针状中孔结构炭基材料的制备及其超电容性能研究
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摘要
电极材料是制约超级电容器性能提高的关键，要获得高功率性能，电解液离子在电极材料中的扩散阻力必须要小。多孔炭作为目前最具实用价值的炭电极材料，如何获得最优的电化学性能，依然是研究者们面临的一个巨大挑战。本论文旨在设计、制备具有针状中孔结构且电导率高的多孔炭，以这种笔直的中孔作为离子传输的通道，离子扩散阻力小，多孔炭可以获得优异的倍率性能，并通过与金属氧化物的复合，构建高比能量、高比功率的超级电容器体系。以自制的针状纳米Mg(OH)2/MgO（Mg(OH)2热解后的产物）为模板剂，采用不同的碳前驱体制备了多孔炭，通过氮气吸附、X-射线衍射、透射电镜、循环伏安及恒流充放电等测试方法对材料的结构与性能进行了表征，研究了材料制备工艺对孔结构、形貌等特性的影响，探索了结构特性与电容性能的关系。
首先以可溶性淀粉为碳前驱体，制备了以中孔为主的多孔炭，总孔容可达3.5cm3g-1，其中中孔孔容占80%以上，中孔炭的结构与性能受炭化工艺影响较大，其比容量较高，倍率性能优异。中孔炭的表面积比容量与其孔径呈对数关系，在约5-12nm的范围内增加较快，随着材料孔径继续增大，其比容量逐渐接近恒定值。发现针状模板剂的存在导致多孔炭中出现局域的类石墨结构，并提出其模板导向形成机制。
为了获得更高的比容量，分别采用间苯二酚/甲醛有机凝胶和易石墨化的煤焦油沥青为碳前驱体，制备了微孔丰富、中孔发达的多孔炭。针状模板的存在促使基元炭颗粒内部形成大量微孔，使多孔炭比表面积很高，这些微孔与模板脱除后留下的针状中孔形成类仙人柱形貌的层次孔结构，该结构有利于提高微孔在大电流下的利用率。并采用低用量的NaOH对材料进行活化，大大提高了多孔炭的表面积，比容量也大大提高。在6M KOH溶液中，以经硝酸/硫酸氧化的沥青制得的多孔炭的比容量最高达到282F g-1，在50A g-1的电流下容量仍能保持65%。
进一步采用炭直接还原高锰酸钾的方法，成功的将无定形MnO2负载到中孔炭的孔内部，制得中孔炭/MnO2复合材料。复合材料仍保持多孔性，孔分布的基本特征与基材中孔炭有相似性。因多孔炭成为导电骨架，复合材料的倍率性能较粉体MnO2大大提高。以复合材料为正极、高比容量多孔炭为负极组装的水系非对称电容器体系，表现出高比能量、高比功率的特性。
Electrode material is a key factor for improving supercapacitors performance. Asmall resistance of electrolyte ion diffusion in the electrode material is necessary tohigher power output. Upto now, porous carbon is the best one among the carbonelectrode materials in practical utility. How to realize the optimal electrochemicalpropereis of the porous carbon is a great challenge for the researchers. The work aimsto design and prepare a sort of porous carbon with needle-like mesoporous structureand high conductivity, and then a composite consisting of the porous carbon andmetallic oxide, and subsequently construct a supercapacitor system with high specificenergy and high specific power. Electrolyte ions transfer in such a straight mesopores,the ion diffusion resistance is really low. As a result, the porous carbon will show anexcellent rate performance. In this work, porous carbons were prepared from differentcarbon precursors by needle-like Mg(OH)2/MgO (MgO is the product of the Mg(OH)2pyrolysis) templates. Some testing techniques, such as N2adsorption, X-ray diffraction,Transmission electron microscope (TEM), cyclic voltammetry (CV) and galvanostaticcharge/discharge, were used to characterize the structure and property of theexperiment samples. The effect of manufacturing parameters on the characteristics ofthose samples, such as pore structure and morphology, were studied in detail, and therelation between the structure characteristics and the capacitive capability was alsoinvestigated.
Firstly, mesoporous carbon was prepared from soluble starch. The highest valueof total pore volume is3.5cm3g-1, in which80%is mesopore volume. Carbonizationtechnics affect the structure and electrochemical property greatly. The prepared carbonmaterials shows a relative high specific capacitance and an excellent rate capability.Specific capacitance normalized by specific surface area and pore diameter show alogarithmic relationship. With the pore diameter increasing, the specific capacitancenormalized by specific surface area increases quickly in the range of5-12nm, thenapproaches a constant value gradually. It is found that a graphite-like domain can beformed in the porous carbon due to the presence of needle like template, and amechanism that the needle-like template act as a director reagent is proposed.
Then, in order to obtain a higher specific capacitance, porous carbons with largemicropores and abundant mesopores were prepared from resorcinol/formaldehyde-based organic aquagel and coal tar pitch. Due to the needle like template, largemicropores are formed in the inner of the basic carbon particles, resulting in that theprepared porous carbon shows a large specific surface area. Those micropores and themesopores remained after removing template in the porous carbon might form acolumnar cactus-like pore texture, which is favorable to improve the utilization ratio ofthe miropores under a high charge/discharge current. Through small amounts of NaOHactivation, the specific surface area of the porous carbon increased greatly, resulting ina great improvement of the capacitance. In6M KOH solution, the porous carbon madefrom coal tar pitch oxidized with nitricacid/vitriol shows a highest specific capacitanceof282F g-1, which could be retained65%under a current density of50A g-1.
