CN106887346A - 一种钼酸锰多孔纳米管的静电纺丝制备方法及钼酸锰多孔纳米管 - Google Patents
一种钼酸锰多孔纳米管的静电纺丝制备方法及钼酸锰多孔纳米管 Download PDFInfo
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000011572 manganese Substances 0.000 title claims abstract description 89
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 89
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002071 nanotube Substances 0.000 title claims abstract description 58
- 238000010041 electrostatic spinning Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 19
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- 239000002243 precursor Substances 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 14
- 239000002121 nanofiber Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
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- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
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- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
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- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
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- 238000010438 heat treatment Methods 0.000 claims 1
- 239000002070 nanowire Substances 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
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- 238000013019 agitation Methods 0.000 description 4
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- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
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- 230000006641 stabilisation Effects 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明公开了一种钼酸锰多孔纳米管的静电纺丝制备方法,将单轴静电纺丝技术应用在钼酸锰多孔纳米管的制备过程中,简化了生产过程,降低了生产成本,并提高了钼酸锰多孔纳米管的产量,使得钼酸锰多孔纳米管能够大规模进行生产,满足了实际需求。本发明的方法流程短,得到的钼酸锰多孔纳米管尺寸均匀、结晶度高、长径比高、比表面积大。本发明还公开了一种钼酸锰多孔纳米管,具有独特的多孔中空结构,多孔纳米管之间形成交联网络状结构,能够有效促进离子/电子的转移和电解液的渗透,缩短电解液离子在材料中的扩散路径,具有较高的比容量、优异的倍率性能和较好的循环稳定性,并且动力学性能也得到了大大提高。
Description
技术领域
本发明涉及纳米材料领域,特别是涉及一种钼酸锰多孔纳米管的静电纺丝制备方法及钼酸锰多孔纳米管。
背景技术
