CN112701268B - 柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极及其制备方法 - Google Patents
柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极及其制备方法 Download PDFInfo
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- CN112701268B CN112701268B CN202110131221.2A CN202110131221A CN112701268B CN 112701268 B CN112701268 B CN 112701268B CN 202110131221 A CN202110131221 A CN 202110131221A CN 112701268 B CN112701268 B CN 112701268B
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- carbon nanotube
- nanotube film
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- tungsten oxide
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- Battery Electrode And Active Subsutance (AREA)
Abstract
柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极的制备方法,属于电化学储能与转换技术领域。在制备碳纳米管薄膜的过程中,采用喷涂技术将钨盐溶液喷洒在碳纳米管管束表面,形成碳纳米管薄膜/钨盐/碳纳米管薄膜层层自组装复合前驱体;将该复合前驱体置于高压反应釜中进行溶剂热反应;反应结束后降至室温,干燥,得到复合膜;将干燥后的复合膜置于管式炉中,于氮气气氛中煅烧,得到碳包覆氧化钨/碳纳米管薄膜复合材料。将上述薄膜材料进行辊压、冲片,即可得到柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极。此电极具有柔性、质轻、无粘结剂、制备工艺简单等特点,有利于批量化生产,可应用于锂离子电池、超级电容器、燃料电池和水电解等电化学储能与转换领域。
Description
技术领域
本发明属于电极材料领域,具体涉及柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极的制备方法。
背景技术
随着电极技术的快速发展,柔性可穿戴器件逐步进入了普通大众的视野。将电极材料负载在各类柔性导电基体上,使得所制备的器件具有可折叠、便携性强的特点,符合各类新型电子设备的发展趋势。氧化钨作为活性物质,可与锂离子发生独特的转换反应,其理论比容量(693 mAh g-1)比商业石墨的(372 mAh g-1)更高,同时具有成本低、固有密度高和安全无污染等特点,成为具有潜力的锂离子电池负极材料。氧化钨虽然比碳材料具有更好的储锂性能,但也存在不足之处,即氧化钨材料在首次充放电循环时,放电比容量很可观,可超过其理论比容量,但在随后循环中,其容量的稳定性较差,衰减较为明显。石墨烯薄膜和碳纳米管薄膜具有机械柔性和高电子迁移率,负载活性物质(如氧化锡、氧化铁、氧化钒、氧化钨等)可用于构建柔性电极。将氧化钨负载在碳材料薄膜等柔性基底上,形成复合物,是制备氧化钨基柔性电极的较佳选择。通常方法是利用超声波和过滤技术制备氧化钨/碳纳米管薄膜(或石墨烯)复合材料,直接作为电极材料,表现出较好的循环性能和倍率性能,然而,直接负载在柔性导电基体上的电极材料往往面临结合力差、折叠过程中易破损脱落的现实问题,使得电池容量衰减较快,甚至会引发一系列安全事故。
发明内容
本发明目的在于提供一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,通过将电极材料表面进行碳包覆并嵌入柔性导电基体网络中,可以有效提高锂离子和电子的迁移速率,缓解氧化钨的体积膨胀,增强材料的结构稳定性,从而提氧化钨材料的储锂性能和循环稳定性。
