMPO和NaBr完全溶解,再向上述体系中加入1g的棉短绒,然后向体系中添加0.1gNaClO,通过滴加0.1mol/L的NaOH溶液保持体系pH值为9,在10℃下反应5h后将氧化后的纤维素进行过滤,再用水洗涤3次以上,干燥得到TEMPO氧化纤维素纳米纤维(TOCN);
2)配制TOCN分散液:将5g的TOCN加入到995g水使用高压均质30min;
3)凝胶化:将0.5wt%TOCN分散液暴露于盐酸雾蒸汽氛围中在25℃下交联凝胶化后取出,经过多次水洗。乙醇、叔丁醇置换得到TOCN凝胶。
4)制备气凝胶膜:将制备的TOCN凝胶使用液氮冷冻后方放置于冻干机中在-55℃和10Pa真空下进行冻干处理48h,完成后将冻干膜放在冷压机上用0.5MPa压缩15min得到TOCN气凝胶膜。
5)高压极化及封装:将上一步制得的TOCN气凝胶膜使用真空蒸镀工艺附上铝电极,使用高压极化仪在20MV/m场强下对气凝胶膜极化3h。极化完成后用导线连接电极并引出,使用PDMS对气凝胶膜进行封装处理,固化后得到最终TOCN气凝胶膜压电发电机。
利用DI NanoscopeⅣ原子力显微镜对得到的TOCN分散液进行形貌测试,测试结果表明,本对比例得到的TOCN直径为2~6nm,平均长度为5μm;使用MicromeriticsASAP2460型BET分析仪测得纯TOCN气凝胶膜的比表面积为107.6m2/g,平均孔径13.4nm;使用吉利德Ke6514静电计测得纯TOCN气凝胶膜开路电压输出为11V,短路状态下电流为0.3μA。
实施例1
1)制备TEMPO氧化纤维素纳米纤维:取0.01g TEMPO、0.1g NaBr,将其共同加入1000mL水中,在10℃、300r/min下磁力搅拌10min使其充分混合均匀至TEMPO和NaBr完全溶解,再向上述体系中加入1g的棉短绒,然后向体系中添加0.1g NaClO,通过滴加0.1mol/L的NaOH溶液保持体系pH值为9,在10℃下反应5h后将氧化后的纤维素进行过滤,再用水洗涤3次以上,干燥得到TEMPO氧化纤维素纳米纤维(TOCN);
2)配制混合分散液:将10g的TOCN加入到990g水使用高压均质30min声破碎仪制得1wt%TOCN分散液,将MoS2纳米片以2wt%加入到TOCN分散液中超声15min及搅拌1h使TOCN与MoS2纳米片混合均匀;
3)凝胶化:将TOCN/MoS2混合分散液暴露于盐酸雾蒸汽氛围中在25℃下交联凝胶化48h后取出,经过多次水洗。乙醇、叔丁醇置换得到TOCN/MoS2凝胶;
4)制备气凝胶膜:将制备的TOCN/MoS2凝胶使用液氮冷冻后方放置于冻干机中在-55℃和10Pa真空下进行冻干处理48h,完成后将冻干膜放在冷压机上用0.5MPa压缩15min得到TOCN/MoS2气凝胶膜;
5)高压极化及封装:将上一步制得的TOCN/MoS2气凝胶膜使用真空蒸镀工艺附上铝电极,使用高压极化仪在20MV/m场强下对气凝胶膜极化3h。极化完成后用导线连接电极并引出,使用PDMS对气凝胶膜进行封装处理,固化后得到最终TOCN/MoS2气凝胶膜压电发电机;
利用DI NanoscopeⅣ原子力显微镜对得到的TOCN分散液进行形貌测试,测试结果表明,本对比例得到的TOCN直径为2~6nm,平均长度为5μm;使用吉利德Ke6514静电计测得TOCN/MoS2气凝胶膜开路电压输出为20V,短路状态下电流为0.5μA。
实施例2
1)制备TEMPO氧化纤维素纳米纤维:取0.01g TEMPO、0.1g NaBr,将其共同加入1000mL水中,在25℃、300r/min下磁力搅拌10min使其充分混合均匀至TEMPO和NaBr完全溶解,再向上述体系中加入1g的棉短绒,然后向体系中添加0.1g NaClO,通过滴加0.1mol/L的NaOH溶液保持体系pH值为9,在25℃下反应5h后将氧化后的纤维素进行过滤,再用水洗涤3次以上,干燥得到TEMPO氧化纤维素纳米纤维(TOCN);
2)配制混合分散液:将5g的TOCN加入到995g水使用高压均质30min声破碎仪制得0.5wt%TOCN分散液,将MoS2纳米片以4wt%加入到TOCN分散液中超声15min及搅拌1h使TOCN与MoS2纳米片混合均匀;
