水溶性炭质中间体的制备及其在电化学领域的应用研究
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摘要
由于日趋严重的环境问题和日益紧缺的化石资源，绿色能源越来越受到人们的关注，尤其是双电层电容器和锂离子电池等储能元件的发展，水溶性炭质中间体在制备炭材料过程中可以避免有机溶剂的使用，降低化学试剂用量，省去氧化稳定化过程，具有经济，节能，环保的特点，符合绿色化工的要求。考察了水溶性中间体的结构，形成机理，拓展其在储能领域的应用，具有一定的科研价值与应用前景。
本文分别在水溶液和丙酮两种不同的溶剂中制备出两种不同形态的水溶性炭质中间体—片状中间体和球状中间体，并通过多种表征手段对其结构和形成机理进行了分析。结果表明，水溶性中间体一级单元是官能化的稠环分子，在碱溶液中以纳米形态稳定存在，在炭层边缘和骨架上均被引入官能团，包括-COOH，-SO_3H，-OH，-NO_2，-C=O等，其中-NO_2的存在是水溶性中间体能够溶于碱溶液的主要原因。使用丙酮置换水溶性中间体乙二胺溶液中的水，可以得到球状中间体，这些微球粒径分布在30~50nm范围内，微球之间粘连聚集成类似炭气凝胶的外貌结构。形成的球状中间体的微晶尺寸比片状中间体小，层间距大。生成的球状中间体比表面积为89.8m~2/g，经过800°C炭化之后比表面积升高到292.3m~2/g，在炭化过程中有许多微孔形成。
以针状焦为原料制备出两种不同氧化深度的水溶性中间体，使用X射线衍射和X射线光电子能谱对两种水溶性中间体进行了表征，然后考察了氧化深度和KOH的用量对孔结构的影响。实验证明以水溶性中间体为前驱体制备的活性炭孔结构发达，氧化程度越深，结构被破坏越严重，微晶尺寸越小，在相同的活化条件下得到的活性炭比表面积越大，中孔率越高，用作双电层电容器电极材料，其传输孔道比较短，孔道结构更有利于离子传输，尤其适用于大电流性能测试。
为了考察不同结构的前驱体对水溶性中间体的结构，以及相应的活性炭的孔结构的影响，本文使用了中温煤沥青为前驱体，并与针状焦基活性炭做对比。实验结果证明，沥青基水溶性中间体活化后得到的活性炭离子传输通道更短，微孔与中孔的分布更加合理，有利于离子的快速移动，提高了电容器的功率密度，最高可以达到5kW/kg。碱炭比为1.5时，得到的活性炭比表面积为2575m~2/g，孔容为1.54cm~3/g，中孔主要分布在2~4nm范围内。做为电极材料表现出优异的功率特性，在100A/g的电流密度下，质量比电容为195F/g。在有机系电容器中，此活性炭也体现出优异的能量特性，在不同的电流密度下能量密度为30~40Wh/kg。这也证明了我们找到了一种在相对较低的碱炭比条件下仍能保持较高中孔率和较高比表面积的前驱体—沥青基水溶性中间体。
利用中间体的水溶性和两亲性，在水相体系下包覆天然鳞片石墨，并考察包覆材料的电化学性能。随着包覆量的增加，样品的比表面积有所减小，拉曼光谱结果显示R（ID/IG）值随着包覆量的增加升高。在电化学测试中，随着包覆量的增加，首次效率呈现先升高后下降的趋势，在最佳包覆条件下得到的包覆样品首次效率能达到92.2%，可逆容量为359.6mAh/g，不可逆容量仅为30.4mAh/g；不同的炭化温度得到的样品首次效率不同，800-1400°C的热处理温度是最优范围，过高的升温速率也会造成样品首次效率的降低，最佳升温速率是1~5°C/min。
In view of environmental pollution and increasingly exhausted of fossil resource,renewable resource as alternate resources attracts more and more attention, especiallyfor the energy storage devices such as lithium ion battery and supercapacitor. Watersoluble carbonaceous intermediate can soluble in water owing to abundant functionalgroups. Based on this property, no organic solvent and stabilization process is neededduring the preparation of carbon materials when using intermediate as precursor.Therefore, ACM is economic, facile, and green in carbon materials production. It isnecessary to study the forming mechanism of intermediate and develop itsapplications in energy storage.
