CN102695824A - 生产纳米纤维的方法 - Google Patents

生产纳米纤维的方法 Download PDF

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Publication number
CN102695824A
CN102695824A CN201080060429XA CN201080060429A CN102695824A CN 102695824 A CN102695824 A CN 102695824A CN 201080060429X A CN201080060429X A CN 201080060429XA CN 201080060429 A CN201080060429 A CN 201080060429A CN 102695824 A CN102695824 A CN 102695824A
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processing step
metal
solution
solvent
alcohol
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R·津巴
F·梅杰
E·克里莫夫
A·特劳特
R·奥斯特曼
L·波狄埃
B·斯马尔斯里
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BASF SE
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BASF SE
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Abstract

本发明涉及一种使用溶胶-凝胶前体生产金属氧化物纳米纤维的方法。与现有技术相比，通过本发明方法生产的纳米纤维的区别在于增加了金属氧化物含量。

Description

生产纳米纤维的方法
本发明涉及一种使用溶胶-凝胶前体生产金属氧化物纳米纤维的方法。通过本发明方法生产的“绿色纤维”值得注意的是其与现有技术相比增加的无机物含量，其中所述纤维包含聚合物组分和无机内容物且具有或不具有溶剂残留物。在本发明方法中，煅烧、热去除聚合物组分并将无机内容物转变为所需金属氧化物产生了本发明金属氧化物纳米纤维。
纳米纤维例如作为过滤和分离介质，在织物生产、光学、电子学、生物技术、药学、药物和塑料技术中的重要性正在提高。术语“纳米纤维”指直径在约0.1-999nm范围内(也称作纳米级)的纤维结构。术语进一步涉及纳米结构，如纳米线和纳米管，这两种都具有纳米级横截面。
生产纳米纤维的目前常规的方法已知为电纺丝。这包括借助两个电极将包含金属化合物如金属盐以及合适的话其它添加剂的聚合物溶液或聚合物熔体引入强电场。静电荷导致溶液中局部不稳定，其首先成型为锥形结构，随后成型为纤维。当纤维在电极方向上移动时，大部分溶剂蒸发且纤维额外伸展。在纤维随后煅烧的过程中，金属化合物转变为相应的金属氧化物。以该方式获得了直径<1μm的氧化纳米纤维。这类纤维例如在过滤应用中，作为气体传感器组件以及在催化剂应用中的用途具有工业意义。
