CN109671514B - 一种柔性透明电极的磁性核壳银纳米线的制备方法 - Google Patents
一种柔性透明电极的磁性核壳银纳米线的制备方法 Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 68
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- 239000002042 Silver nanowire Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 40
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- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 2
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- 229910052709 silver Inorganic materials 0.000 abstract description 21
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- 238000005325 percolation Methods 0.000 abstract description 7
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明涉及柔性电子材料技术领域,具体涉及一种柔性透明电极的磁性核壳银纳米线的制备方法。本发明方法包括准备磁性四氧化三铁纳米线;在磁性四氧化三铁纳米线的表面修饰偶联剂;在经表面修饰后的磁性四氧化三铁纳米线表面原位沉积纳米银层。采用本发明方法制备的电极,由于铁基材料的成本很低,可大幅度降低制备单位银纳米线的材料成本。另外,利用铁基/银核壳纳米线的磁性,在电极表面涂覆时,应用可控磁场引导少量银纳米线在柔性基底有序分布便可形成导电通路,实现低的渗流阈值。
Description
技术领域
本发明涉及柔性电子材料技术领域,具体涉及一种柔性透明电极的磁性核壳银纳米线的制备方法。
背景技术
目前制备银纳米线柔性透明电极面临两大问题:第一,电极表面形成导电通路所需随机分布的银纳米线的量大,即渗流阈值高;第二,形成单位银纳米线所需的银绝对量大。这两个问题直接导致柔性透明电极的高成本,进而限制了其在柔性电子中的大面积应用。
据IDTechEx公司的报告,柔性电子器件在2021年的市场销售额将接近500亿美元。仅在2017年,NanoMarket公司预测仅高端应用所需的柔性透明电极就大于5亿平方米,市值将高达76亿美元,且年增长率为45%。可见,高品质柔性透明电极的市场价值非常巨大。在柔性电子器件中起关键作用的柔性透明电极具有透明、导电、耐弯曲和质轻等特性。目前,氧化铟锡仍作为最成熟的透明电极广泛应用于传统的电子器件,但由于铟元素在地壳中含量低,氧化铟锡质脆且其制备工艺繁琐,难以满足柔性电子的应用需求。在氧化铟锡的潜力替代者中,银纳米线柔性透明电极最具有实际应用潜力。但是,银毕竟为贵金属,其纳米线的制备成本就更高;另外,银纳米线在电极表面随机分布形成导电通路所需的绝对量大,即渗流阈值高,从而进一步增加电极的材料成本,限制了银纳米线柔性透明电极在柔性电子中的大面积应用。所以,降低单位银纳米线的制备成本及银纳米线渗流阈值是必然的趋势。申请号201610028723.1的中国发明专利公开了一种铜/银核壳结构纳米线的制备方法,首先基于乙二胺,硝酸铜和氢氧化钠体系合成的铜纳米线;利用铜对银离子的还原置换作用,在铜纳米线外壳包裹一致密银层即形成核壳结构,用于代替应用于柔性透明电极的银纳米线。申请号201580038664.X的中国发明专利公开了利用哌嗪或六亚甲基二胺的化学法合成铜纳米线,再以化学镀法将银包裹在其表面,经涂覆获取具有良好导电性和透光性的柔性透明电极。
