超级电容器复合电极材料制备及电化学性能研究
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摘要
根据储能机理，超级电容器分为双电层电容器和法拉第电容器。前者电极通常采用高比表面积和高电导率的碳材料，虽循环寿命很长，但比电容较小。后者电极主要采用二氧化锰或聚苯胺，虽然这些材料理论比电容很高，但因导电性能、本身结构等原因限制了其电化学性能的充分发挥。
二氧化锰（聚苯胺）/碳材料复合能够实现材料性能的合理平衡，碳材料提供大比表面积和高导电性，二氧化锰（聚苯胺）提供高比电容。然而实际获得比电容和循环性能仍不理想，研究发现主要存在以下问题：（1）二氧化锰（聚苯胺）分散度不够；（2）界面接触电阻较大；（3）电极结构不合理。为改善上述问题，本论文将以熔融硝酸盐法制备的裁短碳纳米管和电化学电解法制备的石墨烯为载体，使二氧化锰均匀分散在其表面，制备了二氧化锰/裁短碳纳米管（石墨烯）复合材料，该复合材料电极具有高比电容和优异循环性能。采用真空微蒸发镀法制备了金属锰/碳化锰/碳纳米管复合材料，改善了复合材料界面接触电阻高的缺点。采用电泳沉积技术，以柔性石墨纸为集流体制备了3种柔性薄膜电极，优化了电极结构。本文具体研究内容和结果如下：
（1）利用熔融硝酸盐法，刻蚀裁短碳纳米管，并研究反应温度与时间对刻蚀裁短的影响。反应温度越高、时间越长刻蚀裁短效果越明显。对其形貌和结构进行分析，发现碳纳米管的长度变短，部分端帽被打开，管壁内外表面均被刻蚀，结构并没有被破坏。裁短碳纳米管具有好的悬浮稳定性和高比电容。以微波法制备了二氧化锰/裁短碳纳米管复合材料，二氧化锰纳米片能够均匀涂覆在管外表面。该复合材料电极在2mV/s时比电容为475.8F/g。在50mV/s，循环扫描1000圈后，比电容衰减幅度仅为0.8%。
（2）通过电化学电解法，利用石墨纸制备了褶皱、透明的片状石墨烯。经电化学测试，在20mV/s时，该电极比电容为28.6F/g，等效串联电阻值为6.75。以微波法制备了二氧化锰/石墨烯复合材料，二氧化锰纳米片也均匀涂覆在石墨烯表面。复合材料电极在2mV/s时比电容为357F/g、等效串联电阻值为7.9。在50mV/s，循环扫描1000圈后，比电容衰减幅度为4.5%。
（3）采用真空微蒸发镀法制备了金属锰/碳化锰/碳纳米管复合材料。金属锰纳米层均匀地涂覆在碳纳米管表面，同时在它们之间出现碳化锰层，形成低电阻欧姆接触。电极在2mV/s时比电容为378.9F/g、等效串联电阻约为5.3、且具有优异的循环性能。
（4）首次以柔性石墨纸为集流体，采用微波法和电泳沉积技术制备了二氧化锰/碳纳米管/石墨纸柔性薄膜电极。电极未使用粘结剂，并具有柔韧性，在2mV/s时比电容为442.9F/g。在50mV/s时，循环扫描1000圈后，比电容仅衰减1.1%。
（5）通过电泳沉积和恒电位沉积技术，制备两种聚苯胺基柔性薄膜电极。电极未使用粘结剂，柔韧性更佳。聚苯胺/碳纳米管/石墨纸柔性薄膜电极在20mV/s时比电容为521F/g。在50mV/s，循环扫描1000圈后，比电容衰减幅度为12％；聚苯胺/核壳碳化硅晶须/石墨纸柔性薄膜电极在50mV/s时，比电容为190F/g，循环扫描1000圈后，比电容衰减幅度为9.5％。
There are two kinds of supercapacitors depending on charge storage mechanism,namely electrochemical double layer capacitors and pseudo-capacitors. The former oftenuse carbon-based materials with a high surface area and high conductivity as electrodematerials. Despite they have long cycle-life, a major shortcoming is their low specificcapacitance. On the other hand, the pseudo-capacitorsas use MnO_2/PANI as electrodematerials. They have high theoretical specific capacitances, but, low specific capacitancesare exhibited owing to their intrinsically electronic conductivity and structure.