超级电容器是一种电化学能量储存设备,它与目前广泛使用的各种储能装置相比,具有大电流快速充放电、循环使用寿命长、超大比容量等优点。此外,超级电容器还具备对安全性能高、环境无污染、使用温度范围宽等特点,因而在高科技储能技术中占有与日俱增的关键地位。
电极材料是决定超级电容器性能的关键因素之一,根据电化学储能机理的差异,电极材料主要有碳材料、导电聚合物和过渡金属氧化物这三类。由于过渡金属氧化物比碳材料和导电聚合物具有更高的比电容而引起了广大科研人员的关注。由于其可实现的氧化态以及较高的电子电导率等特性,二元金属氧化物在超级电容器电极材料的应用中具有很多优于一元金属氧化物的性能。此外,由于其成本低、来源广和环境友好等特点,使得二元金属氧化物被视为一种高效、前景广阔的超级电容器电极材料。
在众多二元金属氧化物电极材料中,钼酸锰由于比单一的氧化物具有更高的电导率和电化学活性而被认为是一类高性能超级电容器电极材料。目前,不同结构和形貌的钼酸锰电极材料已经被制备出来,包括纳米棒、纳米块、纳米片等。然而,上述制备方法涉及到的水热法、声化学法和溶胶凝胶法由于工艺复杂、成本较高而且产量低很难满足工业化应用的需求。因此,还需要寻找合适的制备方法,使钼酸锰优异的电化学性能可以在开发高比电容、高能量密度、高充放电功率密度的超级电容器的工作中有所应用,为解决能源紧缺问题做出贡献。而且到目前为止,没有利用静电纺丝法制备钼酸锰多孔纳米管的相关报道。
静电纺丝方法具有设备简单、制备过程易控,可以被广泛运用于制备一维纳米材料,更为重要的是可以实现大规模制备与生产,多年来引起了研究者们极大的兴趣。
与实心纳米纤维相比,多孔纳米管在催化、分离、传感、电化学性能等方面具有许多独特的优势。因此,多孔纳米管的制备具有重要的意义。目前,多孔纳米管的制备通常采用同轴静电纺丝的方法。采用同轴的方法虽然能够制备直径较小的中空纤维,但是在实际制备过程中很难形成稳定的同轴泰勒锥,并且虽然理论上成立,但在实际的出丝过程中存在严重的不确定性和不稳定性。因此,同轴静电纺丝制备多孔钼酸锰纳米管的方法很难进行产业化应用。
发明内容
本发明所要解决的技术问题是,克服以上背景技术中提到的不足和缺陷,提供一种单轴静电纺丝技术来制备钼酸锰多孔纳米管的方法,该方法操作简便、反应条件温和、易于规模化生产,通过该方法制备的钼酸锰纳米管具有明显的中空结构和较高的比表面积。
为解决上述技术问题,本发明提出的技术方案为:
一种钼酸锰多孔纳米管的静电纺丝制备方法,包括以下步骤:
S1:将钼盐和锰盐溶于去离子水和有机溶剂组成的混合溶液中,形成钼酸锰前驱体溶液;其中,去离子水和有机溶剂的体积之比为0.2~3,钼盐和锰盐的总质量与混合溶液的体积之比为0.08~0.52g/ml;所述钼盐为钼酸钠或钼酸铵,锰盐为乙酸锰或氯化锰,有机溶剂为无水乙醇或N,N-二甲基甲酰胺;
S2:向步骤S1得到的钼酸锰前驱体溶液中加入络合剂粉体,搅拌形成均一混合溶液;其中,络合剂粉体的质量与钼酸锰前驱体溶液的体积之比为0.114~0.25g/ml,络合剂为聚乙烯吡咯烷酮或柠檬酸;
S3:向步骤S2所得混合溶液中滴加盐酸0.1~0.5ml,搅拌5~12h,得到最终混合溶液;
S4:通过单轴静电纺丝装置进行静电纺丝,将步骤S3得到的最终混合溶液纺成纳米纤维;其中,纺丝电压为15~25kV,喷速为0.1~0.5ml/h,接受距离为15~20cm,空气湿度为25~40%;
S5:将步骤S4得到的纳米纤维在空气中煅烧,得到钼酸锰多孔纳米管;其中,升温速率为1~5℃/min,煅烧温度为500~700℃,煅烧时间2~4h,煅烧气氛为空气。
本发明所述的钼酸锰多孔纳米管,采用钼酸锰多孔纳米管的静电纺丝制备方法制备得到。
有益效果:与现有技术相比,本发明具有如下的有益效果:
(1)本发明的方法将单轴静电纺丝技术应用在钼酸锰多孔纳米管的制备过程中,通过单轴静电纺丝装置将将步骤S3得到的最终混合溶液纺成纳米纤维,然后将纳米纤维在空气中煅烧,此时络合剂在空气中煅烧会转换成二氧化碳和水释放出来,因此络合剂在煅烧过程中又起到了造孔剂的作用。可见,本发明在钼酸锰前驱体溶液中加入多功能的络合剂,并采用单轴静电纺丝工艺,将络合剂造孔原理与单轴静电纺丝技术相结合,简化了生产过程,条件更为温和,减小了纺丝过程中对外界条件的敏感性,出丝稳定,不易出现针头堵塞现象,降低了生产成本,并提高了钼酸锰多孔纳米管的产量,使得钼酸锰多孔纳米管能够大规模进行生产,满足了实际需求;
(2)本发明的方法流程短,得到的钼酸锰多孔纳米管尺寸均匀、结晶度高、长径比高、比表面积大;
(3)本发明的钼酸锰多孔纳米管具有独特的多孔中空结构,多孔纳米管之间形成交联网络状结构,能够有效促进离子/电子的转移和电解液的渗透,缩短电解液离子在材料中的扩散路径,具有较高的比容量、优异的倍率性能和较好的循环稳定性,并且动力学性能也得到了大大提高,在电化学储能领域具有重要的应用前景。
