CAJ | 학술논문

采用循环伏安法、交流阻抗法和方波伏安法等电化学测量技术，考察了KF对Na3AlF6-Al2O3熔盐电解体系的阴极过程的影响。研究结果表明：在Na3AlF6-Al2O3和Na3AlF6-Al2O3-KF电解质体系的循环伏安曲线中，还原峰随着扫描速率的增大而负移，氧化峰随着扫描速率的增大而正移，在扫描速率较低（25～100 mV·s-1）的情况下，反应过程不可逆，反应过程相对平缓稳定；随着扫描速率的提高，电极可逆性相对提高。由于电极附近铝离子的聚合现象，使得在无 KF 的熔盐体系下，交流阻抗的高频区出现了感抗现象；在含 KF 的体系下，反应是由电化学反应过程和扩散过程共同控制的，且随着KF含量的增加，Warburg阻抗系数减小，电化学反应过程控制逐步取代扩散过程控制；反应电流也随之增大，氧化速率加快，还原和氧化过程可逆性降低。同时 KF 的加入抑制了铝的沉积，合金化作用比较明显，通过对阴极前波进行高斯拟合，得到不同KF含量（0、3%、5%）体系下的铝离子的电子转移数分别为1.19、1.02、0.75。
채용순배복안법、교류조항법화방파복안법등전화학측량기술，고찰료KF대Na3AlF6-Al2O3용염전해체계적음겁과정적영향。연구결과표명：재Na3AlF6-Al2O3화Na3AlF6-Al2O3-KF전해질체계적순배복안곡선중，환원봉수착소묘속솔적증대이부이，양화봉수착소묘속솔적증대이정이，재소묘속솔교저（25～100 mV·s-1）적정황하，반응과정불가역，반응과정상대평완은정；수착소묘속솔적제고，전겁가역성상대제고。유우전겁부근려리자적취합현상，사득재무 KF 적용염체계하，교류조항적고빈구출현료감항현상；재함 KF 적체계하，반응시유전화학반응과정화확산과정공동공제적，차수착KF함량적증가，Warburg조항계수감소，전화학반응과정공제축보취대확산과정공제；반응전류야수지증대，양화속솔가쾌，환원화양화과정가역성강저。동시 KF 적가입억제료려적침적，합금화작용비교명현，통과대음겁전파진행고사의합，득도불동KF함량（0、3%、5%）체계하적려리자적전자전이수분별위1.19、1.02、0.75。
The electrochemical behavior of cathodic process was investigated by means of cyclic voltammetry, electrochemical impedance spectroscopy and square wave voltammetry in both Na3AlF6-Al2O3 and Na3AlF6-Al2O3-KF systems. The results showed that the reduction peaks shifted negatively and oxidation peak shifted positively with the increase of scan rate from the measurement of cyclic voltammetry. The reaction process was irreversible under the condition of lower scan rate, and the reaction was relatively flat and stable, but the reduction process became reversible gradually with the increase of scan rate. Because of polymerization phenomenon at the electrode-site, inductance phenomenon appeared in the high frequency area when KF was absent in the molten salt. Under the condition of containing KF, the reaction was predominantly controlled by charge transfer and diffusion. The growth of the concentration of KF could decrease diffusion impedance coefficient and increase reaction current. The charge transfer process gradually replaced the diffusion process and accelerated oxidation rate. Meanwhile the reduction and oxidation process became reversible. Adding KF also suppressed the deposition of aluminum and alloying effect was obvious. Through Gaussian fitting for the cathodic prewave, electron transfer numbers of Al ion were 1.19, 1.02 and 0.75 in different systems of KF concentration(0, 3%,5%)respectively.