纳米纤维，特别是ZnO纳米纤维的生产例如由Siddheswaran等人描述(“preparation and characterisation of ZnO nanofibers byelectrospinning“，Cryst.Rest.Technol.2006，41，447-449)。Siddheswaran等人首先制备了包含聚乙烯醇、乙酸锌和水的前体溶液，将其在升高的温度下转变为粘性凝胶。随后，用基于注射器的电纺丝单元(“针状电纺丝”)将该前体溶液纺成纳米纤维。随后将这些纳米纤维煅烧为ZnO纤维。通过该方法生产的ZnO纳米纤维具有非常不均匀的表面结构和变化的直径且在接触位置相互融合，这额外导致低的长宽比。
制备SnO2纳米纤维的方法由Zhang等人描述(“fabrication andethanol-sensing properties of micro gas sensor based on electrospunSnO2-nanofibers“，Sensors and Actuators B 2008，67-73)。Zhang等人制备了包含聚乙烯醇、氯化锡(IV)和水的前体溶液，且用电纺丝单元将其纺丝以产生纳米纤维。随后将这些纳米纤维煅烧以产生SnO2纳米纤维。借助该方法产生的SnO2纳米纤维具有变化的直径且同样在接触位置相互融合，这导致低的长宽比且额外导致令人不满意的金属负载。
本发明的目的为提供一种生产直径为0.1-999nm的金属氧化物纳米纤维的改进方法。本发明的另一目的为提供一种生产金属氧化物纤维的方法，借助该方法可获得具有高的无机物含量的绿色纤维，随后将其煅烧。
该目的通过用于生产直径为0.1-999nm的金属氧化物纤维的方法实现，其包括以下步骤：
(a)提供一种或多种金属化合物在至少一种选自以下的溶剂中的溶液：水、乙醇、甲醇、异丙醇、正丙醇、四氢呋喃和二甲基甲酰胺，
(b)使存在于金属化合物中的所述至少一种金属以其氢氧化物的形式从(a)中提供的溶液中碱性沉淀，以获得悬浮液，
(c)取出工艺步骤(b)中沉淀的所述至少一种氢氧化物，
(d)将在工艺步骤(c)中取出的所述至少一种氢氧化物再分散或溶解在胺或溶剂-胺混合物中，以获得溶胶-凝胶前体，
(e)制备包含一种或多种聚合物，一种或多种溶剂以及在工艺步骤(d)中获得的溶胶-凝胶前体的溶液，
(f)将在工艺步骤(e)中制备的溶液电纺丝，和
(g)除去聚合物。
借助上述方法，发现可获得直径在纳米范围内的金属氧化物纤维。与现有技术已知的绿色纤维相比，在工艺步骤(f)中生产的“绿色纤维”具有增加的无机物含量。为电纺丝步骤制备的溶液具有高的水解稳定性-在空气中可储存约12月的时间。这是特别有利的，因为当在工艺步骤(g)中除去聚合物时，例如在煅烧中的质量损失因此较低。此外，在工艺步骤(g)中获得的纤维具有较低的孔隙度和粗糙度。由于在工艺步骤(f)之后无机组分已经以(交联的)金属氢氧化物形式存在且因此与在该方法初期所需的金属氧化物形式非常相似，这增强了该效果。在工艺步骤(b)、(c)和(e)中制备的金属氢氧化物的特定前体溶液的使用能够生产具有相应高金属含量的绿色纤维。
在工艺步骤(a)中一种或多种金属化合物的溶液的制备中，将金属化合物或多种金属化合物溶解在选自水、乙醇、异丙醇、正丙醇、四氢呋喃(THF)和二甲基甲酰胺的溶剂中，或两种、三种或更多种上述溶剂的混合物中。溶解在溶剂中的金属化合物的量可在宽的范围内变化。通常而言，存在于金属化合物中的金属离子在溶液中的浓度为0.1-7mol/l，优选0.2-1mol/l。就本发明而言，术语“金属化合物”指其中金属与有机或无机配体阴离子或共价键接的化合物。所述至少一种金属化合物例如为选自以下的一种或多种金属的无机或有机化合物或盐：Cu、Ag、Au、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Ni、Pd、Co、Rh、Ir、Sb、Sn、In、Al、Ga、Er和Zn。在本发明的优选实施方案中，金属化合物的金属选自Sb、Sn、In、Al、Ga和Zn。在特别优选的实施方案中，混合物包含金属Sn、Sb或In的化合物，或混合物包含金属Sn和Sb的化合物。