3)凝胶化:将TOCN/MoS2混合分散液暴露于盐酸雾蒸汽氛围中在25℃下交联凝胶化48h后取出,经过多次水洗。乙醇、叔丁醇置换得到TOCN/MoS2凝胶;
4)制备气凝胶膜:将制备的TOCN/MoS2凝胶使用液氮冷冻后方放置于冻干机中在-55℃和10Pa真空下进行冻干处理48h,完成后将冻干膜放在冷压机上用0.5MPa压缩15min得到TOCN/MoS2气凝胶膜;
5)高压极化及封装:将上一步制得的TOCN/MoS2气凝胶膜使用真空蒸镀工艺附上铝电极,使用高压极化仪在20MV/m场强下对气凝胶膜极化3h。极化完成后用导线连接电极并引出,使用PDMS对气凝胶膜进行封装处理,固化后得到最终TOCN/MoS2气凝胶膜压电发电机;
利用DI NanoscopeⅣ原子力显微镜对得到的TOCN分散液进行形貌测试,测试结果表明,本对比例得到的TOCN直径为2~6nm,平均长度为5μm;使用吉利德Ke6514静电计测得TOCN/MoS2气凝胶膜开路电压输出为32V,短路状态下电流为0.8μA。
实施例3
1)制备TEMPO氧化纤维素纳米纤维:取0.01g TEMPO、0.1g NaBr,将其共同加入1000mL水中,在25℃、300r/min下磁力搅拌10min使其充分混合均匀至TEMPO和NaBr完全溶解,再向上述体系中加入1g的棉短绒,然后向体系中添加0.1gNaClO,通过滴加0.1mol/L的NaOH溶液保持体系pH值为9,在25℃下反应5h后将氧化后的纤维素进行过滤,再用水洗涤3次以上,干燥得到TEMPO氧化纤维素纳米纤维(TOCN);
2)配制混合分散液:将5g的TOCN加入到995g水使用高压均质30min声破碎仪制得0.5wt%TOCN分散液,将MoS2纳米片以6wt%加入到TOCN分散液中超声15min及搅拌1h使TOCN与MoS2纳米片混合均匀;
3)凝胶化:将TOCN/MoS2混合分散液暴露于盐酸雾蒸汽氛围中在25℃下交联凝胶化48h后取出,经过多次水洗。乙醇、叔丁醇置换得到TOCN/MoS2凝胶;
4)制备气凝胶膜:将制备的TOCN/MoS2凝胶使用液氮冷冻后方放置于冻干机中在-55℃和10Pa真空下进行冻干处理48h,完成后将冻干膜放在冷压机上用0.5MPa压缩15min得到TOCN/MoS2气凝胶膜;
5)高压极化及封装:将上一步制得的TOCN/MoS2气凝胶膜使用真空蒸镀工艺附上铝电极,使用高压极化仪在20MV/m场强下对气凝胶膜极化3h。极化完成后用导线连接电极并引出,使用PDMS对气凝胶膜进行封装处理,固化后得到最终TOCN/MoS2气凝胶膜压电发电机;
利用DI NanoscopeⅣ原子力显微镜对得到的TOCN分散液进行形貌测试,测试结果表明,本对比例得到的TOCN直径为2~6nm,平均长度为5μm;使用MicromeriticsASAP2460型BET分析仪测得TOCN/MoS2气凝胶膜的比表面积为94.7m2/g,平均孔径14.3nm;使用吉利德Ke6514静电计测得TOCN/MoS2气凝胶膜开路电压输出为42V,短路状态下电流为1.1μA。
如图1所示为本对比例制备的TOCN/MoS2气凝胶压电膜的SEM断面图,如图可见纯TOCN膜内部结构呈超多孔结构,且较为均匀。相对于对比例1,填料的加入显著增加了压电活性,但降低了比表面积。
实施例4
制备表面氧化纤维素纳米纤维膜,步骤如下:
1)制备TEMPO氧化纤维素纳米纤维:取0.01g TEMPO、0.1g NaBr,将其共同加入1000mL水中,在25℃、300r/min下磁力搅拌10min使其充分混合均匀至TEMPO和NaBr完全溶解,再向上述体系中加入1g的棉短绒,然后向体系中添加0.1g NaClO,通过滴加0.1mol/L的NaOH溶液保持体系pH值为9,在25℃下反应5h后将氧化后的纤维素进行过滤,再用水洗涤3次以上,干燥得到TEMPO氧化纤维素纳米纤维(TOCN);
