CN112708280A - 一种木质素纤维气凝胶及其制备方法和应用 - Google Patents
一种木质素纤维气凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供一种木质素纤维气凝胶及其制备方法和应用,属于木质素纤维合成方法技术领域。该方法先使用低共熔溶剂溶解线形高分子,混合均匀后,继续溶解木质素,形成均匀的溶液作为电纺的待纺液;将待纺液采用电纺装置进行电纺,电纺装置下方采用水浴装置接收,得到木质纤维素混合物;最后将得到的木质纤维素混合物静置后处理得到木质素纤维气凝胶。本发明还提供上述制备方法得到的木质素纤维气凝胶。本发明还提供上述木质素纤维气凝胶在超级电容器的电极材料中的应用。该木质素纤维气凝胶经过预氧化和碳化后得到的木质素基碳纤维气凝胶具有高的相对比表面积和多孔性。
Description
技术领域
本发明属于木质素纤维合成方法技术领域,具体涉及一种木质素纤维气凝胶及其制备方法和应用。
背景技术
木质素广泛存在树木等植物中,是一种可再生资源,是由三种单体(对香豆醇、松柏醇和芥子醇)组成的高分子聚合物,通常难溶于水、乙醇等常见有机溶剂。在传统的造纸工业中,大量木质素作为废料形成“黑液”,被不法企业排放到江河水体中,污染环境。当前主流处理“黑液”的方式是采用碱回收的方式,回收木质素并作为燃料烧掉,这没有充分利用木质素作为可再生资源的价值。木质素可以进一步加工成修饰木质素如碱性木质素等,可以用于碳基材料的合成、树脂和塑料加工的添加剂、矿物的浮选剂等方面。
低共熔溶剂是一种新型的绿色溶剂。低共熔溶剂通常是由两种或多种物质以一定比例相混合,由于氢键等分子力作用下,形成的混合物熔点降低,以致在室温下以液体的形式存在,可以作为溶剂来使用。低共熔溶剂通常具有价格便宜、易于合成、无毒、可生物降解和可回收等特性,是具有工业应用价值和符合环保要求的溶剂。
静电纺丝技术(简称:电纺)原理是采用高压静电将聚合物溶液分散成微小射流,在喷射过程中溶剂挥发、高分子固化形成纤维。传统的电纺采用易挥发的有机溶剂溶解高分子。例如中国发明专利CN 107956001 A提出一种超级电容器用木质素纳米炭纤维的制备。该发明使用易挥发有机溶剂DMF,THF等溶解木质素进行纺丝。再比如中国发明专利CN111223673 A采用木质素与聚苯烯腈共混,再溶解在DMF有机溶剂中作为待纺液,用于电纺合成木质素碳纤维。但是,传统挥发性有机溶剂作为电纺的待纺液有以下缺点:(1)挥发性有机溶剂通常有毒,会污染大气并对人员的身体健康造成损害。(2)有机溶剂通常易燃,电纺装置中的高压设备容易产生电火花,且电纺装置通常需要控温且密闭,因此有易燃易爆的危险。(3)挥发掉的有机溶剂难以回收,会造成成本的提高与资源的浪费。
发明内容
本发明的目的是为了解决现有的电纺合成木质素纤维的方法需要使用有毒溶剂,且电纺装置有易燃易爆的危险的问题,而提供一种木质素纤维气凝胶及其制备方法和应用。
本发明提供一种木质素纤维气凝胶的制备方法,该方法包括:
步骤一:使用低共熔溶剂溶解线形高分子,混合均匀后,继续溶解木质素,形成均匀的溶液作为电纺的待纺液;
所述的低共熔溶剂为氯化胆碱基低共熔溶剂或甜菜碱基低共熔溶剂;
所述的线形高分子为聚乙烯醇、聚乙烯吡咯烷酮或聚氧化乙烯;
步骤二:将步骤一的待纺液采用电纺装置进行电纺,电纺装置下方采用水浴装置接收,得到木质纤维素混合物;
步骤三:将步骤二得到的木质纤维素混合物静置,将上方的低共熔溶剂与水的混合物倒出并收集,继续加入纯水后摇晃,用于洗掉纤维中的低共熔溶剂,反复几次,直至木质素纤维悬浮在水中,将悬浮液进行冷冻干燥,得到木质素纤维气凝胶。
优选的是,所述的步骤一种低共熔溶剂、线形高分子、木质素的质量比为1:0.01~0.03:0.05~0.15。
优选的是,所述的氯化胆碱基低共熔溶剂为氯化胆碱和苹果酸、草酸或乳酸的混合物。
优选的是,所述的氯化胆碱和苹果酸、草酸或乳酸的混合物中,氯化胆碱和苹果酸、草酸或乳酸的摩尔比为1:2~10。
优选的是,所述的甜菜碱基低共熔溶剂为甜菜碱和乳酸或苹果酸的混合物。
优选的是,所述的甜菜碱和乳酸或苹果酸的混合物中,甜菜碱和乳酸或苹果酸的摩尔比为1:2~10。
优选的是,步骤二的电纺装置进行电纺的条件为:针头距离水面5~15cm,电纺过程中,电压设置为10~20kV,温度为10~35℃,喷射速率0.1~1mL/h。