就本发明而言，如果有机阴离子和特定金属阳离子的这些组合存在，则无机化合物例如为氯化物、硫酸盐和硝酸盐。就本发明而言，如果有机阴离子和特定金属阳离子的组合存在，则有机化合物为羧酸的盐，如具有相应金属的甲酸盐、乙酸盐、柠檬酸盐和乙酰基丙酮化物。
在工艺步骤(a)提供一种或多种金属化合物的溶液或其制备之后，所述至少一种金属离子以其氢氧化物的形式碱性沉淀在工艺步骤(b)中进行。在工艺步骤(b)中，所述至少一种金属或金属离子的碱性沉淀通过加入至少一种铵化合物和/或至少一种碱金属氢氧化物而进行。可用于碱性沉淀的化合物通常选自其中R独立地为H或C1-C4烷基的NR4OH、NH4OH、NH3、NaOH、KOH、NH4HCO3和(NH4)2CO3、NH4F、NaF、KF和LiF，或两种、三种或更多种上述化合物的混合物。在工艺步骤(b)中铵化合物和/或碱金属氢氧化物的加入将工艺步骤(a)中提供的溶液的pH调节至8-12，优选9-10的pH。进行碱性沉淀所需的铵化合物或碱金属氢氧化物的量可在宽的范围内变化。本领域熟练技术人员使用合适的量，以使pH建立在上文规定的范围内且金属离子以其氢氧化物的形式从溶液中沉淀出来。
在本发明的优选实施方案中，在工艺步骤(b)中碱性沉淀进行之前，将至少一种选自氨基酸，如丙氨酸、苯丙氨酸、缬氨酸、亮氨酸和ε-己内酰胺的稳定剂加入溶液中。该稳定剂的比例可在宽的范围内变化且通常基于工艺步骤(a)中提供的溶液为0.5-10重量%，优选1-5重量%。
在本发明的另一优选实施方案中，将在工艺步骤(b)的碱性沉淀之后获得的悬浮液在60-200℃的温度下，优选在100-160℃的温度下，经1-24小时时间，优选经2-6小时时间，以及在1-2巴绝对压力下处理。这导致金属氧化物前体的悬浮液呈结晶形式。同样可将该悬浮液以1-99重量%的比例加入工艺步骤(e)中制备的混合物中。在本发明的另一优选实施方案中，该中间步骤，即金属氧化物前体的分散体的制备在选自丙氨酸、苯丙氨酸、缬氨酸、亮氨酸和ε-己内酰胺的稳定剂存在下进行。
在工艺步骤(b)中进行碱性沉淀之后，在随后的工艺步骤(c)中取出沉淀的氢氧化物。借助过滤、倾析和/或离心法从母液中取出氢氧化物。从母液中取出沉淀固体的方法是本领域熟练技术人员已知的且不在这里详细说明。
在本发明的优选实施方案中，将工艺步骤(c)中取出的金属氢氧化物洗涤。就洗涤而言，通常使用选自水、甲醇、乙醇、异丙醇和正丙醇或其混合物的溶剂。这例如从金属氢氧化物中除去了铵离子、碱金属离子和氯离子。为完全除去金属氢氧化物中可能的破坏组分，洗涤操作可重复超过一次。在优选实施方案中，用于洗涤的溶剂或溶剂混合物的pH相应于工艺步骤(b)中碱性沉淀进行时的pH。
在工艺步骤(c)中取出金属氢氧化物之后或在任选的洗涤步骤之后，将沉淀物或金属氢氧化物溶解在胺，或优选溶剂-胺混合物中。在本发明的优选实施方案中，溶剂-胺混合物中的溶剂选自水、甲醇、乙醇、异丙醇、正丙醇、四氢呋喃(THF)和二甲基甲酰胺或其混合物；溶剂更优选为水。存在于溶剂-胺混合物中的胺通常为通式NR3的伯、仲或叔胺，其中R独立地为H、具有1-6个，优选2-4个，更优选两个碳原子的取代或未被取代的直链或支化烷基。