附图说明
图1为本发明实施例2合成的钼酸锰多孔纳米管的XRD图谱;
图2为本发明实施例2合成的钼酸锰多孔纳米管的拉曼图谱;
图3为本发明实施例2合成的钼酸锰多孔纳米管在扫描电子显微镜低放大倍率下的照片;
图4为本发明实施例2合成的钼酸锰多孔纳米管在扫描电子显微镜高放大倍率下的照片;
图5为本发明实施例2合成的钼酸锰多孔纳米管的横截面扫描电子显微镜;
图6为本发明实施例2合成的钼酸锰多孔纳米管的透射电子显微镜照片;
图7为本发明实施例2合成的钼酸锰多孔纳米管的倍率性能与库伦效率图。
具体实施方式
下面结合附图和实施例,对本发明的技术方案作进一步的介绍。
高压静电纺丝技术,是利用高压静电场对高分子溶液的击穿作用来制备聚合物连续纳米纤维的一种方法,其基本原理是在喷射装置和接收装置间施加上万伏的静电场,从纺丝液的锥体端部形成射流,并在电场中被拉伸,最终在接收装置上形成无纺状态的纳米纤维。本具体实施方式将静电纺丝技术应用在钼酸锰多孔纳米管的制备过程中,下面通过多个实施例对钼酸锰多孔纳米管的静电纺丝制备方法进行介绍。
实施例1:
实施例1公开了一种钼酸锰多孔纳米管的静电纺丝制备方法,包括以下步骤:
S1:将3ml去离子水和2ml无水乙醇组成的混合溶液加入称量瓶中,将摩尔比为1:7的七钼酸铵和氯化锰加入称量瓶中,磁力搅拌溶解,形成钼酸锰前驱体溶液;其中,七钼酸铵和氯化锰的总质量与混合溶液的体积之比为0.52g/ml;
S2:向步骤S1得到的钼酸锰前驱体溶液中加入1g分子量为130万的聚乙烯吡咯烷酮粉体,搅拌形成均一的乳白色混合溶液;其中,聚乙烯吡咯烷酮粉体的质量与钼酸锰前驱体溶液的体积之比为0.2g/ml;
S3:向步骤S2所得混合溶液中滴加盐酸0.1ml,搅拌5h,得到最终混合溶液;
S4:通过静电纺丝方法,将步骤S3得到的最终混合溶液纺成纳米纤维;其中,纺丝电压为15kV,喷速为0.1ml/h,接受距离为15cm,空气湿度为28%;
S5:将步骤S4得到的纳米纤维在空气中煅烧,得到钼酸锰多孔纳米管;其中,升温速率为5℃/min,煅烧温度为500℃,煅烧时间2h,煅烧气氛为空气。
实施例2:
实施例2公开了一种钼酸锰多孔纳米管的静电纺丝制备方法,包括以下步骤:
S1:将1ml去离子水和4ml DMF组成的混合溶液加入称量瓶中,将摩尔比为1:1的钼酸钠和乙酸锰加入称量瓶中,磁力搅拌溶解,形成钼酸锰前驱体溶液;其中,钼酸钠和乙酸锰的总质量与混合溶液的体积之比为0.1g/ml;
S2:向步骤S1得到的钼酸锰前驱体溶液中加入0.4g分子量为130万的聚乙烯吡咯烷酮粉体和0.1681g柠檬酸,搅拌形成均一的乳白色混合溶液;其中,聚乙烯吡咯烷酮粉体和柠檬酸的总质量与钼酸锰前驱体溶液的体积之比为0.114g/ml;
S3:向步骤S2所得混合溶液中滴加盐酸0.3ml,搅拌12h,得到最终混合溶液;
S4:通过静电纺丝方法,将步骤S3得到的最终混合溶液纺成纳米纤维;其中,纺丝电压为17kV,喷速为0.3ml/h,接受距离为18cm,空气湿度为25%;
S5:将步骤S4得到的纳米纤维在空气中煅烧,得到钼酸锰多孔纳米管;其中,升温速率为1℃/min,煅烧温度为520℃,煅烧时间2h,煅烧气氛为空气。
本实施例制备得到的钼酸锰多孔纳米管的XRD图谱如图1所示,可见制备得到的钼酸锰多孔纳米管的结晶度很高,没有杂相。在13.1,18.8,22.7,24.6,25.7,26.6,27.7,31.2,33,51.1和54.1°出现了钼酸锰特征衍射峰,分别对应单斜晶系的钼酸锰[001],[-201],[021],[201],[220],[-112],[-311],[112],[-222],[-204],和[530]的点阵平面,与钼酸锰的标准卡片(JCPDS NO.50-1287)的衍射峰完全吻合,说明钼酸锰多孔纳米管具有较好的晶型结构。
本实施例制备得到的钼酸锰多孔纳米管的拉曼图如图2所示,在低波数区域(250-400cm-1)的拉曼峰对应于四面体MoO4 -离子的弯曲振动峰,在高波数区域(820-943cm-1)的拉曼峰对应于四面体MoO4 -离子的伸缩振动峰,该结果进一步证实了所得样品为α相钼酸锰。