优选的是,所述的步骤三的静置时间为6~10h。
本发明还提供上述制备方法得到的木质素纤维气凝胶。
本发明还提供上述木质素纤维气凝胶在超级电容器的电极材料中的应用。
本发明的有益效果
本发明提供一种木质素纤维气凝胶及其制备方法和应用,该木质素纤维气凝胶使用低共熔溶剂作为电纺木质素纤维的待纺液,可以有效避免使用挥发性的有机溶剂造成的有毒、易燃易爆的危险,同时本发明的低共熔溶剂都可以回收再利用,节约成本与资源。该木质素纤维气凝胶经过预氧化和碳化后得到的木质素基碳纤维气凝胶具有高的相对比表面积(756m2/g)和多孔性(孔半径5~25nm),可以用于超级电容器的电容材料方面。
附图说明
图1为本发明一种木质素纤维气凝胶的制备流程图;
图2为本发明实施例1制成的木质素纤维气凝胶的照片;
图3为本发明实施例3得到的木质素基碳纤维气凝胶的N2吸脱附曲线与孔径分布图;
图4为本发明实施例3得到的木质素基碳纤维气凝胶与商业化碳纳米管电容性能对比图。
具体实施方式
本发明提供一种木质素纤维气凝胶的制备方法,该方法包括:
步骤一:使用低共熔溶剂溶解线形高分子,混合均匀后,继续溶解木质素,形成均匀的溶液作为电纺的待纺液;
所述的低共熔溶剂为氯化胆碱基低共熔溶剂或甜菜碱基低共熔溶剂;所述的氯化胆碱基低共熔溶剂优选为氯化胆碱和苹果酸、草酸或乳酸的混合物。所述的氯化胆碱和苹果酸、草酸或乳酸的混合物中,氯化胆碱和苹果酸、草酸或乳酸的摩尔比优选为1:2~10。
所述的甜菜碱基低共熔溶剂为甜菜碱和乳酸或苹果酸的混合物;所述的甜菜碱和乳酸或苹果酸的混合物中,甜菜碱和乳酸或苹果酸的摩尔比优选为1:2~10。
所述的线形高分子为聚乙烯醇、聚乙烯吡咯烷酮或聚氧化乙烯;
所述的步骤一种低共熔溶剂、线形高分子、木质素的质量比优选为1:0.01~0.03:0.05~0.15;
所述的木质素为脱碱木质素、碱木质素、酶解木质素、磺化木质素等化学修饰的木质素原料。
步骤二:将步骤一的待纺液采用电纺装置进行电纺,具体为:使用塑料注射器吸入步骤一制成的待纺液,安装金属针头,将电纺装置竖直设立,朝下喷丝,下方使用装水的塑料盆作为水浴接收装置,里面铺上金属箔并接地,水下放搅拌子在电纺过程中缓慢搅拌,针头距离水面5~15cm,电纺过程中,电压设置为10~20kV,温度为10~35℃,喷射速率0.1~1mL/h,得到木质纤维素混合物;
步骤三:将步骤二得到的木质纤维素混合物静置,所述的静置时间优选为6~10h,木质素纤维会沉降到容器底部,将上方的低共熔溶剂与水的混合物倒出并收集,继续加入纯水后摇晃,用于洗掉纤维中的低共熔溶剂,反复几次,直至木质素纤维悬浮在水中,将悬浮液进行冷冻干燥,得到木质素纤维气凝胶。
按照本发明,所述的步骤三中倒出的低共熔溶剂的水溶液与洗液可以使用旋转蒸仪等类似蒸发装置分离纯水与低共熔溶剂并进行回收利用。
本发明还提供上述制备方法得到的木质素纤维气凝胶。
本发明还提供上述木质素纤维气凝胶在超级电容器的电极材料中应用。具体为:将上述木质素纤维气凝胶继续在空气中预氧化,温度为200~300℃,时间1~5h,预氧化过后,在惰性气体保护下,700~1000℃下碳化1~8h,得到木质素基碳纤维,该碳纤维可以应用于超级电容器的电极材料。
下面结合具体实施例对本发明做进一步详细的描述,实施例中涉及到的原料均为商购获得。
实施例1
(1)使用氯化胆碱-乳酸低共熔溶剂溶解聚乙烯醇高分子,混合均匀后,继续溶解木质素形成均匀的溶液作为电纺的待纺液。低共熔溶剂、聚乙烯醇、木质素的质量比为1:0.02:0.1,其中氯化胆碱-乳酸中氯化胆碱和乳酸的摩尔比为1:2。
(2)使用塑料注射器吸入步骤(1)制成的待纺液,安装金属针头,将电纺装置竖直设立,朝下喷丝。下方使用装水的塑料盆作为接收装置(水浴),里面铺上金属箔并接地,水下放搅拌子在电纺过程中缓慢搅拌。针头距离水面10cm。电纺过程中,电压设置为15kV,温度为25℃,喷射速率0.2mL/h。
(3)纺丝完成后,将步骤(2)中接收器(水浴)中的水与木质素纤维的混合物转移到玻璃容器中,静置10h,木质素纤维会沉降到容器底部。将上方的低共熔溶剂与水的混合物倒出并收集。继续加入纯水后摇晃,用于洗掉纤维中的低共熔溶剂。如此反复几次,直至木质素纤维悬浮在水中。将悬浮液进行冷冻干燥,得到木质素纤维气凝胶,如图2所示。
(4)步骤(3)中倒出的低共熔溶剂的水溶液可以使用旋转蒸发仪等类似蒸发装置分离纯水与低共熔溶剂并进行回收利用。
