CN108914550A - 一种表面包覆二氧化锆纳米层的聚酰亚胺纤维膜的制备方法 - Google Patents
一种表面包覆二氧化锆纳米层的聚酰亚胺纤维膜的制备方法 Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 59
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 27
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
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- BCSOQFLCGQULPX-UHFFFAOYSA-J [Zr+4].[O-]C(=O)C(F)(F)F.FC(C(=O)CC(C)=O)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F Chemical compound [Zr+4].[O-]C(=O)C(F)(F)F.FC(C(=O)CC(C)=O)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F BCSOQFLCGQULPX-UHFFFAOYSA-J 0.000 claims description 2
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- 239000007787 solid Substances 0.000 claims description 2
- 235000008429 bread Nutrition 0.000 claims 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims 1
- SGNLDVYVSFANHW-UHFFFAOYSA-N pentane-2,4-dione;zirconium Chemical compound [Zr].CC(=O)CC(C)=O SGNLDVYVSFANHW-UHFFFAOYSA-N 0.000 claims 1
- 239000008367 deionised water Substances 0.000 abstract description 12
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- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 12
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 12
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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Abstract
一种表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维膜及其制备方法。首先通过静电纺丝法制备聚酰亚胺纳米纤维膜,并用有机锆盐溶液处理,然后置于去离子水中充分浸泡,最后经过热处理,使有机锆盐充分水解在纤维表面形成一层二氧化锆纳米层状结构。本发明的方法实施过程简单,包覆效率高,可以广泛应用于组织工程支架、药物缓释材料、传感器、催化、过滤材料以及电池隔膜等领域,有良好的发展前景。
Description
技术领域
本发明属于聚酰亚胺纤维膜技术领域,尤其是涉及一种表面包覆二氧化锆纳米层的聚酰亚胺纤维膜的制备方法。
背景技术
由于高能源需求的快速增长,锂离子电池由于其循环放电寿命长、能量和功率密度高的高性能而受到广泛关注。锂离子电池主要由正/负极材料、电解质、隔膜及电池外壳包装材料组成。隔膜是锂离子电池的重要组成部分,起着分隔正、负极,防止电池内部短路,允许电解质离子自由通过,完成电化学充放电过程的作用。其性能决定了电池的界面结构、内阻等,直接影响电池的容量、循环性能以及安全性能等特性,性能优异的隔膜对提高电池的综合性能具有重要的作用,被业界称为电池的“第三电极”。
聚酰亚胺材料具有优异的耐高温、耐低温、高强高模、高抗蠕变、高尺寸稳定、低热膨胀系数、高电绝缘、低介电常数与损耗、耐辐射、耐腐蚀等优点。由于聚酰亚胺具有上述诸多优良性质,决定了其具有非常广泛的用途,而且在每一个应用领域尤其是在一些高科技、高附加值的产业中,都发挥了突出的作用。它可加工成聚酰亚胺薄膜、耐高温工程塑料、复合材料用基体树脂、耐高温涂料、耐高温粘结剂、纤维和泡沫塑料等多种材料形式,因此在航空航天、空间、微电子、精密机械、医疗器械等许多高新技术领域具有广阔的应用前景和巨大的商业价值。
目前,经过静电纺丝这一生产方式制得的聚酰亚胺纳米纤维膜已经被人们应用于锂离子电池隔膜这一领域。将无机粒子与聚酰亚胺纳米纤维复合可同时结合无机粒子和聚酰亚胺的优点,从而极大地提高聚酰亚胺纳米纤维膜的综合性能,是当前的一个研究热点。例如专利CN103981634A曾采用将硅源加入到聚酰胺酸纺丝液中并通过静电纺丝法及热处理制备出了聚酰亚胺/二氧化硅复合纳米纤维膜。本发明提出将聚酰亚胺纤维的表面包覆一层二氧化锆,制成聚酰亚胺/二氧化锆(PI/ZrO2)复合纳米纤维膜,在提高纤维膜机械强度的同时还可以提高它对电解液的润湿性,使之进一步适用于锂离子电池隔膜。