本发明另一目的在于提供一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极的制备方法。
在制备碳纳米管薄膜的过程中,采用喷涂技术将钨盐溶液喷洒在碳纳米管管束表面,形成碳纳米管薄膜/钨盐/碳纳米管薄膜层层自组装复合前驱体;将该复合前驱体置于高压反应釜中进行溶剂热反应;反应结束后降至室温,干燥,得到复合膜;将干燥后的复合膜置于管式炉中,于氮气气氛中煅烧,得到碳包覆氧化钨/碳纳米管薄膜复合材料。将上述薄膜材料进行辊压、冲片,即可得到柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极。
主要包括以下步骤:
(1)先将钨盐加入无水乙醇与蒸馏水的混合溶液中,再加入水溶性有机活化剂,配制成钨盐溶液,并对该溶液进行超声分散;
(2)将步骤(1)中的分散溶液倒入喷洒壶中,在制备碳纳米管薄膜过程中,将钨盐溶液喷洒在碳纳米管管束表面,形成碳纳米管薄膜/钨盐/碳纳米管薄膜层层自组装复合前驱体;
(3)把步骤(2)中的复合前驱体置于含有乙醇/水(体积比1:1—5:1)的聚四氟乙烯内胆的反应釜中,进行溶剂热反应,反应温度160—200oC,反应时间1—10 h,反应结束并自然降至室温后,取出复合前驱体,进行干燥;
(4)将步骤(3)中干燥的复合前驱体置于管式炉中,并在氮气气氛中进行煅烧,煅烧温度为400—600 oC,煅烧时间为0.5—4 h;
(5)自然降温至室温,得到碳包覆氧化钨/碳纳米管薄膜复合材料;
(6)将步骤(5)中的复合材料进行辊压、冲片,即可得到柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极。
步骤(1)中的钨盐为六氯化钨、偏钨酸铵、仲钨酸铵、钨酸钠等其中一种或多种组合。
步骤(1)中的水溶性有机活化剂为柠檬酸、醋酸、十二烷基苯磺酸钠、聚乙烯吡咯烷酮、脂肪醇等其中一种或多种组合。
本发明具有以下有益效果:在制备碳纳米管薄膜过程中,以碳纳米管薄膜作为模板,采用喷涂法结合溶剂热合成技术,合成了碳包覆氧化钨/碳纳米管薄膜复合电极。一方面,在制备碳纳米管薄膜时,利用喷涂法将氧化钨嵌入碳纳米管管束的导电性网络中,有益于提高氧化钨的导电性和结构稳定性;另一方面,氧化钨表面包覆了碳层,使得氧化钨具有导电性和体积膨胀空间。所得柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极具有轻质、柔性、无粘结剂、制备工艺简单等特点,可实现批量化生产,具有应用于锂离子电池、超级电容器、燃料电池和水电解等电化学储能与转换领域的潜力。
本发明所提供的柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,无需使用粘结剂,可直接作为一体化复合电极使用,大大降低了电极质量,同时减少了打浆、涂布等环节,精简了工艺步骤。有机活化剂改善了钨盐在碳纳米管薄膜中的分散性;有机活化剂热解产生的薄碳层紧紧包覆在氧化钨表面,可以有效减缓氧化钨在电化学循环过程中存在较大的体积变化问题,提升了氧化钨的电化学性能。一方面多孔结构碳纳米薄膜作为导电剂,具有良好的导电网络,提升氧化钨电极材料的导电性能,降低氧化钨的电荷转移电阻;同时碳纳米管缩短锂离子的扩散距离,提高了电池的导电性;另一方面碳纳米管薄膜作为集流体,具有轻质、柔性等特性,有助于实现传统氧化钨材料在柔性一体化电极中的应用。
附图说明
图1为实施例1中碳包覆氧化钨/碳纳米管薄膜复合材料的宏观图。
图2为实施例1中的碳包覆氧化钨/碳纳米管薄膜复合电极的宏观图。
图3 为实施例1和实施例2中复合电极的锂离子充放电性能对比图。
具体实施方式
以下内容为本发明的具体实施方式。需要指出的是,对于这些实施方式的说明用于帮助理解本发明,但本发明的保护范围不限于下述的实施例。此外,下面所描述的本发明各个具体实施方式中所涉及的技术特征只要彼此之间没有产生冲突就可以相互组合。
实施例1。