“烷基”指可为直链或支化且可在链中具有1-6个碳原子的饱和脂族烃基。“支化”指低级烷基，如甲基、乙基或丙基与线性烷基链相连。烷基例如为甲基、乙基、1-丙基、2-丙基、1-丁基、2-丁基、2-甲基-1-丙基(异丁基)、2-甲基-2-丙基(叔丁基)、1-戊基、2-戊基、3-戊基、2-甲基-1-丁基、3-甲基-1-丁基、2-甲基-2-丁基、3-甲基-2-丁基、2,2-二甲基-1-丙基、1-己基、2-己基、3-己基、2-甲基-1-戊基和3-甲基-1-戊基。特别优选乙基和丙基。
在本发明的特别优选的实施方案中，胺为二乙胺。
溶剂与胺的重量比可在宽度范围内变化且通常为5-10:1-5，优选7-8:3-2。金属氢氧化物的浓度通常为5-30重量%，优选10-20重量%；该比例更优选为15重量%，基于工艺步骤(d)中制备的溶液或分散体的总质量。
将在工艺步骤(d)中制备的混合物(也称作溶胶-凝胶前体)与用于金属氧化物纳米纤维生产的常规溶剂在两个浓度范围内混溶。另外，前体中多种氢氧化物的存在导致氢氧化物的良好混合，这导致随后生产的纳米纤维中非常均匀的金属分布。在本发明方法中使用所谓的溶胶-凝胶前体是有利的，因为电纺丝几乎总是提供相同量的绿色纤维。
在工艺步骤(e)中，制备包含一种或多种聚合物，一种或多种溶剂和在工艺步骤(d)中制备的混合物，溶胶-凝胶前体的溶液，随后由其生产金属氧化物纳米纤维。通常而言，在工艺步骤(e)中，选择溶剂或溶剂混合物，以使所述一种或多种聚合物和溶胶-凝胶前体均可溶于其中。“可溶”应理解为是指聚合物和溶胶-凝胶前体在相应的溶剂或溶剂混合物中各自具有至少1重量%的溶解度。本领域熟练技术人员已知的是，为此必须使聚合物，溶胶-凝胶前体和溶剂的性能相互平衡。这可借助通常的技术知识进行。
通常而言，用于工艺步骤(e)的溶剂选自水、甲醇、乙醇、乙二醇、正丙醇、2-丙醇、正丁醇、异丁醇、叔丁醇、环己醇、甲酸、乙酸、三氟乙酸、二乙胺、二异丙胺、苯乙胺、丙酮、乙酰丙酮、乙腈、二甘醇、甲酰胺、二甲基甲酰胺(DMF)、二甲亚砜(DMSO)、甲苯、二甲基乙酰胺、N-甲基吡咯烷酮(NMP)和四氢呋喃，或为两种或更多种上述溶剂的混合物。用于在工艺步骤(e)中制备溶液的溶剂优选为选自水、甲醇、乙醇、乙二醇和异丙醇的一种或多种。
用于在工艺步骤(e)中制备溶液的聚合物通常选自聚醚、聚氧化乙烯、聚乙烯醇、聚乙酸乙烯酯、聚乙烯基吡咯烷酮、聚丙烯酸、聚氨酯、聚交酯、聚糖苷、聚乙烯基甲酰胺、聚乙烯胺、聚乙烯亚胺和聚丙烯腈，或为两种或更多种上述聚合物的混合物。优选聚合物已经发现为聚乙烯醇、聚乙酸乙烯酯、聚乙烯基吡咯烷酮。上述聚合物的共聚物已经发现是合适的，如聚乙烯醇-聚乙酸乙烯酯共聚物或共聚物的混合物。
通常而言，就本发明而言，所述一种聚合物或多种聚合物包括可通过热、化学、辐射、物理、生物、等离子体、超声法或通过用溶剂萃取而降解的聚合物材料。在工艺步骤(e)中制备的溶液中聚合物的比例可在较宽范围内变化。通常而言，聚合物的比例基于在工艺步骤(e)中制备的溶液为1-20重量%，优选5-15重量%，更优选6-10重量%。
溶胶-凝胶前体的比例基于工艺步骤(e)中制备的溶液通常为1-20重量%，优选5-10重量%，更优选6-10重量%。
