CN106410159B - 一种聚苯胺凝胶包覆锡铜纳米管复合材料的制备方法 - Google Patents
一种聚苯胺凝胶包覆锡铜纳米管复合材料的制备方法 Download PDFInfo
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Abstract
本发明提供一种聚苯胺凝胶包覆锡铜纳米管复合材料的制备方法，利用化学还原法制备锡纳米棒，并利用电流置换法得到锡铜纳米管。进而通过化学原位聚合法制备聚苯胺凝胶包覆锡铜纳米管复合材料。本发明制备的锡铜纳米管平均管径约为40‑60nm。锡铜纳米管较为均匀地分散在三维网络结构的导电聚合物聚苯胺凝胶基体的孔隙中。棒状结构可以避免充放电过程中电极材料的团聚，同时导电聚合物凝胶的高导电性和多孔结构可为锂离子和电子提供快速扩散的通道，实现电极材料的快速充放电性能。在0.1CA·g‑1充放电电流密度下可达约1100mAh·g‑1的高比容量。本发明在改善锂离子电池负极材料的倍率性能方面具有广泛的应用前景。
Description
技术领域
本发明涉及材料技术领域，尤其涉及一种聚苯胺凝胶包覆锡铜纳米管复合材料的制备方法。
背景技术
锂离子电池作为新型的绿色能源，具有比能量高、自放电低、循环性能好、无记忆效应、质量轻、能量密度大、循环寿命长等优点，是目前最具发展前景的化学储能电源。负极材料作为锂离子电池的重要组成部分，直接影响锂离子电池的电池容量和使用寿命。目前商品化的锂离子电池主要用石墨作为负极材料，虽具有优异的循环稳定性，但其理论比容量仅为372mAh·g-1，限制了其在高能量密度化学电源中的应用。近几年，锡基负极材料因具有较好的循环寿命和较高的可逆容量等优点而受到研究者的广泛关注。但是锡基负极材料体系在充放电过程中，锂离子的可逆嵌入和脱出会产生巨大的体积膨胀，引起粉末化和团聚现象，导致材料循环稳定性差、多次循环后电极遭到破坏。这是阻碍锡基负极材料应用于锂离子电池的最主要原因。
将负极材料的尺寸做到纳米级别可以有效地缓解锂离子电池充放电时的体积膨胀，较好地改善其循环性能。另外将负极材料做成中空的结构，当发生体积膨胀时，材料内部中空的空间可以起到缓解应力的作用，很好地缓解体积膨胀，有效提高电池的循环性能。可以集合上述两种方法的优点，改善锡作为锂离子电池负极材料循环性能差的现状。采用中空结构锡铜纳米管做负极材料，其结构不仅具有纳米特性，中空结构以及棒状结构能够缓解纳米锡的团聚，有望提高电池的循环性能。
导电聚合物由于其良好的导电性、优异的加工性能和低成本而被广泛用来包覆纳米结构制备负极材料。导电聚合物兼具活性材料的缓冲剂和导电剂作用，可有效避免传统电极中由于导电剂、粘合剂等非活性材料的添加而导致的容量衰减问题。常见的导电聚合物如聚苯胺、聚吡咯和聚噻吩等，已经广泛应用于包覆层或金属和金属氧化物的结构支撑体系，显著提高了电极的电化学性能。
聚苯胺凝胶是同时兼具凝胶和聚苯胺优异性能的聚合物材料。尤其是纳米结构的聚苯胺凝胶，具有高的表面积和三维连续的导电网络，用它替代传统电极中的粘结剂和导电剂，电解质可进入其内部的微纳米孔道，有利于活性物质与电解质溶液的充分接触。利用该材料替代传统的导电剂和粘结剂，一方面可有效降低电极中非活性物质的比例，提高电池的能量密度；另一方面，利用导电聚合物凝胶的高导电性和多孔结构可为锂离子和电子提供快速扩散的通道，实现电极材料的快速充放电性能，同时缓解活性物质在充放电过程中的体积膨胀，提高锂离子电池充放电循环寿命和倍率性能。
基于纳米管结构、导电聚合物凝胶的优势，可利用化学还原法制备锡纳米棒，采用电流置换法制备锡铜纳米管，并使用化学原位聚合法制备聚苯胺凝胶包覆锡铜纳米管复合材料。
发明内容