实施例2
(1)使用甜菜碱-乳酸低共熔溶剂溶解聚乙烯吡咯烷酮高分子,混合均匀后,继续溶解木质素形成均匀的溶液作为电纺的待纺液。低共熔溶剂、聚乙烯吡咯烷酮、木质素的含量质量比为1:0.02:0.15,其中甜菜碱-乳酸中甜菜碱和乳酸的摩尔比为1:2。
(2)使用塑料注射器吸入步骤(1)制成的待纺液,安装金属针头,将电纺装置竖直设立,朝下喷丝。下方使用装水的塑料盆作为接收装置(水浴),里面铺上金属箔并接地,水下放搅拌子在电纺过程中缓慢搅拌。针头距离水面10cm。电纺过程中,电压设置为15kV,温度为25℃,喷射速率0.2mL/h。
(3)纺丝完成后,将步骤(2)中接收器(水浴)中的水与木质素纤维的混合物转移到玻璃容器中,静置10h,木质素纤维会沉降到容器底部。将上方的低共熔溶剂与水的混合物倒出并收集。继续加入纯水后摇晃,用于洗掉纤维中的低共熔溶剂。如此反复几次,直至木质素纤维悬浮在水中。将悬浮液进行冷冻干燥,得到木质素纤维气凝胶。
(4)步骤(3)中倒出的低共熔溶剂的水溶液可以使用旋转蒸发仪等类似蒸发装置分离纯水与低共熔溶剂并进行回收利用。
实施例3
将实施例2制备得到的木质素纤维气凝胶继续在空气中预氧化,温度为280℃,时间5h,预氧化过后,在惰性气体保护下,800℃下碳化2h,得到木质素基碳纤维。
图3本发明实施例3制备得到的木质素基碳纤维气凝胶的N2吸脱附曲线(a)与孔径分布图(b);图3说明制备得到的木质素基碳纤维气凝胶具有高的比表面积(756m2/g),其表面富含微孔与介孔(孔半径<15nm)。
图4本发明实施例3制备得到的木质素基碳纤维气凝胶与商业化碳纳米管电容性能对比图。从图4可以看出,本发明的木质素基碳纤维气凝胶电容性能优于传统的碳纳米管材料。
Claims (10)
1.一种木质素纤维气凝胶的制备方法,其特征在于,该方法包括:
步骤一:使用低共熔溶剂溶解线形高分子,混合均匀后,继续溶解木质素,形成均匀的溶液作为电纺的待纺液;
所述的低共熔溶剂为氯化胆碱基低共熔溶剂或甜菜碱基低共熔溶剂;
所述的线形高分子为聚乙烯醇、聚乙烯吡咯烷酮或聚氧化乙烯;
步骤二:将步骤一的待纺液采用电纺装置进行电纺,电纺装置下方采用水浴装置接收,得到木质纤维素混合物;
步骤三:将步骤二得到的木质纤维素混合物静置,将上方的低共熔溶剂与水的混合物倒出并收集,继续加入纯水后摇晃,用于洗掉纤维中的低共熔溶剂,反复几次,直至木质素纤维悬浮在水中,将悬浮液进行冷冻干燥,得到木质素纤维气凝胶。
2.根据权利要求1所述的一种木质素纤维气凝胶的制备方法,其特征在于,所述的步骤一种低共熔溶剂、线形高分子、木质素的质量比为1:0.01~0.03:0.05~0.15。
3.根据权利要求1所述的一种木质素纤维气凝胶的制备方法,其特征在于,所述的氯化胆碱基低共熔溶剂为氯化胆碱和苹果酸、草酸或乳酸的混合物。
4.根据权利要求3所述的一种木质素纤维气凝胶的制备方法,其特征在于,所述的氯化胆碱和苹果酸、草酸或乳酸的混合物中,氯化胆碱和苹果酸、草酸或乳酸的摩尔比为1:2~10。
5.根据权利要求1所述的一种木质素纤维气凝胶的制备方法,其特征在于,所述的甜菜碱基低共熔溶剂为甜菜碱和乳酸或苹果酸的混合物。
6.根据权利要求5所述的一种木质素纤维气凝胶的制备方法,其特征在于,所述的甜菜碱和乳酸或苹果酸的混合物中,甜菜碱和乳酸或苹果酸的摩尔比为1:2~10。
7.根据权利要求1所述的一种木质素纤维气凝胶的制备方法,其特征在于,步骤二的电纺装置进行电纺的条件为:针头距离水面5~15cm,电纺过程中,电压设置为10~20kV,温度为10~35℃,喷射速率0.1~1mL/h。
8.根据权利要求1所述的一种木质素纤维气凝胶的制备方法,其特征在于,所述的步骤三的静置时间为6~10h。
9.权利要求1-8任何一项所述的制备方法得到的木质素纤维气凝胶。