在工艺步骤(e)中制备的溶液的残留组分由溶剂或由溶剂和存在的任何其它添加剂形成。
在本发明的一个实施方案中，将平均粒度通常为1-100nm的结晶和/或无定形金属氧化物纳米颗粒加入在工艺步骤(e)制备的溶液中。所加入颗粒的比例基于在工艺步骤(e)中制备的溶液或悬浮液为1-99重量%，优选1-40重量%，更优选1-20重量%。在优选实施方案中，结晶的金属氧化物纳米颗粒为ATO颗粒(锑掺杂的氧化锡颗粒)和/或ITO颗粒(锡掺杂的氧化铟颗粒)。
在本发明的一个实施方案中，将平均粒度通常为1-100nm的结晶和/或无定形金属纳米颗粒加入在工艺步骤(e)中制备的溶液。所加入颗粒的比例基于在工艺步骤(e)中制备的溶液为1-99重量%。在优选实施方案中，纳米颗粒为银、金、铜或铝的颗粒。
纳米纤维(包含一种或多种聚合物，一种或多种金属氧化物前体)借助从工艺步骤(e)中制备的溶液电纺丝而由该溶液生产。电纺丝方法是本领域熟练技术人员已知的。电纺丝例如可用电纺丝单元进行，该单元的构造与文献(Xia等人，Advanced Materials 2004，16，1151)中所述电纺丝单元相同或相似。电纺丝也可用例如在WO 2006/131081A1或WO 2007/137530A2中描述的电纺丝单元进行。
在本发明方法的工艺步骤(g)中聚合物的去除通常通过热、化学、辐射、物理、生物、等离子体、超声法或通过用溶剂萃取而完成。聚合物的去除优选借助煅烧而热完成。煅烧通常经1-24小时，优选经3-6小时，在250-900℃的温度下，优选在300-800℃的温度下，更优选在400-700℃的温度下进行。气氛通常可为空气气氛，以及可额外包含氧气或氢气的氮气气氛。在本发明的优选实施方案中，煅烧在约78体积%氮气，21体积%氧气的气氛或在纯氮气或在氮气与氢气(1-4体积%)的混合物或在氮气与氧气(>21体积%)的混合物中进行。煅烧之后获得的金属氧化物纤维的直径为0.1-999nm，优选10-300nm，优选50-200nm。长宽比为10-1000，优选100-500。
在本发明的优选实施方案中，将纳米纤维在电纺丝之后和煅烧之前干燥。纳米纤维通常在80-180℃的温度下，优选在100-150℃的温度下，在环境气氛下，在空气中或在减压下干燥。
在本发明的另一实施方案中，提供了一种生产金属纤维的方法，其中将在工艺步骤(g)中产生的金属氧化物纤维还原为相应的金属纤维。如何将金属氧化物还原为相应的金属是本领域熟练技术人员通常已知的。合适的还原剂为氢气、一氧化碳、气态烃、碳以及与待还原金属相比较不贵重，即具有更负标准电势的金属，以及额外地为硼氢化钠、氢化铝锂、醇和醛。在本发明的另一实施方案中，可将金属氧化物纤维电化学还原或部分还原。本领域熟练技术人员可借助通常的技术知识使用这些还原方法，并因此获得了直径<1μm的相应金属纤维。
纳米纤维也可用于金属氧化物和金属的电化学沉积。
所获得的纳米纤维具有多种令人关注的磁、电和催化性能，这使它们在其实际应用中非常有用。因此，它们有望使新材料用于微电子和光电子中不同组件。还存在各种在催化或过滤中应用的可能性。因此，本发明进一步提供了本发明金属氧化物纤维作为用于聚合物，用于机械增强，用于抗静电/导电改性，用于阻燃性，用于聚合物热导性改进的添加剂的用途；以及作为用于气体和液体过滤，特别是高温过滤的过滤器和过滤部件的组件的用途，作为催化剂组件的用途；作为锂离子电池、太阳能电池、燃料电池的组件和其它电子部件/元件的用途。
通过以下实施例详细阐述本发明：