然而,用于柔性透明电极的铜/银核壳纳米线存在以下问题:首先,铜虽为非贵金属,成本比银相对低,但其绝对成本仍是偏高;其次,无法降低纳米线在电极表面的高渗流阈值。所以,铜/银核壳纳米线依然没有解决柔性透明电极的高成本问题。
发明内容
有鉴于此,有必要针对上述的问题,提供一种柔性透明电极的磁性核壳银纳米线的制备方法。本发明目的在于开发一种磁性铁基/银核壳纳米线,由于铁基材料的成本很低,可大幅度降低制备单位银纳米线的材料成本。另外,利用铁基/银核壳纳米线的磁性,在电极表面涂覆时,应用可控磁场引导少量银纳米线在柔性基底有序分布便可形成导电通路,实现低的渗流阈值。因此,基于磁性铁基/银核壳纳米线,可获取低成本的柔性透明电极。
为实现上述目的,本发明采取以下的技术方案:
本发明的柔性透明电极的磁性核壳银纳米线的制备方法,包括:
步骤1:准备磁性四氧化三铁纳米线;
步骤2:在磁性四氧化三铁纳米线的表面修饰偶联剂;
步骤3:在经表面修饰后的磁性四氧化三铁纳米线表面原位沉积纳米银层。
进一步的,步骤1所述的磁性四氧化三铁纳米线,具体由下述方式制备而得:将聚乙二醇、硫代硫酸盐、铁盐、氢氧化钠按质量比100∶2~7∶5~20∶10~35,室温搅拌混合形成铁基纳米线前驱体液;
将所得的铁基纳米线前驱体液转移至反应釜中,混合、干燥、洗涤干净后待用。更具体地,将铁基纳米线前驱体液转移至反应釜中,常温搅拌15min,随后置于干燥箱恒温120℃干燥24h,待冷却后,将产物磁性四氧化三铁纳米线分别用水和乙醇离心洗涤三次。
优选地,步骤1)所述的聚乙二醇的重均分子量为200~2000。
优选地,步骤1)所述的硫代硫酸盐为硫代硫酸钠、硫代硫酸钾、硫代硫酸铵中的一种。
优选地,步骤1)所述的铁盐为硫酸亚铁、硝酸亚铁、磷酸亚铁的一种。
进一步的,步骤2)所述在磁性四氧化三铁纳米线的表面修饰偶联剂,具体为:将水、乙醇、硅烷偶联剂按体积比25∶10~30∶0.6~1.5,于室温搅拌混合形成表面修饰液;
将磁性四氧化三铁纳米线与所述的表面修饰液加热搅拌一段时间,随后洗涤干净待用。更具体地,磁性四氧化三铁纳米线与表面修饰液加热搅拌、洗涤为:于50℃恒温下搅拌24h,分别用水和乙醇离心洗涤三次。
优选地,所述的硅烷偶联剂为氨丙基三乙氧基硅烷、甲基乙烯基二甲基硅烷、3-异氰酸丙基三甲氧基硅烷或3-哌嗪基丙基甲基二甲氧基硅烷中的一种或两种。
进一步的,步骤3)所述磁性四氧化三铁纳米线表面原位沉积纳米银层,具体为:将水与银盐按质量比10∶0.2~0.9,室温搅拌混合后,调节酸碱度pH至9~13,形成纳米银前驱体液;
向经偶联剂表面修饰的磁性四氧化三铁纳米线加入按体积比为1∶0.6~1.2的乙醇水溶液调节铁元素浓度至0.01-0.05mmol/L,并分散,加入5mL所述纳米银前驱体液恒温35~60℃下搅拌2-4h,随后缓慢滴加10mL的弱还原剂溶液,并恒温45-70℃搅拌1~5h。期间,银缓慢均匀在磁性四氧化三铁纳米线表面还原沉积,制备出具有磁性的四氧化三铁/银核壳纳米线。
优选地,步骤3)所述的银盐为硫酸银、硝酸银、碳酸银的一种。
优选地,步骤3)所述的弱还原剂为柠檬酸、葡萄糖、抗坏血酸、壳聚糖中的一种,其溶液的浓度为0.1~0.4mol/L。