将1g六氯化钨溶于50 mL混合溶液(25 mL无水乙醇与25 mL去离子水)中,超声分散,置于喷洒壶中。在制备碳纳米管薄膜(10*30 cm2)的同时,将混合溶液均匀喷涂在碳纳米管管束表面。将喷涂完的复合膜进行静置、风干、裁剪。将裁剪好的复合薄膜置于高压反应釜中进行溶剂热反应。反应釜中溶剂为无水乙醇与水混合溶液,体积比为1:1(60 mL水:60 mL无水乙醇);反应温度为180 ℃,反应时间为4 h。反应完自然冷却,取出复合薄膜,自然晾干。将晾干的复合薄膜置于高温反应炉中,在氮气气氛下,煅烧温度为500 ℃,保温时间为1 h,冷却后即可获得一体化的碳包覆氧化钨/碳纳米管薄膜复合材料。将上述薄膜进行辊压、冲片,即可得到一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,放电比容量达到900 mAh g-1,循环50圈后比容量达到400mAh g-1,外电阻达到30欧姆。可应用于锂离子电池、超级电容器、燃料电池和水电解等领域。
实施例2。
将1g六氯化钨和1g柠檬酸溶于50 mL混合溶液(25 mL无水乙醇与25 mL去离子水)中,超声分散,置于喷洒壶中。在制备碳纳米管薄膜(10*30 cm2)的同时,将混合溶液均匀喷涂在碳纳米管管束表面。将喷涂完的复合膜进行静置、风干、裁剪。将裁剪好的复合薄膜置于高压反应釜中进行溶剂热反应。反应釜中溶剂为无水乙醇与水混合溶液,体积比为1:1(60 mL水:60 mL无水乙醇);反应温度为180 ℃,反应时间为4 h。反应完自然冷却,取出复合薄膜,自然晾干。将晾干的复合薄膜置于高温反应炉中,在氮气气氛下,煅烧温度为500℃,保温时间为1 h,冷却后即可获得一体化的碳包覆氧化钨/碳纳米管薄膜复合材料。将上述薄膜进行辊压、冲片,即可得到一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,放电比容量达到1100 mAh g-1,循环50圈后比容量达到500mAh g-1,外电阻达到20欧姆。可应用于锂离子电池、超级电容器、燃料电池和水电解等领域。
实施例3。
将1 g六氯化钨和2 g柠檬酸溶于 50 mL 混合溶液(25 mL无水乙醇与25 mL去离子水)中,超声分散,置于喷洒壶中。在制备碳纳米管薄膜(10*30 cm2)的同时,将混合溶液均匀喷涂在碳纳米管管束表面。将喷涂的复合碳膜进行静置、风干、裁剪。将裁剪好的复合薄膜置于高压反应釜中进行溶剂热反应。反应釜中溶剂为无水乙醇与水混合溶液,体积比例2:1(80 mL无水乙醇:40 mL水);反应温度为180℃,反应时间为4 h。反应完自然冷却,取出复合薄膜,自然晾干。将晾干的复合薄膜置于高温反应炉中,在氮气气氛下,煅烧温度为500 ℃,保温时间为2 h,冷却后即可获得一体化的碳包覆氧化钨/碳纳米管薄膜复合材料。将上述薄膜进行辊压、冲片,即可得到一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,放电比容量达到1000 mAh g-1,循环50圈后比容量达到450mAh g-1,外电阻达到20欧姆。可应用于锂离子电池、超级电容器、燃料电池和水电解等领域。
实施例4。
将1 g六氯化钨和3 g柠檬酸 溶于50 mL混合溶液(25 mL无水乙醇与25 mL去离子水)中,超声分散,置于喷洒壶中。在制备碳纳米管薄膜(10*30 cm2)的同时,将混合溶液均匀喷涂在碳纳米管管束表面。将喷涂的复合碳膜进行静置、风干、裁剪。将裁剪好的复合薄膜置于高压反应釜中进行溶剂热反应。反应釜中溶剂为无水乙醇与水混合溶液,体积比例3:1(90 mL无水乙醇:30 mL水);反应温度为180℃,反应时间为4 h。反应完自然冷却,取出复合薄膜,自然晾干。将晾干的复合薄膜置于高温反应炉中,在氮气气氛下,煅烧温度为500℃,保温时间为1 h,冷却后即可获碳包覆氧化钨/碳纳米管薄膜复合材料。将上述薄膜进行辊压、冲片,即可得到一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,放电比容量达到1100 mAh g-1,循环50圈后比容量达到500mAh g-1,外电阻达到25欧姆。可应用于锂离子电池、超级电容器、燃料电池和水电解等领域。