2)配制混合分散液:将1g的TOCN加入到999g水使用高压均质30min声破碎仪制得0.1wt%TOCN分散液,将MoS2纳米片以8wt%加入到TOCN分散液中超声15min及搅拌1h使TOCN与MoS2纳米片混合均匀,再使用旋蒸仪将混合分散液浓缩至0.5wt.%;
3)凝胶化:将TOCN/MoS2混合分散液暴露于盐酸雾蒸汽氛围中在25℃下交联凝胶化48h后取出,经过多次水洗。乙醇、叔丁醇置换得到TOCN/MoS2凝胶;
4)制备气凝胶膜:将制备的TOCN/MoS2凝胶使用液氮冷冻后方放置于冻干机中在-55℃和10Pa真空下进行冻干处理48h,完成后将冻干膜放在冷压机上用0.5MPa压缩15min得到TOCN/MoS2气凝胶膜;
5)高压极化及封装:将上一步制得的TOCN/MoS2气凝胶膜使用真空蒸镀工艺附上铝电极,使用高压极化仪在20MV/m场强下对气凝胶膜极化3h。极化完成后用导线连接电极并引出,使用PDMS对气凝胶膜进行封装处理,固化后得到最终TOCN/MoS2气凝胶膜压电发电机;
利用DI NanoscopeⅣ原子力显微镜对得到的TOCN分散液进行形貌测试,测试结果表明,本实施例得到的TOCN直径为2~6nm,平均长度为5μm;使用吉利德Ke6514静电计测得TOCN/MoS2气凝胶膜开路电压输出为37V,短路状态下电流为0.9μA。
Claims (10)
1.一种压电气凝胶膜,其特征在于由直径为2~6nm、平均长度为0.5~10μm的表面氧化的纤维素纳米纤维与层状金属二硫化物在水中混合,通过凝胶化、溶剂置换、冷冻干燥、冷压制膜并高压极化制备得到。
2.如权利要求1所述压电气凝胶膜,其特征在于所述表面氧化的纤维素纳米纤维按以下方式制备而来:
将TEMPO与NaBr按质量比1:(1~10)加入水中,搅拌至完全溶解;
按质量比TEMPO:天然纤维素=(0.01~0.1):1加入天然纤维素;
然后按质量比TEMPO:NaClO=(0.01~0.1):1加入NaClO;
用NaOH溶液调节体系pH值为7~14,在10~60℃下氧化反应0.5~6h后过滤、洗涤、干燥得到表面氧化的纤维素纳米纤维。
3.如权利要求1所述压电气凝胶膜,其特征在于所述层状金属二硫化物为已剥离的单片层或少片奇数层二硫化钼粉末。
4.权利要求1-3任一项所述压电气凝胶膜的制备方法,其特征在于包括以下步骤:
1)将TEMPO与NaBr按质量比1:(1~10)加入水中,搅拌至完全溶解;按质量比TEMPO:天然纤维素=(0.01~0.1):1加入天然纤维素;然后按质量比TEMPO:NaClO=(0.01~0.1):1加入NaClO;用NaOH溶液调节体系pH值为7~14,在10~60℃下氧化反应0.5~6h后过滤、洗涤、干燥得到表面氧化的纤维素纳米纤维;
2)将所得表面氧化的纤维素纳米纤维加入到水中分散得到TOCN分散液;将已剥离的的单片层或少片奇数层二硫化钼粉末加入到所述TOCN分散液中经分散得到混合分散液;将混合分散液凝胶化,冷冻干燥,冷压及高压极化得到表面氧化纤维素纳米纤维/层状金属二硫化物压电气凝胶膜。
5.如权利要求4所述压电气凝胶膜的制备方法,其特征在于骤1中所述天然纤维素为棉花纤维素、木浆、苎麻纤维、甘蔗渣、细菌纤维素、海鞘纤维素中的一种或任意混合。
6.如权利要求4所述压电气凝胶膜的制备方法,其特征在于步骤2中所述混合分散液中TOCN的浓度为0.1~1wt%;所述混合分散液中MoS2浓度为2~8wt%。
7.如权利要求4所述压电气凝胶膜的制备方法,其特征在于步骤2中凝胶化方法为浓盐酸酸雾交联或离子交联;交联时间为24~48h。
8.如权利要求4所述压电气凝胶膜的制备方法,其特征在于步骤2中冷冻干燥温度为-60~-50℃,干燥时间为24~48h。
9.如权利要求4所述压电气凝胶膜的制备方法,其特征在于步骤2中冷压条件为0.5~5MPa,冷压时间为15~60min。
10.如权利要求4所述压电气凝胶膜的制备方法,其特征在于步骤2中高压极化的条件为室温电场场强20MV/m下极化2h。
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