优选地,步骤3)所述乙醇水溶液为水和乙醇等体积混合物。
本发明突出的特点和有益效果为:
本发明由于铁基材料的成本很低,可大幅度降低制备单位银纳米线的材料成本;利用铁基/银核壳纳米线的磁性,在表面涂覆时,应用可控磁场引导少量银纳米线在柔性基底有序分布,便可形成导电通路,实现低的渗流阈值。因此,基于磁性四氧化三铁/银核壳纳米线可获取低成本柔性透明电极。
附图说明
图1为磁性四氧化三铁纳米线的扫描电子显微镜图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将结合本发明实施例,对本发明的技术方案作进一步清楚、完整地描述。需要说明的是,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明可先分别配制铁基纳米线前驱体液、表面修饰液、纳米银前驱体液。采用水热法将铁基纳米线前驱体液转化为磁性四氧化三铁纳米线;通过表面修饰液处理,在四氧化三铁纳米线表面引入分子桥;在纳米银前驱体液中,弱还原剂在经表面修饰的四氧化三铁纳米线表面原位沉积纳米银层,最终形成具有磁性的银核壳纳米线。具体操作实例如下:
实施例1
将15g聚乙二醇-1000、0.9g硫代硫酸钠、2.0g硫酸亚铁、2.8g氢氧化钠室温搅拌混合形成铁基纳米线前驱体液;将25mL水、25mL乙醇、0.7mL氨丙基三乙氧基硅烷室温搅拌混合形成表面修饰液;将5mL水与0.5g硝酸银室温搅拌混合后,滴加1mol/L氢氧化钠溶液调节酸碱度pH至12,形成纳米银前驱体液;将铁基纳米线前驱体液转移至反应釜中常温搅拌15min,随后置于干燥箱恒温120℃干燥24h,待冷却后,将产物磁性四氧化三铁纳米线(图1)分别用水和乙醇离心洗涤三次;将磁性四氧化三铁纳米线与表面修饰液恒温50℃下搅拌24h,随后分别用水和乙醇离心洗涤三次;经表面修饰的磁性四氧化三铁纳米线加入等体积混合的水和乙醇调节铁元素浓度至0.02mmol/L,超声分散1h,加入5mL纳米银前驱体液恒温50℃下搅拌3h,随后用恒压滴斗缓慢滴加10mL的0.1mol/L葡萄糖溶液,并恒温50℃搅拌1.5h。最终,制备出具有磁性的四氧化三铁/银核壳纳米线,纳米银层的厚度与四氧化三铁纳米线直径比为1∶1.5~5。
实施例2
将15g聚乙二醇-600、0.9g硫代硫酸钠、1.0g硝酸亚铁、2.8g氢氧化钠室温搅拌混合形成铁基纳米线前驱体液;将25mL水、25mL乙醇、0.7mL氨丙基三乙氧基硅烷室温搅拌混合形成表面修饰液;将5mL水与0.5g硝酸银室温搅拌混合后,滴加1mol/L氢氧化钠溶液调节酸碱度pH至12,形成纳米银前驱体液;将铁基纳米线前驱体液转移至反应釜中常温搅拌15min,随后置于干燥箱恒温120℃干燥24h,待冷却后,将产物磁性四氧化三铁纳米线分别用水和乙醇离心洗涤三次;将磁性四氧化三铁纳米线与表面修饰液恒温50℃下搅拌24h,随后分别用水和乙醇离心洗涤三次;经表面修饰的磁性四氧化三铁纳米线加入等体积混合的水和乙醇调节铁元素浓度至0.02mmol/L,超声分散1h,加入5mL纳米银前驱体液恒温50℃下搅拌3h,随后用恒压滴斗缓慢滴加10mL的0.1mol/L壳聚糖溶液,并恒温50℃搅拌3h。最终,制备出具有磁性的四氧化三铁/银核壳纳米线。
实施例3