The MnO_2(PANI)/carbon-based material composites combine the excellentconducting and mechanical properties of carbon-based materials and highpseudocapacitance property of MnO_2(PANI). However, the actual specific capacitanceand cycle performance is not ideal. There are mainly three problems:(1) the poordispersity of MnO_2/PANI;(2) the large contact resistance of the interface;(3) theunreasonable structure of the electrodes. In order to slove these problems, we developsome active composite electrodes material with high electrochemical performance, suchas MnO_2/short multi-walled carbon nanotubes (s-MWNT) composite electrode,MnO_2/Graphenes (GNs) composite electrode, Manganese(manganous oxide)/manganesecarbide/CNTs (Mn(MnO)/Mn_5C_2/CNTs) electrode, MnO_2-coated CNTs-flexible graphitesheet (FGS) electrode, PANI/CNTs/FGS electrode and PANI/G-βSiCw/FGS electrode.The specific research contents are as follows:
(1) Selective etching in molten nitrate was used to cut MWNTs. MWNTs were cutinto different lengths by controlling the etching temperature and time. The cuttingproduced s-MWNTs were opened ends and rough surfaces. The present method did notintroduce any more destruction to the intrinsic graphitic structure of MWNTs. Thes-MWNTs formed more stable suspensions than did the pristine MWNTs, and showing anenhancement of the capacitive performance. MnO_2/s-MWNT composite was synthesizedby microwave irradiation. Uniform and conformal MnO_2coatings were formed on thesurfaces of individual s-MWNTs. The specific capacitance of MnO_2/s-MWNT compositewas475.8at2mV/s. After1000cycles at50mV/s, it lossed no more than0.8%of initial capacitance, showing good cycling stability.
(2) GNs with the thin wrinkled structure were prepared by electrolytic exfoliationfrom FGS. The specific capacitance of GNs electrode was28.6at20mV/s and the EISwas6.75. MnO
2/GNs composite electrode was synthesized by microwave irradiation.MnO_2coatings were formed on the surfaces of individual GNs. The specific capacitanceof MnO_2/GNs electrode was442.9at2mV/s. After1000cycles at50mV/s, it lossed nomore than4.5%of initial capacitance, showing good cycling stability
(3)Mn(MnO)/Mn_5C_2/CNTs composite was prepared by vacuum evaporationmethod for supercapacitors. The carbide Mn_5C_2interlayer obtained by in-situ reactionprovided a low-resistance ohmic contact and a strong interface bonding between CNTsand Mn(MnO), and consequently enhanced the conductivity and stability of thecomposite. The Mn(MnO)/Mn_5C_2/CNTs composite displayed maximum specificcapacitance of378.9F/g at2mV/s, and the EIS was5.3. The Mn(MnO)/Mn
5C2/CNTselectrode also had an excellent cycling stability.
(4) A flexible electrode was prepared by microwave heating deposition of MnO_2onCNTs followed by electrophoretic deposition of the MnO_2-coated CNTs on an FGS. Auniformly thin nano-scale MnO_2coating was formed on the surface of the CNTs. TheMnO_2-coated CNTs-FGS electrode showed highly capacitive behaviour with a specificcapacitance of442.9F/g at2mV/s. It exhibited an excellent cycling stability with nomore than1.1%capacitance loss after1000cycles at50mV/s.
(5) Two flexible electrodes were prepared by electrophoretic deposition and directeletrodeposition of polyaniline method. The PANI/CNTs/FGS electrode displayed highspecific capacitances of521F/g at20mV/s and good cycling stability with no more than12%capacitance loss after1000cycles at50mV/s. The PANI/G-βSiCw/FGS electrodedisplayed the specific capacitance as high as190F/g at50mV/s. It exhibited an excellentcycling stability with no more than9.5%capacitance loss after1000cycles at50mV/s.