10.权利要求9所述的木质素纤维气凝胶在超级电容器的电极材料中的应用。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114854155A (zh) * | 2022-04-06 | 2022-08-05 | 杭州师范大学 | 一种高强度、抗冻和透明的导电pva/季铵盐弹性体 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170027168A1 (en) * | 2015-07-27 | 2017-02-02 | Stephan HEATH | Methods, products, and systems relating to making, providing, and using nanocrystalline (nc) products comprising nanocrystalline cellulose (ncc), nanocrystalline (nc) polymers and/or nanocrystalline (nc) plastics or other nanocrystals of cellulose composites or structures, in combination with other materials |
CN106987922A (zh) * | 2017-05-26 | 2017-07-28 | 四川大学 | 中空多孔结构的纤维素纳米纤维静电纺丝制备方法 |
CN107200851A (zh) * | 2017-07-17 | 2017-09-26 | 陕西科技大学 | 一种低共熔溶剂制备纳米木质素的方法 |
CN109019590A (zh) * | 2018-07-23 | 2018-12-18 | 北京林业大学 | 木质素基多级孔碳材料及其制备方法 |
-
2020
- 2020-12-22 CN CN202011524823.6A patent/CN112708280B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170027168A1 (en) * | 2015-07-27 | 2017-02-02 | Stephan HEATH | Methods, products, and systems relating to making, providing, and using nanocrystalline (nc) products comprising nanocrystalline cellulose (ncc), nanocrystalline (nc) polymers and/or nanocrystalline (nc) plastics or other nanocrystals of cellulose composites or structures, in combination with other materials |
CN106987922A (zh) * | 2017-05-26 | 2017-07-28 | 四川大学 | 中空多孔结构的纤维素纳米纤维静电纺丝制备方法 |
CN107200851A (zh) * | 2017-07-17 | 2017-09-26 | 陕西科技大学 | 一种低共熔溶剂制备纳米木质素的方法 |
CN109019590A (zh) * | 2018-07-23 | 2018-12-18 | 北京林业大学 | 木质素基多级孔碳材料及其制备方法 |
Non-Patent Citations (5)
Title |
---|
KAI RONG 等: "Deep eutectic solvent assisted zero-waste electrospinning of lignin fiber aerogels", 《GREEN CHEMISTRY》 * |
李利芬等: "低共熔溶剂在木质纤维类生物质研究中的应用", 《林业工程学报》 * |
李正一等: "木质素基纳米炭纤维制备与电容性能研究", 《炭素技术》 * |
狄莹莹等: "废弃物基纤维素气凝胶的研究进展", 《合成材料老化与应用》 * |
陶鑫等: "木质素的分离及其综合利用研究进展", 《天津造纸》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114854155A (zh) * | 2022-04-06 | 2022-08-05 | 杭州师范大学 | 一种高强度、抗冻和透明的导电pva/季铵盐弹性体 |
CN114854155B (zh) * | 2022-04-06 | 2023-08-22 | 杭州师范大学 | 一种高强度、抗冻和透明的导电pva/季铵盐弹性体 |
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