CN106898731A - 一种复合膜及其制备和应用 - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 239000012528 membrane Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000009987 spinning Methods 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 10
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 8
- 239000000446 fuel Substances 0.000 claims abstract description 5
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 5
- 229920005594 polymer fiber Polymers 0.000 claims abstract description 5
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 4
- 239000010439 graphite Substances 0.000 claims abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001523 electrospinning Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- -1 alkene nitrile Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
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- 239000000463 material Substances 0.000 abstract description 34
- 230000005540 biological transmission Effects 0.000 abstract description 3
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
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- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000006250 one-dimensional material Substances 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
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Abstract
一种复合膜,所述复合膜微观上由石墨烯片层和穿插于石墨烯片层中的高分子聚合物纤维构成的网络结构构成;所述高分子聚合物为聚丙烯酸PAA、聚丙烯腈PAN、聚环氧乙烷PEO中的一种;所述石墨烯片层于复合膜中的质量含量为5-90%。本发明设计的复合材料一维材料组分包括了各类纺丝高分子、碳材料、金属氧化物材料等,二维材料主要基于石墨基材料,极大地增加了电极的比表面积,并通过三维多孔结构的构建,有效地强化了电极中的物质传递,同时静电纺丝技术可实现批量化的规模制备,制备过程简单、结构可控、制备效率高,为先进能源技术的高性能、低成本发展提供了新的思路。本方法所制备的材料适用于燃料电池、锂离子电池、超级电容器等多种能源体系。
Description
技术领域
本发明涉及纳米材料制备领域,具体的说涉及复合膜及其制备和应用。
背景技术