实施例1：ATO(氧化锡锑)纳米纤维的合成
如下制备包含6.7重量%PVP(Kollidon 92F，来自BASF SE)，6.7重量%ATO前体，26.4重量%水，48.9重量%乙醇和11.3重量%二乙胺的溶胶-凝胶前体溶液：
将200g 25重量%氢氧化铵水溶液引入玻璃烧瓶。当激烈搅拌时，加入78.4g氯化锡(IV)和5.2g氯化锑(III)在960g乙醇和16g浓缩HCl中的溶液。将所形成的沉淀借助离心机取出并用pH为10(用氨溶液设定)的水洗涤4次，并每次用Ultraturrax再分散。将所获得的沉淀溶解在水和二乙胺的7:3混合物中，以获得15重量%(基于金属氧化物含量)ATO前体溶液。将200g上述ATO前体溶液用200g 15%PVP在乙醇中的溶液溶解，然后加入50ml乙醇。所得溶液具有以下特征：
粘度(23.5℃):0.22Pa x s
电导率(23.5℃):383μS/cm
该溶液的电纺丝使用Nanospider单元进行(NS Lab 500S，来自Elmarco，Czech Republic)。电极类型：6-线电极；电极间距25cm；电压：82kV。
将所得纤维(已知为绿色纤维)在空气气氛下煅烧。为此，以5℃/分钟的加热速率将它们加热至550℃并将该550℃的温度保持两小时，以获得呈浅蓝色固体形式的ATO纳米纤维。
纤维的平均直径为100-130nm。
长宽比(长度/直径)：>>100:1
比电导率：0.9S/cm，通过四点法在包含ATO纤维和3重量%PVDF(粘合剂)的压片上测量
实施例2：ATO(氧化锡锑)纳米纤维的合成
如下制备包含6.7重量%PVP(Kollidon 92F，来自BASF SE)，6.7重量%ATO前体，26.4重量%水，48.9重量%乙醇和11.3重量%二乙胺的溶胶-凝胶前体溶液：
当激烈搅拌时，制备66g氯化锡(IV)和5.8g氯化锑(III)和2.24g ε-己内酰胺在560g水中的溶液。将该溶液加热至50℃，并在该温度下加入142g 25重量%氢氧化铵水溶液。将所得悬浮液在50℃下搅拌10小时。将所形成的沉淀借助离心机取出并用pH为10(用氨溶液设定)的水洗涤4次，并每次用Ultraturrax再分散。将所获得的沉淀溶解在水和二乙胺的7:3混合物中，以获得15重量%(基于金属氧化物含量)ATO前体溶液。将200g上述ATO前体溶液用200g 15%PVP在乙醇中的溶液溶解，然后加入50ml乙醇。所得溶液具有以下特征：
粘度(23.5℃):0.22Pa.s
电导率(23.5℃):383μS/cm
电纺丝使用Nanospider单元进行(NS Lab 500S，来自Elmarco，CzechRepublic)。电极类型：6-线电极；电极间距25cm；电压：82kV。
将所得纤维(已知为绿色纤维)在空气气氛下煅烧。为此，以5℃/分钟的加热速率将它们加热至550℃并将该550℃的温度保持两小时，以获得呈浅蓝色固体形式的ATO纳米纤维。
实施例3：ATO(氧化锡锑)纳米纤维的合成
如下制备包含6.7重量%PVP(Kollidon 92F，来自BASF SE)，6.7重量%ATO前体，26.4重量%水，48.9重量%乙醇和11.3重量%二乙胺的溶胶-凝胶前体溶液：