导电聚合物由于其良好的导电性、优异的加工性能和低成本，被广泛用来包覆纳米结构制备负极材料。棒状结构可以避免充放电过程中电极材料的团聚，纳米结构的聚苯胺凝胶，具有高的表面积和三维连续的导电网络，其高导电性和多孔结构可为锂离子和电子提供快速扩散的通道，实现电极材料的快速充放电性能，同时缓解活性物质在充放电过程中的体积膨胀。故本发明用化学原位聚合法制备聚苯胺凝胶包覆锡铜纳米管复合材料，更好地改善锂离子电池负极材料的倍率性能。
本发明提供了聚苯胺凝胶包覆锡铜纳米管复合材料的制备方法。利用化学还原法制备锡纳米棒，并利用电流置换法得到锡铜纳米管。进而通过化学原位聚合法制备聚苯胺凝胶包覆锡铜纳米管复合材料。本发明制备的锡铜纳米管平均管径约为40-60nm。
一种聚苯胺凝胶包覆锡铜纳米管复合材料的制备方法，步骤如下：
(1)按照硼氢化钠:聚二烯丙基二甲基氯化铵质量比0.75～1.25:1称取上述物质溶于去离子水中得到溶液A；然后配置浓度为5～6.5mg/mL的四氯化锡溶液，在室温搅拌的条件下将四氯化锡溶液逐滴滴加到溶液A中，待反应结束，将溶液离心干燥得到锡纳米棒；
(2)配置浓度为3～5mg/mL的锡纳米棒无水乙醇溶液，超声分散；然后在磁力搅拌器中搅拌使锡纳米棒在溶液中分散；称取氯化铜溶解在上述溶液中，在50～80℃下进行电流置换反应；反应结束后，将溶液离心干燥得到锡铜纳米管；
(3)配置浓度为0.05～0.15g/mL的锡铜纳米管溶液，超声分散；然后在磁力搅拌器中搅拌10～30min，在搅拌条件下向上述溶液中加入次氮基三亚甲基三磷酸、苯胺单体，冰水条件下搅拌均匀得到溶液B；然后配置浓度为0.18～0.3g/mL的过硫酸铵溶液，并与溶液B混合，冰水条件下搅拌3～5min，静置反应；反应完成后，用去离子水清洗得到最终产物。
所述硼氢化钠和四氯化锡的质量比为1:1.56～2。
所述锡纳米棒和氯化铜的质量比为1:4.8～6.7。
所述的锡铜纳米管尺寸范围为40～60nm。
所述步骤(3)溶液中物质的质量份数配比为：锡铜中空纳米管5～15份、次氮基三亚甲基三磷酸8～12份、苯胺单体4～6份、过硫酸铵9～15份。
本发明使锡铜纳米管较为均匀地分散在三维网络结构的导电聚合物聚苯胺凝胶基体的孔隙中。棒状结构可以避免充放电过程中电极材料的团聚，同时导电聚合物凝胶的高导电性和多孔结构可为锂离子和电子提供快速扩散的通道，实现电极材料的快速充放电性能，同时缓解活性物质在充放电过程中的体积膨胀。作为锂离子电池负极材料具有良好的倍率性能，本发明的聚苯胺凝胶包覆锡铜纳米管复合材料用于锂离子电池负极材料，将制备好的涂有活性电极材料的铜箔剪为直径为8mm的铜箔若干个直接作为电极材料备用。电化学测试采用扣式电池体系(CR2032)，以聚苯胺凝胶包覆锡铜纳米管复合材料为工作电极，采用金属锂作为对电极，隔膜采用Colgard-2300锂离子电池隔膜，电解液体系为1mol/LLiPF6/EC+DMC+EMC(体积比1:1:1)，测试聚苯胺凝胶包覆锡铜纳米管复合材料作为负极材料的倍率性能。在0.1CA·g-1充放电电流密度下可达约1100mAh·g-1的高比容量，即使电流密度增加到2CA·g-1仍然有400mAh·g-1的比容量；同时，当电流密度恢复到初始电流密度0.1CA·g-1时，容量仍可回复到750mAh·g-1。由此可见，用聚苯胺凝胶包覆锡铜纳米管复合材料作为负极材料能显著改善电池的倍率性能。本发明以聚苯胺凝胶包覆锡铜纳米管，为提高锡基材料作为锂离子电池负极的倍率性能提供了一种新的研究方法。
附图说明
图1实施例3中聚苯胺凝胶包覆锡铜纳米管透射电镜图。
图2实施例3中锡铜纳米管透射电镜图。
图3实施例3中聚苯胺凝胶包覆锡铜纳米管电极材料的倍率性能曲线图。
具体实施方式
