Fe304/腐殖酸铵基炭复合材料的制备及其电化学性能
Preparation and electrochemical properties of Fe3 O4 / ammonium⁃humate based carbon composites
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摘要: 制备 Fe3 O4 / 炭复合材料,既可以有效解决 Fe3 O4 颗粒团聚和导电性差的问题,又能充分利 用Fe3O4 的高容量,从而提供优异的电化学性能。 以煤系腐殖酸铵和氯化铁为原料,采用水热-炭 化工艺制备 Fe3O4 /腐殖酸铵基炭复合材料(Fe3O4 /SHAC-X),借助扫描电镜(SEM)、透射电 镜(TEM)、X 射线衍射(XRD)、低温氮吸附和 X 射线光电子能谱(XPS)等分析手段,对样品的微观 形貌、孔结构以及表面化学组成进行表征,并利用恒流充放电、循环伏安、交流阻抗等电化学测试技 术评价其作为超级电容器电极材料的电化学性能。 结果表明:Fe3 O4 / SHAC-X 的孔隙结构以中孔 为主,随着FeCl3·6H2O用量的增加,所制样品的中孔孔容和平均孔径逐渐增加。 Fe3O4 颗粒的负 载量和分布特性与FeCl3·6H2O用量紧密相关,Fe3O4/SHAC-3的Fe含量最高,Fe3O4 颗粒分散性 较好、颗粒尺寸均一;相应电极材料在 3 mol / L KOH 电解液中存在明显的赝电容效应,且电化学阻 抗较小,成型密度较高(1.48 g/ cm3 ),在 42.5 mA/ g 电流密度下的体积比电容高达 253 F/ cm3。Fe3 O4 / SHAC-2 具有良好的倍率性能,当电流密度从 42.5 mA / g 增加到 4 250 mA / g 时,其电容保持 率高达 73.1 %;循环稳定性较好,在 2 125 mA / g 的电流密度下经过 10 000 次恒流充放电之后,其 电容保持率为 88.3%。 研究有利于推动煤系腐殖酸的洁净高效利用,并对 Fe3 O4 / 炭复合材料的研 究应用具有借鉴意义。Abstract: The preparation of Fe3 O4 / carbon composites can not only effectively solve the problems of the agglomeration and poor electrical conductivity of Fe3O4particles,but also take advantage of the high capacity of Fe3O4,and provide some excellent electrochemical properties. In this study, the Fe3 O4 / ammonium⁃humate based carbon composites (Fe3O4 /SHAC⁃X)were prepared by hydrothermal⁃carbonization process using coal⁃based ammonium humate and fer⁃ ric chloride as raw materials. Scanning electron microscopy(SEM),transmission electron microscopy(TEM),X⁃ ray diffraction(XRD),nitrogen adsorption/desorption and X⁃ray photoelectron spectroscopy(XPS)were used to characterize the morphology,pore structure and surface chemistry of the samples. The electrochemical properties of the cor⁃ responding supercapacitor electrode materials were evaluated by constant current charge⁃discharge,cyclic voltammetry and alternating⁃current impedance measurements. The results show that the pore structure of Fe3 O4 / SHAC⁃X main⁃ ly consists of mesopores,the mesopore volume and average pore size increase gradually with the increase of the dosage of FeCl3·6H2O,which are also closely related to the mass loading and distribution characteristics of Fe3O4 particles. The Fe3 O4 / SHAC⁃3 has the highest Fe content among three samples,and the Fe3 O4 particles exhibit good dispersivity with uniform particle size. The corresponding electrode material has obvious pseudocapacitance effect in the 3 mol / L KOH electrolyte,showing a small electrochemical impedance and high volumetric capacitance of 253 F / cm3 at the cur⁃ rent density of 42.5 mA/g based on its high forming density(1.48 g/cm3). Moreover,the Fe3O4 /SHAC⁃2 displays a better rate performance,delivering a high capacitance retention of 73.1% with the current density increasing from 42.5 to 4 250 mA / g. The specific capacitance can still maintain 88.3% after 10 000 cycles at 2 125 mA / g,indicating a superior cycle performance. This work is conducive to promote the clean and efficient utilization of coal based humic acid,and also has reference significance for the research and application of the Fe3 O4 / carbon composites.