实施例5。
将2 g六氯化钨和2 g柠檬酸 溶于50 mL混合溶液(25 mL无水乙醇与25 mL去离子水)中,超声分散,置于喷洒壶中。在制备碳纳米管薄膜(10*30 cm2)的同时,将混合溶液均匀喷涂在碳纳米管管束表面。将喷涂的复合碳膜进行静置、风干、裁剪。将裁剪好的复合薄膜置于高压反应釜中进行溶剂热反应。反应釜中溶剂为无水乙醇与水混合溶液,体积比例1:1(60 mL无水乙醇:60 mL水);反应温度为180℃,反应时间为4 h。反应完自然冷却,取出复合薄膜,自然晾干。将晾干的复合薄膜置于高温反应炉中,在氮气气氛下,煅烧温度为400℃,保温时间为1 h,冷却后即可获得碳包覆氧化钨/碳纳米管薄膜复合材料。将上述薄膜进行辊压、冲片,即可得到一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,放电比容量达到1100 mAh g-1,循环50圈后比容量达到500mAh g-1,外电阻达到20欧姆。可应用于锂离子电池、超级电容器、燃料电池和水电解等领域。
实施例6。
将2 g六氯化钨和2 g葡萄糖溶于50 mL混合溶液(25 mL无水乙醇与25 mL去离子水)中,超声分散,置于喷洒壶中。在制备碳纳米管薄膜(10*30 cm2)的同时,将混合溶液均匀喷涂在碳纳米管管束表面。将喷涂的复合碳膜进行静置、风干、裁剪。将裁剪好的复合薄膜置于高压反应釜中进行溶剂热反应。反应釜中溶剂为无水乙醇与水混合溶液,体积比例1:1(60 mL无水乙醇:60 mL水);反应温度为180 ℃,反应时间为4 h。反应完自然冷却,取出复合薄膜,自然晾干。将晾干的复合薄膜置于高温反应炉中,在氮气气氛下,煅烧温度为450℃,保温时间为2 h,冷却后即可获得碳包覆氧化钨/碳纳米管薄膜复合材料。将上述薄膜进行辊压、冲片,即可得到一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,放电比容量达到1200 mAh g-1,循环50圈后比容量达到500mAh g-1,外电阻达到25欧姆。可应用于锂离子电池、超级电容器、燃料电池和水电解等领域。
实施例7。
将2 g偏钨酸铵和1 g柠檬酸溶于 50 mL 混合溶液(25 mL无水乙醇与25 mL去离子水)中,超声分散,置于喷洒壶中。在制备碳纳米管薄膜(10*30 cm2)的同时,将混合溶液均匀喷涂在碳纳米管管束表面。将喷涂的复合碳膜进行静置、风干、裁剪。将裁剪好的复合薄膜置于高压反应釜中进行溶剂热反应。反应釜中溶剂为无水乙醇与水混合溶液,体积比例1:1(60 mL无水乙醇:60 mL水);反应温度为180 ℃,反应时间为8 h。反应完自然冷却,取出复合薄膜,自然晾干。将晾干的复合薄膜置于高温反应炉中,在氮气气氛下,煅烧温度为500 ℃,保温时间为0.5 h,冷却后即可获得碳包覆氧化钨/碳纳米管薄膜复合材料。将上述薄膜进行辊压、冲片,即可得到一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,放电比容量达到1000 mAh g-1,循环50圈后比容量达到400mAh g-1,外电阻达到30欧姆。可应用于锂离子电池、超级电容器、燃料电池和水电解等领域。
Claims (8)
1.一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,其特征在于:在制备碳纳米管薄膜的过程中,采用喷涂技术将加入水溶性有机活化剂的钨盐溶液喷洒在碳纳米管管束表面,形成碳纳米管薄膜/钨盐/碳纳米管薄膜层层自组装复合前驱体;将该复合前驱体置于高压反应釜中进行溶剂热反应;反应结束后降至室温,干燥,得到复合膜;将干燥后的复合膜置于管式炉中,于氮气气氛中煅烧,得到碳包覆氧化钨/碳纳米管薄膜复合材料;将上述薄膜复合材料进行辊压、冲片,即可得到柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极;所述水溶性有机活化剂为柠檬酸、醋酸、十二烷基苯磺酸钠、聚乙烯吡咯烷酮、脂肪醇中的一种或多种组合。