发明内容
本发明的目的在于解决现有技术的不足,提供一种简单有效的制备表面包覆二氧化锆纳米层的聚酰亚胺纤维膜的工艺方法。
本发明的另一个目的在于利用表面包覆二氧化锆纳米层的聚酰亚胺纤维膜制备出一种新型锂离子电池隔膜材料,与目前市售的聚烯烃膜相比,具有热稳定性高,机械强度高和对电解液浸润性强等优点。
一种表面包覆二氧化锆纳米层的聚酰亚胺纤维膜的制备方法,其特征在于包括以下步骤:
A:通过静电纺丝法将固含量为5%~30%的聚酰胺酸溶液制得聚酰胺酸纳米纤维膜,并进行热酰亚胺化处理,从室温升温至300℃,保温时间为2h,得到聚酰亚胺纳米纤维膜;
B:将步骤A制得的聚酰亚胺纳米纤维膜置于有机锆盐溶液中浸泡5-30min,取出后在去离子水中超声1-10min,并继续浸泡1-2h;
C:将步骤B处理后的聚酰亚胺纳米纤维膜放入烘箱中,40-70℃恒温处理5-12h,得到表面包覆二氧化锆的聚酰亚胺纳米纤维膜。
其中步骤B中所述的有机锆盐为正丁醇锆、乙酰丙酮锆、三氟乙酰丙酮锆、六氟乙酰丙酮锆,有机锆盐溶液的浓度为5-50wt%。
与现有技术相比,本方法具有以下优良效果:
1.实施工艺过程简单,条件易满足,步骤简便,并且在处理过程中对聚酰亚胺基体纤维无损伤,适用范围广,可用于所有体系的聚酰亚胺纤维膜,易于实现流程化生产,实际应用前景良好。
2.二氧化锆纳米颗粒对聚酰亚胺基体纤维的包覆效率高,形成的二氧化锆无机纳米层的致密性好,粘附性高。
3.提高了聚酰亚胺纳米纤维膜的机械强度。
4.作为锂离子电池隔膜对电解液有很好的浸润性,孔隙率高,耐热性好。
附图说明
图1是按照实施例1制备的表面包覆二氧化锆纳米层的聚酰亚胺纤维膜的扫描电镜图,放大倍数左图200000倍,右图5000倍。
图2是按照实施例2制备的表面包覆二氧化锆纳米层的聚酰亚胺纤维膜的扫描电镜图,放大倍数左图200000倍,右图5000倍。
图3是按照实施例3制备的表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维膜的扫描电镜图,放大倍数左图200000倍,右图5000倍。
图4是按照实施例4制备的表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维膜的扫描电镜图,放大倍数左图200000倍,右图5000倍。
图5是按照实施例5制备的具表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维膜的扫描电镜图,放大倍数左图200000倍,右图5000倍。
具体实施方式
下面结合具体实施例,进一步阐述发明。应该说明的是:以下实施例仅用以说明本发明而并非限制本发明所描述的技术方案。因此,尽管本说明书参照下述的实施例对本发明已进行了详细的说明,但是,本领域的技术人员应当理解,仍然可以对本发明进行修改或等同替换;而一切不脱离本发明的精神和范围的技术方案及其改进,其均应涵盖在本发明的权利要求范围当中。
实施例1
制备PMDA/ODA体系聚酰胺酸纤维膜,热亚胺化后得聚酰亚胺纳米纤维膜,置于8wt%的锆酸四丁酯溶液中浸泡半小时,在去离子水中超声5min再浸泡2h,最后放入烘箱中60℃恒温12h得到表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维膜。(1)称取摩尔比为1:1的均苯四甲酸二酐(PMDA)2.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入PMDA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;将所得聚酰胺酸纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得聚酰亚胺纳米纤维膜。(2)量取1ml锆酸四丁酯,9ml正丁醇,在烧杯中混合均匀。(3)将聚酰亚胺纳米纤维膜浸泡在锆酸四丁酯溶液中30min。(4)将上一步得到的纳米纤维膜在去离子水中超声处理5min再浸泡2h,取出晾干。(5)将上一步处理得到的的纳米纤维膜置于烘箱中,保持60℃恒温处理12h,所得纤维形貌如附图所示。
实施例2
制备PMDA/ODA体系聚酰胺酸纤维膜,热亚胺化后得聚酰亚胺纳米纤维膜,置于4wt%的锆酸四丁酯溶液中浸泡半小时,在去离子水中超声5min再浸泡2h,最后放入烘箱中60℃恒温12h得到表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维膜。(1)称取摩尔比为1:1的均苯四甲酸二酐(PMDA)2.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入PMDA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;将所得聚酰胺酸纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得聚酰亚胺纳米纤维膜。(2)量取0.5ml锆酸四丁酯,9.5ml正丁醇,在烧杯中混合均匀。(3)将聚酰亚胺纳米纤维膜浸泡在锆酸四丁酯溶液中30min。(4)将上一步得到的纳米纤维膜在去离子水中超声处理5min再浸泡2h,取出晾干。(5)将上一步处理得到的的纳米纤维膜置于烘箱中,保持60℃恒温处理12h,所得纤维形貌如附图所示。