将15g聚乙二醇-2000、0.7g硫代硫酸胺、2.0g硫酸亚铁、2.8g氢氧化钠室温搅拌混合形成铁基纳米线前驱体液;将25mL水、25mL乙醇、0.5mL3-哌嗪基丙基甲基二甲氧基硅烷室温搅拌混合形成表面修饰液;将5mL水与0.5g硝酸银室温搅拌混合后,滴加1mol/L氢氧化钠溶液调节酸碱度pH至9,形成纳米银前驱体液;将铁基纳米线前驱体液转移至反应釜中常温搅拌15min,随后置于干燥箱恒温120℃干燥24h,待冷却后,将产物磁性四氧化三铁纳米线分别用水和乙醇离心洗涤三次;将磁性四氧化三铁纳米线与表面修饰液恒温50℃下搅拌24h,随后分别用水和乙醇离心洗涤三次;经表面修饰的磁性四氧化三铁纳米线加入等体积混合的水和乙醇调节铁元素浓度至0.02mmol/L,超声分散1h,加入5mL纳米银前驱体液恒温50℃下搅拌3h,随后用恒压滴斗缓慢滴加10mL的0.2mol/L柠檬酸溶液,并恒温50℃搅拌1.5h。最终,制备出具有磁性的四氧化三铁/银核壳纳米线。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对本发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (8)
1.一种柔性透明电极的磁性核壳银纳米线的制备方法,其特征在于,包括:
步骤1:准备磁性四氧化三铁纳米线;
步骤2:在磁性四氧化三铁纳米线的表面修饰偶联剂;
所述在磁性四氧化三铁纳米线的表面修饰偶联剂,具体为:将水、乙醇、硅烷偶联剂按体积比25:10~30:0.6~1.5,于室温搅拌混合形成表面修饰液;
将磁性四氧化三铁纳米线与所述的表面修饰液加热搅拌一段时间,随后洗涤干净待用;
步骤3:在经表面修饰后的磁性四氧化三铁纳米线表面原位沉积纳米银层;
所述磁性四氧化三铁纳米线表面原位沉积纳米银层,具体为:将水与银盐按质量比10:0.2~0.9,室温搅拌混合后,调节酸碱度pH至9~13,形成纳米银前驱体液;
向经偶联剂表面修饰的磁性四氧化三铁纳米线加入按体积比为1:0.6~1.2的乙醇水溶液调节铁元素浓度至0.01-0.05mmol/L,并分散,加入5mL所述纳米银前驱体液恒温35~60℃下搅拌2-4h,随后缓慢滴加10mL的弱还原剂溶液,并恒温45-70℃搅拌1~5h。
2.根据权利要求1所述的柔性透明电极的磁性核壳银纳米线的制备方法,其特征在于,步骤1所述的磁性四氧化三铁纳米线,具体由下述方式制备而得:将聚乙二醇、硫代硫酸盐、铁盐、氢氧化钠按质量比100:2~7:5~20:10~35,室温搅拌混合形成铁基纳米线前驱体液;
将所得的铁基纳米线前驱体液转移至反应釜中,混合、干燥、洗涤干净后待用。
3.根据权利要求2所述的柔性透明电极的磁性核壳银纳米线的制备方法,其特征在于,所述的聚乙二醇的重均分子量为200~2000。
4.根据权利要求2所述的柔性透明电极的磁性核壳银纳米线的制备方法,其特征在于,所述的硫代硫酸盐为硫代硫酸钠、硫代硫酸钾、硫代硫酸铵中的一种。
5.根据权利要求2所述的柔性透明电极的磁性核壳银纳米线的制备方法,其特征在于,所述的铁盐为硫酸亚铁、硝酸亚铁、磷酸亚铁的一种。
6.根据权利要求1所述的柔性透明电极的磁性核壳银纳米线的制备方法,其特征在于,所述的硅烷偶联剂为氨丙基三乙氧基硅烷、甲基乙烯基二甲基硅烷、3-异氰酸丙基三甲氧基硅烷或3-哌嗪基丙基甲基二甲氧基硅烷中的一种或两种。
7.根据权利要求1所述的柔性透明电极的磁性核壳银纳米线的制备方法,其特征在于,所述的银盐为硫酸银、硝酸银、碳酸银的一种。
8.根据权利要求1所述的柔性透明电极的磁性核壳银纳米线的制备方法,其特征在于,所述的弱还原剂为柠檬酸、葡萄糖、抗坏血酸、壳聚糖中的一种,其溶液的浓度为0.1~0.4mol/L。
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