2.根据权利要求1所述的一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,其特征在于:该复合电极的制备方法包括以下步骤:
(1)先将钨盐加入无水乙醇与蒸馏水的混合溶液中,再加入水溶性有机活化剂,配制成钨盐溶液,并对该溶液进行超声分散;
(2)将步骤(1)中的分散溶液倒入喷洒壶中,在制备碳纳米管薄膜过程中,将钨盐溶液喷洒在碳纳米管管束表面,形成碳纳米管薄膜/钨盐/碳纳米管薄膜层层自组装复合前驱体;
(3)把步骤(2)中的复合前驱体置于含有乙醇/水的聚四氟乙烯内胆的反应釜中,进行溶剂热反应,反应温度160—200oC,反应时间1—10 h,反应结束并自然降至室温后,取出复合前驱体,进行干燥;
(4)将步骤(3)中干燥的复合前驱体置于管式炉中,并在氮气气氛中进行煅烧,煅烧温度为400—600 oC,煅烧时间为0.5—4 h;
(5)自然降温至室温,得到碳包覆氧化钨/碳纳米管薄膜复合材料;
(6)将步骤(5)中的复合材料进行辊压、冲片,即可得到柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极。
3.根据权利要求2所述的一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,其特征在于:步骤(1)中的钨盐为六氯化钨、偏钨酸铵、仲钨酸铵、钨酸钠中的一种或多种组合。
4.根据权利要求2所述的一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极,其特征在于:步骤(3)中所述乙醇和水的体积比1:1—5:1。
5.一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极的制备方法,其特征在于:在制备碳纳米管薄膜的过程中,采用喷涂技术将加入水溶性有机活化剂的钨盐溶液喷洒在碳纳米管管束表面,形成碳纳米管薄膜/钨盐/碳纳米管薄膜层层自组装复合前驱体;将该复合前驱体置于高压反应釜中进行溶剂热反应;反应结束后降至室温,干燥,得到复合膜;将干燥后的复合膜置于管式炉中,于氮气气氛中煅烧,得到碳包覆氧化钨/碳纳米管薄膜复合材料;将上述薄膜复合材料进行辊压、冲片,即可得到柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极;所述水溶性有机活化剂为柠檬酸、醋酸、十二烷基苯磺酸钠、聚乙烯吡咯烷酮、脂肪醇中的一种或多种组合。
6.根据权利要求5所述的一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极的制备方法,其特征在于:包括以下步骤:
(1)先将钨盐加入无水乙醇与蒸馏水的混合溶液中,再加入水溶性有机活化剂,配制成钨盐溶液,并对该溶液进行超声分散;
(2)将步骤(1)中的分散溶液倒入喷洒壶中,在制备碳纳米管薄膜过程中,将钨盐溶液喷洒在碳纳米管管束表面,形成碳纳米管薄膜/钨盐/碳纳米管薄膜层层自组装复合前驱体;
(3)把步骤(2)中的复合前驱体置于含有乙醇/水的聚四氟乙烯内胆的反应釜中,进行溶剂热反应,反应温度160—200oC,反应时间1—10 h,反应结束并自然降至室温后,取出复合前驱体,进行干燥;
(4)将步骤(3)中干燥的复合前驱体置于管式炉中,并在氮气气氛中进行煅烧,煅烧温度为400—600 oC,煅烧时间为0.5—4 h;
(5)自然降温至室温,得到碳包覆氧化钨/碳纳米管薄膜复合材料;
(6)将步骤(5)中的复合材料进行辊压、冲片,即可得到柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极。
7.根据权利要求6所述的一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极的制备方法,其特征在于:步骤(1)中的钨盐为六氯化钨、偏钨酸铵、仲钨酸铵、钨酸钠中的一种或多种组合。
8.根据权利要求6所述的一种柔性一体化碳包覆氧化钨/碳纳米管薄膜复合电极的制备方法,其特征在于:步骤(3)中所述乙醇和水的体积比1:1—5:1。
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