本实施例制备得到的钼酸锰多孔纳米管不同放大倍率下的SEM图,如图3和4所示,经过高温煅烧后聚乙烯吡咯烷酮和柠檬酸完全分解,形成钼酸锰多孔纳米管,管壁由粒径为40~70nm的钼酸锰颗粒组成,煅烧后保持了较好的一维结构,平均外径约130nm,而且管壁上有很多纳米级的小孔,多孔纳米管结构赋予了钼酸锰较大的比表面积。图5是本实施例制备得到的钼酸锰多孔纳米管横截面的扫描电镜图,可以清楚看出钼酸锰具有显著的中空结构,内径约50nm,钼酸锰独特的多孔中空管结构可以有效促进离子/电子的转移和电解液的渗透,提高超级电容器电极材料的动力学和电化学储能性能。图6是本实施例制备得到的钼酸锰多孔纳米管的透射电镜图,可以发现钼酸锰具有明显的多孔纳米管结构,平均外径约130nm与扫描电镜结果一致。
本实施例制备得到的钼酸锰多孔纳米管电极的循环性能曲线如图7所示,这种中空的一维纳米结构在逐渐增加电流密度的情况下仍具有稳定的电容量。在充放电电流密度为2Ag-1的前2400圈循环过程中,比电容出现逐渐上升的趋势,并测得最大比容量2145Fg-1,这是电极材料活化过程中的常见现象。在接下来的5700圈循环中,电流密度逐步升至20Ag-1,当电流密度再次降到2Ag-1时,电容值仍可达到最大电容值的96%,在最后循环测试1900圈后,电容才损失了5%。同时,还计算了整个循环充放电10000圈对应的库伦效率,尽管前几百圈电极材料未完全活化,但整体平均的库伦效率高于98%。
实施例3:
实施例3公开了一种钼酸锰多孔纳米管的静电纺丝制备方法,包括以下步骤:
S1:将1ml去离子水和5ml DMF组成的混合溶液加入称量瓶中,将摩尔比为1:1的钼酸钠和乙酸锰加入称量瓶中,磁力搅拌溶解,形成钼酸锰前驱体溶液;其中,钼酸钠和乙酸锰的总质量与混合溶液的体积之比为0.08g/ml;
S2:向步骤S1得到的钼酸锰前驱体溶液中加入1.5g分子量为130万的聚乙烯吡咯烷酮粉体,搅拌形成均一的乳白色混合溶液;其中,聚乙烯吡咯烷酮粉体的质量与钼酸锰前驱体溶液的体积之比为0.25g/ml;
S3:向步骤S2所得混合溶液中滴加盐酸0.5ml,搅拌10h,得到最终混合溶液;
S4:通过静电纺丝方法,将步骤S3得到的最终混合溶液纺成纳米纤维;其中,纺丝电压为17kV,喷速为0.2ml/h,接受距离为20cm,空气湿度为30%;
S5:将步骤S4得到的纳米纤维在空气中煅烧,得到钼酸锰多孔纳米管;其中,升温速率为2℃/min,煅烧温度为600℃,煅烧时间3h,煅烧气氛为空气。
实施例4:
实施例4公开了一种钼酸锰多孔纳米管的静电纺丝制备方法,包括以下步骤:
S1:将3ml去离子水和1ml DMF组成的混合溶液加入称量瓶中,将摩尔比为1:1的钼酸钠和乙酸锰加入称量瓶中,磁力搅拌溶解,形成钼酸锰前驱体溶液;其中,钼酸钠和乙酸锰的总质量与混合溶液的体积之比为0.12g/ml;
S2:向步骤S1得到的钼酸锰前驱体溶液中加入0.3g分子量为130万的聚乙烯吡咯烷酮粉体和0.2g柠檬酸,搅拌形成均一的乳白色混合溶液;其中,聚乙烯吡咯烷酮粉体和柠檬酸的总质量与钼酸锰前驱体溶液的体积之比为0.125g/ml;
S3:向步骤S2所得混合溶液中滴加盐酸0.5ml,搅拌7h,得到最终混合溶液;
S4:通过静电纺丝方法,将步骤S3得到的最终混合溶液纺成纳米纤维;其中,纺丝电压为25kV,喷速为0.5ml/h,接受距离为20cm,空气湿度为40%;
S5:将步骤S4得到的纳米纤维在空气中煅烧,得到钼酸锰多孔纳米管;其中,升温速率为2℃/min,煅烧温度为700℃,煅烧时间4h,煅烧气氛为空气。
Claims (2)
1.一种钼酸锰多孔纳米管的静电纺丝制备方法,其特征在于:包括以下步骤:
S1:将钼盐和锰盐溶于去离子水和有机溶剂组成的混合溶液中,形成钼酸锰前驱体溶液;其中,去离子水和有机溶剂的体积之比为0.2~3,钼盐和锰盐的总质量与混合溶液的体积之比为0.08~0.52g/ml;所述钼盐为钼酸钠或钼酸铵,锰盐为乙酸锰或氯化锰,有机溶剂为无水乙醇或N,N-二甲基甲酰胺;
S2:向步骤S1得到的钼酸锰前驱体溶液中加入络合剂粉体,搅拌形成均一混合溶液;其中,络合剂粉体的质量与钼酸锰前驱体溶液的体积之比为0.114~0.25g/ml,络合剂为聚乙烯吡咯烷酮或柠檬酸;
S3:向步骤S2所得混合溶液中滴加盐酸0.1~0.5ml,搅拌5~12h,得到最终混合溶液;
S4:通过单轴静电纺丝装置进行静电纺丝,将步骤S3得到的最终混合溶液纺成纳米纤维;其中,纺丝电压为15~25kV,喷速为0.1~0.5ml/h,接受距离为15~20cm,空气湿度为25~40%;
S5:将步骤S4得到的纳米纤维在空气中煅烧,得到钼酸锰多孔纳米管;其中,升温速率为1~5℃/min,煅烧温度为500~700℃,煅烧时间2~4h,煅烧气氛为空气。
2.一种钼酸锰多孔纳米管,其特征在于:采用如权利要求1所述的钼酸锰多孔纳米管的静电纺丝制备方法制备得到。
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