Further, mesoporous carbon/MnO2composite was prepared by the method thatcarbon reduces potassium permanganate directly. Amorphous MnO2is loaded in thepore inner of mesoporous carbon, and the composite shows a porous characteristic.The basic feature of pore size distribution of the composite is similar as that of themesoporous carbon. Carbon acts as the conductive framework, thus the compositeshows a more better rate capability than powder MnO2. An asymmetric aqueoussupercapacitor system is constructed by the carbon/MnO2composite as anode materialand the porous carbon with high capacitance as cathode material, and shows a highspecific energy and high specific power characteristic.
首先以可溶性淀粉为碳前驱体，制备了以中孔为主的多孔炭，总孔容可达3.5cm3g-1，其中中孔孔容占80%以上，中孔炭的结构与性能受炭化工艺影响较大，其比容量较高，倍率性能优异。中孔炭的表面积比容量与其孔径呈对数关系，在约5-12nm的范围内增加较快，随着材料孔径继续增大，其比容量逐渐接近恒定值。发现针状模板剂的存在导致多孔炭中出现局域的类石墨结构，并提出其模板导向形成机制。
为了获得更高的比容量，分别采用间苯二酚/甲醛有机凝胶和易石墨化的煤焦油沥青为碳前驱体，制备了微孔丰富、中孔发达的多孔炭。针状模板的存在促使基元炭颗粒内部形成大量微孔，使多孔炭比表面积很高，这些微孔与模板脱除后留下的针状中孔形成类仙人柱形貌的层次孔结构，该结构有利于提高微孔在大电流下的利用率。并采用低用量的NaOH对材料进行活化，大大提高了多孔炭的表面积，比容量也大大提高。在6M KOH溶液中，以经硝酸/硫酸氧化的沥青制得的多孔炭的比容量最高达到282F g-1，在50A g-1的电流下容量仍能保持65%。
进一步采用炭直接还原高锰酸钾的方法，成功的将无定形MnO2负载到中孔炭的孔内部，制得中孔炭/MnO2复合材料。复合材料仍保持多孔性，孔分布的基本特征与基材中孔炭有相似性。因多孔炭成为导电骨架，复合材料的倍率性能较粉体MnO2大大提高。以复合材料为正极、高比容量多孔炭为负极组装的水系非对称电容器体系，表现出高比能量、高比功率的特性。
Electrode material is a key factor for improving supercapacitors performance. Asmall resistance of electrolyte ion diffusion in the electrode material is necessary tohigher power output. Upto now, porous carbon is the best one among the carbonelectrode materials in practical utility. How to realize the optimal electrochemicalpropereis of the porous carbon is a great challenge for the researchers. The work aimsto design and prepare a sort of porous carbon with needle-like mesoporous structureand high conductivity, and then a composite consisting of the porous carbon andmetallic oxide, and subsequently construct a supercapacitor system with high specificenergy and high specific power. Electrolyte ions transfer in such a straight mesopores,the ion diffusion resistance is really low. As a result, the porous carbon will show anexcellent rate performance. In this work, porous carbons were prepared from differentcarbon precursors by needle-like Mg(OH)2/MgO (MgO is the product of the Mg(OH)2pyrolysis) templates. Some testing techniques, such as N2adsorption, X-ray diffraction,Transmission electron microscope (TEM), cyclic voltammetry (CV) and galvanostaticcharge/discharge, were used to characterize the structure and property of theexperiment samples. The effect of manufacturing parameters on the characteristics ofthose samples, such as pore structure and morphology, were studied in detail, and therelation between the structure characteristics and the capacitive capability was alsoinvestigated.
Firstly, mesoporous carbon was prepared from soluble starch. The highest valueof total pore volume is3.5cm3g-1, in which80%is mesopore volume. Carbonizationtechnics affect the structure and electrochemical property greatly. The prepared carbonmaterials shows a relative high specific capacitance and an excellent rate capability.Specific capacitance normalized by specific surface area and pore diameter show alogarithmic relationship. With the pore diameter increasing, the specific capacitancenormalized by specific surface area increases quickly in the range of5-12nm, thenapproaches a constant value gradually. It is found that a graphite-like domain can beformed in the porous carbon due to the presence of needle like template, and amechanism that the needle-like template act as a director reagent is proposed.
Then, in order to obtain a higher specific capacitance, porous carbons with largemicropores and abundant mesopores were prepared from resorcinol/formaldehyde-based organic aquagel and coal tar pitch. Due to the needle like template, largemicropores are formed in the inner of the basic carbon particles, resulting in that theprepared porous carbon shows a large specific surface area. Those micropores and themesopores remained after removing template in the porous carbon might form acolumnar cactus-like pore texture, which is favorable to improve the utilization ratio ofthe miropores under a high charge/discharge current. Through small amounts of NaOHactivation, the specific surface area of the porous carbon increased greatly, resulting ina great improvement of the capacitance. In6M KOH solution, the porous carbon madefrom coal tar pitch oxidized with nitricacid/vitriol shows a highest specific capacitanceof282F g-1, which could be retained65%under a current density of50A g-1.
Further, mesoporous carbon/MnO2composite was prepared by the method thatcarbon reduces potassium permanganate directly. Amorphous MnO2is loaded in thepore inner of mesoporous carbon, and the composite shows a porous characteristic.The basic feature of pore size distribution of the composite is similar as that of themesoporous carbon. Carbon acts as the conductive framework, thus the compositeshows a more better rate capability than powder MnO2. An asymmetric aqueoussupercapacitor system is constructed by the carbon/MnO2composite as anode materialand the porous carbon with high capacitance as cathode material, and shows a highspecific energy and high specific power characteristic.
引文
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