实施例3
制备PMDA/ODA体系聚酰胺酸纤维膜,热亚胺化后得聚酰亚胺纳米纤维膜,置于0.8wt%的锆酸四丁酯溶液中浸泡半小时,在去离子水中超声5min再浸泡2h,最后放入烘箱中60℃恒温12h得到表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维膜。(1)称取摩尔比为1:1的均苯四甲酸二酐(PMDA)2.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入PMDA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;将所得聚酰胺酸纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得聚酰亚胺纳米纤维膜。(2)量取0.1ml锆酸四丁酯,9.9ml正丁醇,在烧杯中混合均匀。(3)将聚酰亚胺纳米纤维膜浸泡在锆酸四丁酯溶液中30min。(4)将上一步得到的纳米纤维膜在去离子水中超声处理5min再浸泡2h,取出晾干。(5)将上一步处理得到的的纳米纤维膜置于烘箱中,保持60℃恒温处理12h,所得纤维形貌如附图所示。
实施例4
制备ODPA/ODA体系聚酰胺酸纤维膜,热亚胺化后得聚酰亚胺纳米纤维膜,置于8wt%的锆酸四丁酯溶液中浸泡半小时,在去离子水中超声5min再浸泡2h,最后放入烘箱中60℃恒温12h得到表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维膜。(1)称取摩尔比为1:1的ODPA 2.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入ODPA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;将所得聚酰胺酸纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得聚酰亚胺纳米纤维膜。(2)量取1ml锆酸四丁酯,9ml正丁醇,在烧杯中混合均匀。(3)将聚酰亚胺纳米纤维膜浸泡在锆酸四丁酯溶液中30min。(4)将上一步得到的纳米纤维膜在去离子水中超声处理5min再浸泡2h,取出晾干。(5)将上一步处理得到的的纳米纤维膜置于烘箱中,保持60℃恒温处理12h,所得纤维形貌如附图所示。
实施例5
制备6FDA/ODA体系聚酰胺酸纤维膜,热亚胺化后得聚酰亚胺纳米纤维膜,置于8wt%的锆酸四丁酯溶液中浸泡半小时,在去离子水中超声5min再浸泡2h,最后放入烘箱中60℃恒温12h得到表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维膜。(1)称取摩尔比为1:1的6FDA 4.0g、4,4’-二氨基二苯醚(ODA)1.8g,将ODA全部溶于30ml的N,N-二甲基甲酰胺(DMF)溶剂中,机械搅拌,待ODA全部溶解于DMF后,冰水浴的条件下,分步加入6FDA,得到粘度适中的聚酰胺酸溶液后,机械搅拌2h后,将聚酰胺酸溶液装入20ml的注射器中,应用静电纺丝技术制备出聚酰胺酸纤维膜,静电纺丝机具体参数为纺丝电压:20kV;纺丝温度:室温;纺丝湿度:20%;注射器针头直径:12号;接受辊转速:80.0m/min;接收距离:20cm。将制备出的聚酰胺酸纤维膜置于超净台中12h;将所得聚酰胺酸纤维膜置于热炉中,以2℃/min的升温速度逐步升温至300℃,并保持2h,从而制得聚酰亚胺纳米纤维膜。(2)量取1ml锆酸四丁酯,9ml正丁醇,在烧杯中混合均匀。(3)将聚酰亚胺纳米纤维膜浸泡在锆酸四丁酯溶液中30min。(4)将上一步得到的纳米纤维膜在去离子水中超声处理5min再浸泡2h,取出晾干。(5)将上一步处理得到的的纳米纤维膜置于烘箱中,保持60℃恒温处理12h,所得纤维形貌如附图所示。
Claims (3)
1.一种表面包覆二氧化锆纳米层的聚酰亚胺纤维膜,其特征在于该纳米纤维膜是由表面包覆二氧化锆纳米层的聚酰亚胺纳米纤维堆积而成,其中二氧化锆纳米层的厚度为10~100nm,聚酰亚胺纤维直径为100~800nm;包覆二氧化锆纳米层的聚酰亚胺纤维膜的厚度为10~90μm,孔隙率为30~80%,拉伸强度为5~50MPa。
2.一种表面包覆二氧化锆纳米层的聚酰亚胺纤维膜的制备方法,其特征在于包括以下步骤:
A:通过静电纺丝法将固含量为5%~30%的聚酰胺酸溶液制得聚酰胺酸纳米纤维膜,并进行热酰亚胺化处理,从室温升温至300℃,保温时间为2h,得到聚酰亚胺纳米纤维膜;
B:将步骤A制得的聚酰亚胺纳米纤维膜置于有机锆盐溶液中浸泡5-30min,取出后在去离子水中超声1-10min,并继续浸泡1-2h;
C:将步骤B处理后的聚酰亚胺纳米纤维膜放入烘箱中,40-70℃恒温处理5-12h,得到表面包覆二氧化锆的聚酰亚胺纳米纤维膜。
3.按照权利要求2所述的方法,其特征在于,步骤B中所述的有机锆盐为正丁醇锆、乙酰丙酮锆、三氟乙酰丙酮锆、六氟乙酰丙酮锆中的任意一种或几种,有机锆盐溶液的浓度为5-50wt%。
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