包括石墨烯在内的二维纳米材料由于其极为优异的电学性能、机械性能、热学性能以及极大的比表面积,将在未来的能源、环境、材料、生物医药等领域发挥巨大的作用。在先进能源器件领域,如燃料电池、二次电池、超级电容器等,对于电极材料的需求包括大的比表面积、高电子导电性、物质传输顺畅、微纳尺度结构可控等。由于二维纳米材料特殊的结构特征,往往在实际应用中难以同时满足电极材料的需求。因此,石墨烯等材料尽管具有诸多优异的性能,但在电极材料的应用中,还存在诸多的问题亟待解决。例如二维材料的片层堆积与组装,使得气、液、离子等难以实现有效的迁移与传输,制约了电极性能的提高。
鉴于此,开发一种具有三维网络结构的复合纳米材料,可能为二维纳米材料的实际应用提供一种可行的解决思路。目前针对石墨烯等材料的三维结构构建,通常有包括冷冻干燥还原、化学气相沉积、物理气相沉积等,这些方法都实现了二维纳米材料的三维化构建。可由于此类制备手段工艺的复杂性,难以有效实现批量化的放大制备,在电极材料方面的规模化应用仍存在诸多的困难需要解决。
发明内容
本发明针对现有技术的不足,提供了复合膜及其制备方法,本发明采用以下具体方案来实现。
一种复合膜,其特征在于:所述复合膜微观上由石墨烯片层和穿插于石墨烯片层中的高分子聚合物纤维构成的网络结构构成;所述高分子聚合物为聚丙烯酸PAA、聚丙烯腈PAN、聚环氧乙烷PEO中的一种;所述石墨烯片层于复合膜中的质量含量为5-90%。所述相邻石墨片层间的距离为0.5-10nm;所述高分子聚合物纤维的直径为10-500nm。
所述电导率0.1-500S/cm范围内。
所述复合膜的制备方法,包括以下步骤,
(1)纺丝溶液的配制:
于溶剂中加入高分子聚合物和氧化石墨烯粉末得溶液,所述高分子聚合物于溶液中的质量含量为2-20wt.%,持续搅拌至混合均匀得纺丝溶液;
(2)静电纺丝制备:
将步骤(1)所得纺丝溶液置于静电纺丝设备的针管内,纺丝收集基底置于旋转滚轮上进行静电纺丝成膜;所述纺丝过程中针尖偏压为10-50kV,间距5-30cm;进料速率0.01-5mL/min;
(3)还原处理:
采用氢气还原、热处理还原、水合肼还原、硼氢化钠还原中的一种对步骤(2)所得纺丝膜进行还原处理,得一维-二维纳米复合膜。
所述复合膜的制备方法,当步骤(1)所述高分子聚合物为聚丙烯酸PAA时,所述溶剂为水;当步骤(1)所述高分子聚合物为聚丙烯腈PAN时,所述溶剂为乙醇;当步骤(1)所述高分子聚合物为聚环氧乙烷PEO时,所述溶剂为乙醇。
所述复合膜的制备方法,步骤(2)所述静电纺丝的环境温度为5-80℃;旋转滚轮转速为0-500转/min;于纺丝收集基底上收集的纺丝膜的载量为0.1-10mg/cm2时结束纺丝。
当步骤(3)所述还原处理为氢气还原时,于氢气体积为5%的氢氩混合气气氛中、100-500℃条件下进行还原,还原时间为30-240min;还原时氢氩混合气气体流速为10-100mL/min;
当步骤(3)所述还原处理为热处理还原时,于氮气气氛中、300-1000℃条件下进行还原,还原时间为30-240min;还原时氮气气体流速为10-100mL/min;
当步骤(3)所述还原方法为水合肼还原时,将样品于室温条件下置于质量浓度为5-20%的水合肼溶液中,反应时间为10-60min;
当步骤(3)所述还原方法为硼氢化钠还原时,将样品于室温条件下置于摩尔浓度为0.01-5M的硼氢化钠水溶液中,pH值调节至3-11范围内,反应时间为10-60min。
所述复合膜可作为燃料电池气体扩散电极、超级电容器电极或锂离子电池正极使用。
本发明针对目前在能源器件领域对于电极等材料能量密度的较高需求,设计并制备了一种基于静电纺丝技术的复合材料。其中一维材料组分包括了各类纺丝高分子、碳材料、金属氧化物材料等,二维材料主要基于石墨基材料。这种复合结构材料极大地增加了电极的比表面积,并通过三维多孔结构的构建,有效地强化了电极中的物质传递,同时静电纺丝技术可实现批量化的规模制备,制备过程简单、结构可控、制备效率高,为先进能源技术的高性能、低成本发展提供了新的思路。本方法所制备的材料适用于燃料电池、锂离子电池、超级电容器等多种能源体系。