本发明实施例中所用的原料均为市购产品，纯度为分析纯。本发明制备的聚苯胺凝胶包覆锡铜纳米管复合材料的形貌通过透射电子显微镜进行表征。电化学测试采用扣式电池体系(CR2032)，以聚苯胺凝胶包覆锡铜纳米管复合材料为工作电极，采用金属锂作为对电极，隔膜采用Colgard-2300锂离子电池隔膜，电解液体系为1mol/L LiPF6/EC+DMC+EMC(体积比1:1:1)。
实施例1
首先通过化学还原方法制备锡纳米棒。称取0.2g聚二烯丙基二甲基氯化铵(PDDA)、0.15g硼氢化钠溶于100mL去离子水中得到溶液A。称取0.3g四氯化锡溶于60mL去离子水中。在室温搅拌的条件下将四氯化锡溶液逐滴滴加到溶液A中，控制滴加时间在五分钟内。滴加完成后，静置反应五分钟。反应结束后，进行离心分离。分别用去离子水和无水乙醇清洗杂质，清洗后，放在真空干燥箱中干燥，得到产物。
其次利用电流置换法制备锡铜纳米管。称取制备的纳米锡棒0.3g，溶于100mL无水乙醇中，超声分散10min。然后在磁力搅拌器中搅拌15min，使锡棒在溶液中均匀分散。称取2g氯化铜溶解在上述溶液中。在50℃反应条件下，进行电流置换反应24h。反应结束后，进行离心分离，分别用无水乙醇和去离子水清洗杂质。清洗结束后，将产物放在真空干燥箱中真空干燥，冷冻备用。
最后通过化学原位聚合法制备聚苯胺凝胶包覆锡铜纳米管复合材料。称取制备的锡铜纳米管0.05g，溶于1mL去离子水中，超声分散15min。然后在磁力搅拌器中搅拌10min，使锡铜纳米管在溶液中均匀分散。然后在磁力搅拌的条件下向上述溶液中加入0.08g次氮基三亚甲基三磷酸。用微量移液器移取苯胺单体40μL加入上述溶液中，控制温度在4℃，搅拌均匀，得到溶液B。然后称取0.09g过硫酸铵，溶解在0.5mL去离子水中。在温度为4℃条件下，将配好的过硫酸铵溶液加入溶液B中，搅拌3min后，静置反应1h，生成墨绿色黏稠状样品。反应完成后，向所得复合材料中加入去离子水反复清洗，得到最终产物。
实施例2
首先通过化学还原方法制备锡纳米棒。称取0.2g聚二烯丙基二甲基氯化铵(PDDA)、0.2g硼氢化钠溶于100mL去离子水中得到溶液A。称取0.33g四氯化锡溶于60mL去离子水中。在室温搅拌的条件下将四氯化锡溶液逐滴滴加到溶液A中，控制滴加时间在五分钟内。滴加完成后，静置反应五分钟。反应结束后，进行离心分离。分别用去离子水和无水乙醇清洗杂质，清洗后，放在真空干燥箱中干燥，得到产物。
其次利用电流置换法制备锡铜纳米管。称取制备的纳米锡棒0.4g，溶于100mL无水乙醇中，超声分散10min。然后在磁力搅拌器中搅拌15min，使锡棒在溶液中均匀分散。称取2.2g氯化铜溶解在上述溶液中。在60℃反应条件下，进行电流置换反应24h。反应结束后，进行离心分离，分别用无水乙醇和去离子水清洗杂质。清洗结束后，将产物放在真空干燥箱中真空干燥，冷冻备用。
最后通过化学原位聚合法制备聚苯胺凝胶包覆锡铜纳米管复合材料。称取制备的锡铜纳米管0.1g，溶于1mL去离子水中，超声分散15min。然后在磁力搅拌器中搅拌20min，使锡铜纳米管在溶液中均匀分散。然后在磁力搅拌的条件下向上述溶液中加入0.1g次氮基三亚甲基三磷酸。用微量移液器移取苯胺单体50μL加入上述溶液中，控制温度在4℃，搅拌均匀，得到溶液B。然后称取0.12g过硫酸铵，溶解在0.5mL去离子水中。在温度为4℃条件下，将配好的过硫酸铵溶液加入溶液B中，搅拌4min后，静置反应1h，生成墨绿色黏稠状样品。反应完成后，向所得复合材料中加入去离子水反复清洗，得到最终产物。
实施例3
首先通过化学还原方法制备锡纳米棒。称取0.2g聚二烯丙基二甲基氯化铵(PDDA)、0.25g硼氢化钠溶于100mL去离子水中得到溶液A。称取0.39g四氯化锡溶于60mL去离子水中。在室温搅拌的条件下将四氯化锡溶液逐滴滴加到溶液A中，控制滴加时间在五分钟内。滴加完成后，静置反应五分钟。反应结束后，进行离心分离。分别用去离子水和无水乙醇清洗杂质，清洗后，放在真空干燥箱中干燥，得到产物。