二氧化锰（聚苯胺）/碳材料复合能够实现材料性能的合理平衡，碳材料提供大比表面积和高导电性，二氧化锰（聚苯胺）提供高比电容。然而实际获得比电容和循环性能仍不理想，研究发现主要存在以下问题：（1）二氧化锰（聚苯胺）分散度不够；（2）界面接触电阻较大；（3）电极结构不合理。为改善上述问题，本论文将以熔融硝酸盐法制备的裁短碳纳米管和电化学电解法制备的石墨烯为载体，使二氧化锰均匀分散在其表面，制备了二氧化锰/裁短碳纳米管（石墨烯）复合材料，该复合材料电极具有高比电容和优异循环性能。采用真空微蒸发镀法制备了金属锰/碳化锰/碳纳米管复合材料，改善了复合材料界面接触电阻高的缺点。采用电泳沉积技术，以柔性石墨纸为集流体制备了3种柔性薄膜电极，优化了电极结构。本文具体研究内容和结果如下：
（1）利用熔融硝酸盐法，刻蚀裁短碳纳米管，并研究反应温度与时间对刻蚀裁短的影响。反应温度越高、时间越长刻蚀裁短效果越明显。对其形貌和结构进行分析，发现碳纳米管的长度变短，部分端帽被打开，管壁内外表面均被刻蚀，结构并没有被破坏。裁短碳纳米管具有好的悬浮稳定性和高比电容。以微波法制备了二氧化锰/裁短碳纳米管复合材料，二氧化锰纳米片能够均匀涂覆在管外表面。该复合材料电极在2mV/s时比电容为475.8F/g。在50mV/s，循环扫描1000圈后，比电容衰减幅度仅为0.8%。
（2）通过电化学电解法，利用石墨纸制备了褶皱、透明的片状石墨烯。经电化学测试，在20mV/s时，该电极比电容为28.6F/g，等效串联电阻值为6.75。以微波法制备了二氧化锰/石墨烯复合材料，二氧化锰纳米片也均匀涂覆在石墨烯表面。复合材料电极在2mV/s时比电容为357F/g、等效串联电阻值为7.9。在50mV/s，循环扫描1000圈后，比电容衰减幅度为4.5%。
（3）采用真空微蒸发镀法制备了金属锰/碳化锰/碳纳米管复合材料。金属锰纳米层均匀地涂覆在碳纳米管表面，同时在它们之间出现碳化锰层，形成低电阻欧姆接触。电极在2mV/s时比电容为378.9F/g、等效串联电阻约为5.3、且具有优异的循环性能。
（4）首次以柔性石墨纸为集流体，采用微波法和电泳沉积技术制备了二氧化锰/碳纳米管/石墨纸柔性薄膜电极。电极未使用粘结剂，并具有柔韧性，在2mV/s时比电容为442.9F/g。在50mV/s时，循环扫描1000圈后，比电容仅衰减1.1%。
（5）通过电泳沉积和恒电位沉积技术，制备两种聚苯胺基柔性薄膜电极。电极未使用粘结剂，柔韧性更佳。聚苯胺/碳纳米管/石墨纸柔性薄膜电极在20mV/s时比电容为521F/g。在50mV/s，循环扫描1000圈后，比电容衰减幅度为12％；聚苯胺/核壳碳化硅晶须/石墨纸柔性薄膜电极在50mV/s时，比电容为190F/g，循环扫描1000圈后，比电容衰减幅度为9.5％。
There are two kinds of supercapacitors depending on charge storage mechanism,namely electrochemical double layer capacitors and pseudo-capacitors. The former oftenuse carbon-based materials with a high surface area and high conductivity as electrodematerials. Despite they have long cycle-life, a major shortcoming is their low specificcapacitance. On the other hand, the pseudo-capacitorsas use MnO_2/PANI as electrodematerials. They have high theoretical specific capacitances, but, low specific capacitancesare exhibited owing to their intrinsically electronic conductivity and structure.