将200g 25重量%包含16.9g DL-丙氨酸的氢氧化铵水溶液引入玻璃烧瓶。当激烈搅拌时，加入78.4g氯化锡(IV)和5.2g氯化锑(III)在960g乙醇和16g浓缩HCl中的溶液。然后在高压釜中经3.5小时将所形成的悬浮液加热至150℃。在冷却之后，将沉淀借助离心机取出并用水洗涤4次，并每次用Ultraturrax再分散。将所获得的沉淀溶解在水和二乙胺的7:3混合物中，以获得15重量%(基于金属氧化物含量)ATO前体溶液。将200g上述ATO前体溶液用200g 15%PVP在乙醇中的溶液溶解，然后加入50ml乙醇。
电纺丝使用Nanospider单元进行(NS Lab 500S，来自Elmarco，CzechRepublic)。电极类型：6-线电极；电极间距25cm；电压：82kV。
将所得纤维(已知为绿色纤维)在空气气氛下煅烧。为此，以5℃/分钟的加热速率将它们加热至550℃并将该550℃的温度保持两小时，以获得呈浅蓝色固体形式的ATO纳米纤维。
实施例4：ATO(氧化锡锑)纳米纤维的合成
如下制备包含6.7重量%PVP(Kollidon 92F，来自BASF SE)，6.7重量%ATO前体，26.4重量%水，48.9重量%乙醇和11.3重量%二乙胺的溶胶-凝胶前体溶液：
当激烈搅拌时，制备66g氯化锡(IV)和5.8g氯化锑(III)和2.24g ε-己内酰胺在560g水中的溶液。将该溶液加热至50℃，并在该温度下加入142g 25重量%氢氧化铵水溶液。将所得悬浮液在50℃下搅拌10小时。然后将所形成的悬浮液引入高压釜并经3.5小时加热至150℃。在冷却之后，将沉淀借助离心机取出并用水洗涤4次，并每次用Ultraturrax再分散。将所获得的沉淀溶解在水和二乙胺的7:3混合物中，以获得15重量%(基于金属氧化物含量)ATO前体溶液。将200g上述ATO前体溶液用200g 15%PVP在乙醇中的溶液溶解，然后加入50ml乙醇。
电纺丝使用Nanospider单元进行(NS Lab 500S，来自Elmarco，CzechRepublic)。电极类型：6-线电极；电极间距25cm；电压：82kV。
将所得纤维(已知为绿色纤维)在空气气氛下煅烧。为此，以5℃/分钟的加热速率将它们加热至550℃并将该550℃的温度保持两小时。
实施例5：ATO(氧化锡锑)纳米纤维的合成
如下制备包含4.8重量%PVP(Sigma-Aldrich，MW 1300000)，11.5重量%ATO前体，25.7重量%水，10重量%乙醇，35.2重量%甲醇和12.8重量%二乙胺的溶胶-凝胶前体溶液：
将200g 25重量%氢氧化铵水溶液引入玻璃烧瓶。当激烈搅拌时，加入78.4g氯化锡(IV)和5.2g氯化锑(III)在960g乙醇和16g浓缩HCl中的溶液。将所形成的沉淀借助离心机取出并用pH为10(用氨溶液设定)的水洗涤4次，并每次用Ultraturrax再分散。将所获得的沉淀溶解在水和二乙胺的2:1混合物中，以获得23重量%(基于金属氧化物含量)ATO前体溶液。将200g上述ATO前体溶液用160g 12%PVP在甲醇中的溶液溶解，然后加入40g乙醇。
用电纺丝单元将该溶液电纺丝为纳米纤维(“针状电纺丝”，即注射泵与高压单元组合)。将注射泵的钻速设定为0.5ml/h；在7kV电压下电极间距为8cm。
将所得纤维(已知为绿色纤维)在空气气氛下煅烧。为此，以5℃/分钟的加热速率将它们加热至550℃并将该550℃的温度保持两小时，以获得呈浅蓝色固体形式的ATO纳米纤维。

Claims (15)

1.一种生产直径为0.1-999nm的金属氧化物纤维的方法，其包括以下步骤：