Two kinds of intermediate with different morphology were prepared in water andacetone respectively, and then various tools were used to study the structure andforming mechanism of intermediates. The results showed that the primary units ofintermediate are functionalized condensed nucleus molecular, which can disperse inalkaline solution in nanoscale. All these units were introduced onto variousO-containing groups, such as–COOH,-SO_3H,-OH,-NO_2,-C=O and so on, of which-NO_2is one of the main groups that influence the solubility of intermediate. Sphericalintermediate can be obtained using acetone to replace the water of alkaline solution.The resulting product was piled up by highly connected nano-particles with diametersof30~50nm, which constructed a3-D architecture also providing certain mesoporesand macropores. N2sorption analysis showed that the SBETof carbonized sphericalintermediate is292m2/g and had a wide pore size distribution from micropores tomacropores.
The properties of water soluble carbonaceous intermediates derived from greenneedle coke (GNC) and their influence on the subsequent porous carbon materialswere studied. Using the intermediates is an effective way for preparingwell-developed porous carbons by KOH activation. The degree of oxidation hadsignificant effects on the structures of the intermediates and further determined thestructure and EDLC performance of the final porous carbon. Soluble intermediatesproduced better high-rate-capacitive EDLC’s electrode materials than insoluble intermediates, which can be attributed that soluble intermediates have fewercarbonaceous stacked layers, which give the short diffusion path for the electrolyteand enable a high utilization rate of the micropores.
In order to further study the effect of microcrystalline structure on the poroustexture of activated carbon, another contrastive precursor, coal tar pitch from (CP)was taken into account. At the KOH/intermediate mass ratio of1.5, the porous carbonobtained exhibited surface area as high as2575m~2/g and pore volume as large as1.54cm~3/g, the pore size centered at2~4nm. Electrochemical characterizationsdemonstrated that CP-derived porous carbon showed superior capacitances both inaqueous (6M KOH) and organic (1M Et4NBF4/acetonitrile) electrolytes. In aqueoussystem, the specific capacitance of CP-A5-1.5reached284F/g at a current density of0.05A/g and still maintained at195F/g at current density of100A/g. In organicsystem, the energy density of CP-A5-1.5can reach to40Wh/Kg.
Based on the unique property of water solubility, intermediate was employed tocoat natural graphite, results showed that coated natural graphite show lessirreversible capacity and improved coulombic efficiency than unmodified naturalgraphite. The BET specific surface area of unmodified NFG drastically decreases aftercarbon coating. On the contrary, the R (ID/IG) value increases with the increase ofcoated amount. In order to have certain improvement in anode performance, optimumconditions for carbon coating had to be applied, under the optimum conditions, thereversible and irreversible capacity of coated sample is359.6mAh/g and30.4mAh/g,heat treatment temperature should be in the range of800-1400°C and heating rate inthe range of1-5°C/min.
本文分别在水溶液和丙酮两种不同的溶剂中制备出两种不同形态的水溶性炭质中间体—片状中间体和球状中间体，并通过多种表征手段对其结构和形成机理进行了分析。结果表明，水溶性中间体一级单元是官能化的稠环分子，在碱溶液中以纳米形态稳定存在，在炭层边缘和骨架上均被引入官能团，包括-COOH，-SO_3H，-OH，-NO_2，-C=O等，其中-NO_2的存在是水溶性中间体能够溶于碱溶液的主要原因。使用丙酮置换水溶性中间体乙二胺溶液中的水，可以得到球状中间体，这些微球粒径分布在30~50nm范围内，微球之间粘连聚集成类似炭气凝胶的外貌结构。形成的球状中间体的微晶尺寸比片状中间体小，层间距大。生成的球状中间体比表面积为89.8m~2/g，经过800°C炭化之后比表面积升高到292.3m~2/g，在炭化过程中有许多微孔形成。
以针状焦为原料制备出两种不同氧化深度的水溶性中间体，使用X射线衍射和X射线光电子能谱对两种水溶性中间体进行了表征，然后考察了氧化深度和KOH的用量对孔结构的影响。实验证明以水溶性中间体为前驱体制备的活性炭孔结构发达，氧化程度越深，结构被破坏越严重，微晶尺寸越小，在相同的活化条件下得到的活性炭比表面积越大，中孔率越高，用作双电层电容器电极材料，其传输孔道比较短，孔道结构更有利于离子传输，尤其适用于大电流性能测试。
为了考察不同结构的前驱体对水溶性中间体的结构，以及相应的活性炭的孔结构的影响，本文使用了中温煤沥青为前驱体，并与针状焦基活性炭做对比。实验结果证明，沥青基水溶性中间体活化后得到的活性炭离子传输通道更短，微孔与中孔的分布更加合理，有利于离子的快速移动，提高了电容器的功率密度，最高可以达到5kW/kg。碱炭比为1.5时，得到的活性炭比表面积为2575m~2/g，孔容为1.54cm~3/g，中孔主要分布在2~4nm范围内。做为电极材料表现出优异的功率特性，在100A/g的电流密度下，质量比电容为195F/g。在有机系电容器中，此活性炭也体现出优异的能量特性，在不同的电流密度下能量密度为30~40Wh/kg。这也证明了我们找到了一种在相对较低的碱炭比条件下仍能保持较高中孔率和较高比表面积的前驱体—沥青基水溶性中间体。