其次利用电流置换法制备锡铜纳米管。称取制备的纳米锡棒0.5g，溶于100mL无水乙醇中，超声分散10min。然后在磁力搅拌器中搅拌15min，使锡棒在溶液中均匀分散。称取2.4g氯化铜溶解在上述溶液中。在70℃反应条件下，进行电流置换反应24h。反应结束后，进行离心分离，分别用无水乙醇和去离子水清洗杂质。清洗结束后，将产物放在真空干燥箱中真空干燥，冷冻备用。
最后通过化学原位聚合法制备聚苯胺凝胶包覆锡铜纳米管复合材料。称取制备的锡铜纳米管0.15g，溶于1mL去离子水中，超声分散15min。然后在磁力搅拌器中搅拌30min，使锡铜纳米管在溶液中均匀分散。然后在磁力搅拌的条件下向上述溶液中加入0.12g次氮基三亚甲基三磷酸。用微量移液器移取苯胺单体60μL加入上述溶液中，控制温度在4℃，搅拌均匀，得到溶液B。然后称取0.15g过硫酸铵，溶解在0.5mL去离子水中。在温度为4℃条件下，将配好的过硫酸铵溶液加入溶液B中，搅拌5min后，静置反应1h，生成墨绿色黏稠状样品。反应完成后，向所得复合材料中加入去离子水反复清洗，得到最终产物。
利用透射电子显微镜对制得的锡铜纳米管样品进行形貌观察，从说明书附图2可看出所得的锡铜纳米管管径较均匀，平均管径约为50nm。利用透射电子显微镜对制得的聚苯胺凝胶包覆锡铜纳米管样品进行形貌观察，从说明书附图1可看出锡铜纳米管周围包裹了聚苯胺导电高分子凝胶。将此产物应用于锂离子电池负极材料，组装电池进行电化学表征，由图3可知，在0.1CA·g-1充放电电流密度下可达约1100mAh·g-1的高比容量，即使电流密度增加到2CA·g-1仍然有400mAh·g-1的比容量；同时，当电流密度恢复到初始电流密度0.1CA·g-1时，容量仍可回复到750mAh·g-1。用聚苯胺凝胶包覆锡铜纳米管复合材料作为负极材料能显著改善电池的倍率性能。
由这三个实例可以看出，聚苯胺凝胶的加入对增强体系的倍率性能有着重要作用。
以上实施例仅是为说明本发明而举，本发明的保护范围不限于此。本技术领域内技术人员在本发明基础上所做的等同替代和变换，均在本发明的保护范围之内。
Claims (5)
1.一种聚苯胺凝胶包覆锡铜纳米管复合材料的制备方法，其特征是步骤如下：
(1)按照硼氢化钠:聚二烯丙基二甲基氯化铵质量比0.75～1.25:1称取上述物质溶于去离子水中得到溶液A；然后配置浓度为5～6.5mg/mL的四氯化锡溶液，在室温搅拌的条件下将四氯化锡溶液逐滴滴加到溶液A中，待反应结束，将溶液离心干燥得到锡纳米棒；
(2)配置浓度为3～5mg/mL的锡纳米棒无水乙醇溶液，超声分散；然后在磁力搅拌器中搅拌使锡纳米棒在溶液中分散；称取氯化铜溶解在上述溶液中，在50～80℃下进行电流置换反应；反应结束后，将溶液离心干燥得到锡铜纳米管；
(3)配置浓度为0.05～0.15g/mL的锡铜纳米管溶液，超声分散；然后在磁力搅拌器中搅拌10～30min，在搅拌条件下向上述溶液中加入次氮基三亚甲基三磷酸、苯胺单体，冰水条件下搅拌均匀得到溶液B；然后配置浓度为0.18～0.3g/mL的过硫酸铵溶液，并与溶液B混合，冰水条件下搅拌3～5min，静置反应；反应完成后，用去离子水清洗得到最终产物。
2.如权利要求1所述方法，其特征是硼氢化钠和四氯化锡的质量比为1:1.56～2。
3.如权利要求1所述方法，其特征是锡纳米棒和氯化铜的质量比为1:4.8～6.7。
4.如权利要求1所述的制备方法，其特征在于所述的锡铜纳米管管径尺寸范围为40-60nm。
5.如权利要求1所述方法，其特征是步骤(3)溶液中物质的质量份数配比为：锡铜纳米管5～15份、次氮基三亚甲基三磷酸8～12份、苯胺单体4～6份、过硫酸铵9～15份。
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Non-Patent Citations (2)