(a)提供一种或多种金属化合物在至少一种选自以下的溶剂中的溶液：水、乙醇、甲醇、异丙醇、正丙醇、四氢呋喃和二甲基甲酰胺，
(b)使所述至少一种金属化合物的至少一种金属以其氢氧化物的形式从(a)中提供的溶液中碱性沉淀，以获得悬浮液，
(c)取出工艺步骤(b)中沉淀的所述至少一种氢氧化物，
(d)将在工艺步骤(c)中取出的所述至少一种氢氧化物再分散在胺或溶剂-胺混合物中，
(e)制备包含一种或多种聚合物，一种或多种溶剂以及在工艺步骤(d)中制备的混合物的溶液，
(f)将在工艺步骤(e)中制备的溶液电纺丝，和
(g)除去聚合物。
2.根据权利要求1的方法，其中所述金属化合物为选自Cu、Ag、Au、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Ru、Ni、Pd、Co、Rh、Ir、Sb、Sn、In、Al、Ga、Er和Zn的金属的金属化合物。
3.根据权利要求1或2的方法，其中在工艺步骤(b)中碱性沉淀在8-12的pH下进行。
4.根据权利要求1-3中任一项的方法，其中在工艺步骤(b)中碱性沉淀通过加入至少一种铵化合物和/或至少一种碱金属氢氧化物而进行。
5.根据权利要求1-4中任一项的方法，其中在工艺步骤(b)中碱性沉淀进行之前，将至少一种选自丙氨酸、苯丙氨酸、缬氨酸、亮氨酸和ε-己内酰胺的稳定剂加入溶液中。
6.根据权利要求1-5中任一项的方法，其中在工艺步骤(c)进行之前，将在工艺步骤(b)中获得的悬浮液加热至60-200℃的温度。
7.根据权利要求1-6中任一项的方法，其中在工艺步骤(c)中将金属氢氧化物取出之后，洗涤氢氧化物。
8.根据权利要求1-7中任一项的方法，其中在工艺步骤(d)中所述溶剂-胺混合物包含至少一种选自水、甲醇、乙醇、异丙醇、正丙醇、四氢呋喃(THF)和二甲基甲酰胺的溶剂，以及至少一种选自具有通式NR3的伯、仲或叔胺的胺，其中R独立地为H、具有1-6个碳原子的取代或未被取代的直链或支化烷基。
9.根据权利要求1-8中任一项的方法，其中在工艺步骤(e)中所述聚合物选自聚醚、聚氧化乙烯、聚乙烯醇、聚乙烯醇-聚乙酸乙烯酯共聚物、聚乙酸乙烯酯、聚乙烯基吡咯烷酮、聚丙烯酸、聚氨酯、聚交酯、聚糖苷、聚乙烯基甲酰胺、聚乙烯胺、聚乙烯亚胺和聚丙烯腈，或为两种或更多种上述聚合物的混合物。
10.根据权利要求1-9中任一项的方法，其中在工艺步骤(e)中所述至少一种溶剂选自水、甲醇、乙醇、乙二醇、正丙醇、2-丙醇、正丁醇、异丁醇、叔丁醇、环己醇、甲酸、乙酸、三氟乙酸、二乙胺、二异丙胺、苯乙胺、丙酮、乙酰丙酮、乙腈、二甘醇、甲酰胺、二甲基甲酰胺(DMF)、二甲亚砜(DMSO)、甲苯、二甲基乙酰胺、N-甲基吡咯烷酮和四氢呋喃，或为两种或更多种的混合物。
11.根据权利要求1-10中任一项的方法，其中在工艺步骤(g)中所述聚合物通过热、化学、辐射、生物、物理、等离子体或超声法或通过用溶剂萃取而除去。
12.根据权利要求1-11中任一项的方法，其中在工艺步骤(g)中除去聚合物之后，将金属氧化物纤维还原为相应的金属纤维。
13.根据权利要求1-12中任一项的方法，其中将结晶和/或无定形金属氧化物纳米颗粒和/或金属纳米颗粒加入在工艺步骤(e)制备的溶液中。
14.可通过根据权利要求1-13中任一项的方法获得的金属氧化物纤维。
15.根据权利要求13的金属氧化物纤维作为添加剂在聚合物中的用途。
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