The MnO_2(PANI)/carbon-based material composites combine the excellentconducting and mechanical properties of carbon-based materials and highpseudocapacitance property of MnO_2(PANI). However, the actual specific capacitanceand cycle performance is not ideal. There are mainly three problems:(1) the poordispersity of MnO_2/PANI;(2) the large contact resistance of the interface;(3) theunreasonable structure of the electrodes. In order to slove these problems, we developsome active composite electrodes material with high electrochemical performance, suchas MnO_2/short multi-walled carbon nanotubes (s-MWNT) composite electrode,MnO_2/Graphenes (GNs) composite electrode, Manganese(manganous oxide)/manganesecarbide/CNTs (Mn(MnO)/Mn_5C_2/CNTs) electrode, MnO_2-coated CNTs-flexible graphitesheet (FGS) electrode, PANI/CNTs/FGS electrode and PANI/G-βSiCw/FGS electrode.The specific research contents are as follows:
(1) Selective etching in molten nitrate was used to cut MWNTs. MWNTs were cutinto different lengths by controlling the etching temperature and time. The cuttingproduced s-MWNTs were opened ends and rough surfaces. The present method did notintroduce any more destruction to the intrinsic graphitic structure of MWNTs. Thes-MWNTs formed more stable suspensions than did the pristine MWNTs, and showing anenhancement of the capacitive performance. MnO_2/s-MWNT composite was synthesizedby microwave irradiation. Uniform and conformal MnO_2coatings were formed on thesurfaces of individual s-MWNTs. The specific capacitance of MnO_2/s-MWNT compositewas475.8at2mV/s. After1000cycles at50mV/s, it lossed no more than0.8%of initial capacitance, showing good cycling stability.
(2) GNs with the thin wrinkled structure were prepared by electrolytic exfoliationfrom FGS. The specific capacitance of GNs electrode was28.6at20mV/s and the EISwas6.75. MnO
2/GNs composite electrode was synthesized by microwave irradiation.MnO_2coatings were formed on the surfaces of individual GNs. The specific capacitanceof MnO_2/GNs electrode was442.9at2mV/s. After1000cycles at50mV/s, it lossed nomore than4.5%of initial capacitance, showing good cycling stability
(3)Mn(MnO)/Mn_5C_2/CNTs composite was prepared by vacuum evaporationmethod for supercapacitors. The carbide Mn_5C_2interlayer obtained by in-situ reactionprovided a low-resistance ohmic contact and a strong interface bonding between CNTsand Mn(MnO), and consequently enhanced the conductivity and stability of thecomposite. The Mn(MnO)/Mn_5C_2/CNTs composite displayed maximum specificcapacitance of378.9F/g at2mV/s, and the EIS was5.3. The Mn(MnO)/Mn
5C2/CNTselectrode also had an excellent cycling stability.
(4) A flexible electrode was prepared by microwave heating deposition of MnO_2onCNTs followed by electrophoretic deposition of the MnO_2-coated CNTs on an FGS. Auniformly thin nano-scale MnO_2coating was formed on the surface of the CNTs. TheMnO_2-coated CNTs-FGS electrode showed highly capacitive behaviour with a specificcapacitance of442.9F/g at2mV/s. It exhibited an excellent cycling stability with nomore than1.1%capacitance loss after1000cycles at50mV/s.
(5) Two flexible electrodes were prepared by electrophoretic deposition and directeletrodeposition of polyaniline method. The PANI/CNTs/FGS electrode displayed highspecific capacitances of521F/g at20mV/s and good cycling stability with no more than12%capacitance loss after1000cycles at50mV/s. The PANI/G-βSiCw/FGS electrodedisplayed the specific capacitance as high as190F/g at50mV/s. It exhibited an excellentcycling stability with no more than9.5%capacitance loss after1000cycles at50mV/s.
引文
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