| Title |
|---|
| Solvothermal synthesis of carbon-coated tin nanorods for superior reversible lithium ion storage;Ping Wu 等;《Materials Research Bulletin》;20110906;第46卷;第2278-2282页 |
| 锡/聚吡咯三维纳米结构锂离子电池负极材料的制备及稳定性研究;范欣;《万方数据知识服务平台》;20151203 |
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Effective date of registration: 20221019 Address after: Room 107, Building 6, No. 91, Fahuasi Street, Dongcheng District, Beijing 100062 Patentee after: Beijing Legend Yousheng Culture Media Co.,Ltd. Address before: 300304 room 1-2050, Block E, No. 6, Huafeng Road, Huaming high tech Industrial Zone, Dongli District, Tianjin Patentee before: Zhongzhi online Co.,Ltd. |
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Application publication date: 20170215 Assignee: Tianjin aisida New Material Technology Co.,Ltd. Assignor: Beijing Legend Yousheng Culture Media Co.,Ltd. Contract record no.: X2023980040791 Denomination of invention: A preparation method of polyaniline gel coated tin copper nanotube composite Granted publication date: 20190719 License type: Common License Record date: 20230829 |
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Application publication date: 20170215 Assignee: TIANJIN ZHUJIN TECHNOLOGY DEVELOPMENT Corp. Assignor: Beijing Legend Yousheng Culture Media Co.,Ltd. Contract record no.: X2024980004064 Denomination of invention: A preparation method of polyaniline gel coated tin copper nanotube composite Granted publication date: 20190719 License type: Common License Record date: 20240408 |
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