附图说明
图1,纳米复合膜微观结构示意图;
图2,从左至右依次为对比例1、实施例1-4所制备复合材料数码照片;
图3,对比例1(a)与实施例1(b)、2(c、d)所制备复合材料扫描电子显微镜照片。
具体实施方式
实施例1
a.纺丝溶液的配置:
将一定量的PVP粉末按照10wt.%的比例溶解在乙醇中。将采用改进的Hummer法制备的氧化石墨粉末按照5wt.%的比例分散至同样的乙醇中,超声分散1h至均匀。将上述两种分散浆液按照5:1的质量比例混合,持续搅拌至混合均匀。
b.静电纺丝制备:
将上述制备的纺丝溶液置于静电纺丝设备的针管内,纺丝收集基底置于旋转滚轮上,连接好电源后,在一定针尖偏压(30kV)、环境温度与湿度(25摄氏度,50%相对湿度)、滚轮转速(50转每分钟)条件下进行纺丝操作。当基底上纺丝材料达到一定载量(2mg/cm2)后,结束纺丝操作。
c.材料还原后处理
将上述纺丝材料按照需求裁剪成一定尺寸的方块,采用氢气还原法进行还原处理,操作条件为通入5%氢氩气混合气,流速为50mL/min,温度为200摄氏度,还原时间为120min。
实施例2
a.纺丝溶液的配置:
将一定量的PVP粉末按照10wt.%的比例溶解在乙醇中。将采用改进的Hummer法制备的氧化石墨粉末按照5wt.%的比例分散至同样的乙醇中,超声分散1h至均匀。将上述两种分散浆液按照5:2的质量比例混合,持续搅拌至混合均匀。
b.静电纺丝制备:
将上述制备的纺丝溶液置于静电纺丝设备的针管内,纺丝收集基底置于旋转滚轮上,连接好电源后,在一定针尖偏压(30kV)、环境温度与湿度(25摄氏度,50%相对湿度)、滚轮转速(50转每分钟)条件下进行纺丝操作。当基底上纺丝材料达到一定载量(2mg/cm2)后,结束纺丝操作。
c.材料还原后处理
将上述纺丝材料按照需求裁剪成一定尺寸的方块,采用氢气还原法进行还原处理,操作条件为通入5%氢氩气混合气,流速为50mL/min,温度为200摄氏度,还原时间为120min。
实施例3
a.纺丝溶液的配置:
将一定量的PVP粉末按照10wt.%的比例溶解在乙醇中。将采用改进的Hummer法制备的氧化石墨粉末按照5wt.%的比例分散至同样的乙醇中,超声分散1h至均匀。将上述两种分散浆液按照5:3的质量比例混合,持续搅拌至混合均匀。
b.静电纺丝制备:
将上述制备的纺丝溶液置于静电纺丝设备的针管内,纺丝收集基底置于旋转滚轮上,连接好电源后,在一定针尖偏压(30kV)、环境温度与湿度(25摄氏度,50%相对湿度)、滚轮转速(50转每分钟)条件下进行纺丝操作。当基底上纺丝材料达到一定载量(2mg/cm2)后,结束纺丝操作。
c.材料还原后处理
将上述纺丝材料按照需求裁剪成一定尺寸的方块,采用氢气还原法进行还原处理,操作条件为通入5%氢氩气混合气,流速为50mL/min,温度为200摄氏度,还原时间为120min。
实施例4
a.纺丝溶液的配置:
将一定量的PVP粉末按照10wt.%的比例溶解在乙醇中。将采用改进的Hummer法制备的氧化石墨粉末按照5wt.%的比例分散至同样的乙醇中,超声分散1h至均匀。将上述两种分散浆液按照5:4的质量比例混合,持续搅拌至混合均匀。
b.静电纺丝制备:
将上述制备的纺丝溶液置于静电纺丝设备的针管内,纺丝收集基底置于旋转滚轮上,连接好电源后,在一定针尖偏压(30kV)、环境温度与湿度(25摄氏度,50%相对湿度)、滚轮转速(50转每分钟)条件下进行纺丝操作。当基底上纺丝材料达到一定载量(2mg/cm2)后,结束纺丝操作。
c.材料还原后处理
将上述纺丝材料按照需求裁剪成一定尺寸的方块,采用氢气还原法进行还原处理,操作条件为通入5%氢氩气混合气,流速为50mL/min,温度为200摄氏度,还原时间为120min。
对比例1
a.纺丝溶液的配置:
将一定量的PVP粉末按照10wt.%的比例溶解在乙醇中,持续搅拌至溶解均匀。
b.静电纺丝制备:
将上述制备的纺丝溶液置于静电纺丝设备的针管内,纺丝收集基底置于旋转滚轮上,连接好电源后,在一定针尖偏压(30kV)、环境温度与湿度(25摄氏度,50%相对湿度)、滚轮转速(50转每分钟)条件下进行纺丝操作。当基底上纺丝材料达到一定载量(2mg/cm2)后,结束纺丝操作。
实施例5
a.纺丝溶液的配置:
将一定量的PEO粉末按照5wt.%的比例溶解在乙醇中。将采用改进的Hummer法制备的氧化石墨粉末按照10wt.%的比例分散至同样的乙醇中,超声分散4h至均匀。将上述两种分散浆液按照1:1的质量比例混合,持续搅拌至混合均匀。
b.静电纺丝制备:
将上述制备的纺丝溶液置于静电纺丝设备的针管内,纺丝收集基底置于旋转滚轮上,连接好电源后,在一定针尖偏压(50kV)、环境温度与湿度(50摄氏度,50%相对湿度)、滚轮转速(50转每分钟)条件下进行纺丝操作。当基底上纺丝材料达到一定载量(2mg/cm2)后,结束纺丝操作。
c.材料还原后处理
将上述纺丝材料按照需求裁剪成一定尺寸的方块,采用热处理还原法进行还原处理,操作条件为通入高纯氮气,流速为20mL/min,温度为500摄氏度,还原时间为60min。
Claims (8)
1.一种复合膜,其特征在于:所述复合膜微观上由石墨烯片层和穿插于石墨烯片层中的高分子聚合物纤维构成的网络结构构成;所述高分子聚合物为聚丙烯酸PAA、聚丙烯腈PAN、聚环氧乙烷PEO中的一种;所述石墨烯片层于复合膜中的质量含量为5-90%。
2.如权利要求1所述复合膜,其特征在于:所述相邻石墨片层间的距离为0.5-10nm;所述高分子聚合物纤维的直径为10-500nm。
3.如权利要求1所述复合膜,其特征在于:所述电导率为0.1-500S/cm范围内。
4.一种如权利要求1-3任一所述复合膜的制备方法,其特征在于:包括以下步骤,
(1)纺丝溶液的配制:
于溶剂中加入高分子聚合物和氧化石墨烯粉末得溶液,所述高分子聚合物于溶液中的质量含量为2-20wt.%,持续搅拌至混合均匀得纺丝溶液;
(2)静电纺丝制备:
将步骤(1)所得纺丝溶液置于静电纺丝设备的针管内,纺丝收集基底置于旋转滚轮上进行静电纺丝成膜;所述纺丝过程中针尖偏压为10-50kV,间距5-30cm;进料速率0.01-5mL/min;
(3)还原处理:
采用氢气还原、热处理还原、水合肼还原、硼氢化钠还原中的一种对步骤(2)所得纺丝膜进行还原处理,得复合膜。
5.如权利要求4所述复合膜的制备方法,其特征在于:
当步骤(1)所述高分子聚合物为聚丙烯酸PAA时,所述溶剂为水;当步骤(1)所述高分子聚合物为聚丙烯腈PAN时,所述溶剂为乙醇;当步骤(1)所述高分子聚合物为聚环氧乙烷PEO时,所述溶剂为乙醇。
6.如权利要求4所述复合膜的制备方法,其特征在于:
步骤(2)所述静电纺丝的环境温度为5-80℃;旋转滚轮转速为0-500转/min;于纺丝收集基底上收集的纺丝膜的载量为0.1-10mg/cm2时结束纺丝。
7.如权利要求4所述复合膜的制备方法,其特征在于:
当步骤(3)所述还原处理为氢气还原时,于氢气体积为5%的氢氩混合气气氛中、100-500℃条件下进行还原,还原时间为30-240min;还原时氢氩混合气气体流速为10-100mL/min;
当步骤(3)所述还原处理为热处理还原时,于氮气气氛中、300-1000℃条件下进行还原,还原时间为30-240min;还原时氮气气体流速为10-100mL/min;
当步骤(3)所述还原方法为水合肼还原时,将样品于室温条件下置于质量浓度为5-20%的水合肼溶液中,反应时间为10-60min;
当步骤(3)所述还原方法为硼氢化钠还原时,将样品于室温条件下置于摩尔浓度为0.01-5M的硼氢化钠水溶液中,pH值调节至3-11范围内,反应时间为10-60min。
8.一种权利要求1-3任一所述复合膜的应用,其特征在于:所述复合膜可作为燃料电池气体扩散电极、超级电容器电极或锂离子电池正极使用。
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