利用中间体的水溶性和两亲性，在水相体系下包覆天然鳞片石墨，并考察包覆材料的电化学性能。随着包覆量的增加，样品的比表面积有所减小，拉曼光谱结果显示R（ID/IG）值随着包覆量的增加升高。在电化学测试中，随着包覆量的增加，首次效率呈现先升高后下降的趋势，在最佳包覆条件下得到的包覆样品首次效率能达到92.2%，可逆容量为359.6mAh/g，不可逆容量仅为30.4mAh/g；不同的炭化温度得到的样品首次效率不同，800-1400°C的热处理温度是最优范围，过高的升温速率也会造成样品首次效率的降低，最佳升温速率是1~5°C/min。
In view of environmental pollution and increasingly exhausted of fossil resource,renewable resource as alternate resources attracts more and more attention, especiallyfor the energy storage devices such as lithium ion battery and supercapacitor. Watersoluble carbonaceous intermediate can soluble in water owing to abundant functionalgroups. Based on this property, no organic solvent and stabilization process is neededduring the preparation of carbon materials when using intermediate as precursor.Therefore, ACM is economic, facile, and green in carbon materials production. It isnecessary to study the forming mechanism of intermediate and develop itsapplications in energy storage.
Two kinds of intermediate with different morphology were prepared in water andacetone respectively, and then various tools were used to study the structure andforming mechanism of intermediates. The results showed that the primary units ofintermediate are functionalized condensed nucleus molecular, which can disperse inalkaline solution in nanoscale. All these units were introduced onto variousO-containing groups, such as–COOH,-SO_3H,-OH,-NO_2,-C=O and so on, of which-NO_2is one of the main groups that influence the solubility of intermediate. Sphericalintermediate can be obtained using acetone to replace the water of alkaline solution.The resulting product was piled up by highly connected nano-particles with diametersof30~50nm, which constructed a3-D architecture also providing certain mesoporesand macropores. N2sorption analysis showed that the SBETof carbonized sphericalintermediate is292m2/g and had a wide pore size distribution from micropores tomacropores.
The properties of water soluble carbonaceous intermediates derived from greenneedle coke (GNC) and their influence on the subsequent porous carbon materialswere studied. Using the intermediates is an effective way for preparingwell-developed porous carbons by KOH activation. The degree of oxidation hadsignificant effects on the structures of the intermediates and further determined thestructure and EDLC performance of the final porous carbon. Soluble intermediatesproduced better high-rate-capacitive EDLC’s electrode materials than insoluble intermediates, which can be attributed that soluble intermediates have fewercarbonaceous stacked layers, which give the short diffusion path for the electrolyteand enable a high utilization rate of the micropores.
In order to further study the effect of microcrystalline structure on the poroustexture of activated carbon, another contrastive precursor, coal tar pitch from (CP)was taken into account. At the KOH/intermediate mass ratio of1.5, the porous carbonobtained exhibited surface area as high as2575m~2/g and pore volume as large as1.54cm~3/g, the pore size centered at2~4nm. Electrochemical characterizationsdemonstrated that CP-derived porous carbon showed superior capacitances both inaqueous (6M KOH) and organic (1M Et4NBF4/acetonitrile) electrolytes. In aqueoussystem, the specific capacitance of CP-A5-1.5reached284F/g at a current density of0.05A/g and still maintained at195F/g at current density of100A/g. In organicsystem, the energy density of CP-A5-1.5can reach to40Wh/Kg.
Based on the unique property of water solubility, intermediate was employed tocoat natural graphite, results showed that coated natural graphite show lessirreversible capacity and improved coulombic efficiency than unmodified naturalgraphite. The BET specific surface area of unmodified NFG drastically decreases aftercarbon coating. On the contrary, the R (ID/IG) value increases with the increase ofcoated amount. In order to have certain improvement in anode performance, optimumconditions for carbon coating had to be applied, under the optimum conditions, thereversible and irreversible capacity of coated sample is359.6mAh/g and30.4mAh/g,heat treatment temperature should be in the range of800-1400°C and heating rate inthe range of1-5°C/min.
引文
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