The ionic structure of the KF-AlF₃-Al₂O₃ system was studied using in situ high-temperature Raman spectroscopy and quantum mechanics calculations. The complexes in the KF-AlF₃-Al₂O₃ system with different molar ratios of KF to AlF₃ were AlF₆³⁻, AlF₅²⁻, AlF₄⁻, Al₂OF₄, Al₂OF₈⁴⁻, Al₂OF₆²⁻, and Al₂O₂F₄²⁻. The structures of Al₂OF₄, Al₂OF₈⁴⁻, Al₂OF₆²⁻, and Al₂O₂F₄²⁻ were optimized considering that the counterion K⁺, Al₂OF₄ exhibits D_2d point group symmetry, K₄Al₂OF₈ and K₂Al₂OF₆ exhibit C_2v point group symmetry, and K₂Al₂O₂F₄ exhibits C_2h point group symmetry. The experimental main Raman bands of Al₂OF₈⁴⁻, Al₂OF₆²⁻, and Al₂O₂F₄²⁻ were at 495 cm⁻¹, 465 cm⁻¹, and 410 cm⁻¹, respectively, after comparing their theoretical Raman spectra. The forms and contents of the oxygen-containing complex ions in the system were related to the molar ratio of KF to AlF₃ and to the concentration of alumina. AlF₆³⁻, AlF₅²⁻, AlF₄⁻, and Al₂OF₄ were found in the molten KF-AlF₃-Al₂O₃ system with a KF-to-AlF₃ molar ratio of 1.22 at a temperature of 1003 K. In the KF-AlF₃-Al₂O₃ system with a KF-to-AlF₃ molar ratio of 2 at a temperature of 1273 K, when the alumina concentration was less than or equal to 10 wt%, it contained AlF₆³⁻, AlF₅²⁻, AlF₄⁻, Al₂OF₄, and Al₂OF₈⁴⁻, and when the alumina concentration reached 12 wt%, Al₂OF₆²⁻ and Al₂O₂F₄²⁻ appeared. In the KF-AlF₃-Al₂O₃ system with a KF-to-AlF₃ molar ratio of 3 at a temperature of 1273 K, when the alumina concentration was less than or equal to 10 wt%, the system contained AlF₆³⁻, AlF₅²⁻, AlF₄⁻, Al₂OF₄, and Al₂OF₈⁴⁻. When the alumina concentration increased to 14 wt%, Al₂OF₆²⁻ and Al₂O₂F₄²⁻ began to appear but AlF₄⁻ disappeared. As the concentration of alumina increased, the contents of Al₂OF₆²⁻ and Al₂O₂F₄²⁻ increased. The ionic reactions that formed the various oxygen-containing complexes were obtained. The occurrence of these chemical reactions was related to the molar ratio of KF to AlF₃ in the system and the alumina concentration. When the KF-AlF₃-Al₂O₃ molten system with KF-to-AlF₃ molar ratios of 1.22, 2 and 3 were used as the aluminum electrolytes, the ion discharged at the anode was Al₂OF₈⁴⁻(except for the system with a KF-to-AlF₃ molar ratio of 1.22 in which the Al₂OF₄ was discharged at the anode), and the ion discharged at the cathode was Al₂OF₄ according to wave function analyses.

利用原位高温拉曼光谱和量子力学计算研究了KF-AlF ₃ -Al ₂ O ₃体系的离子结构。在KF-的AlF络合物₃ -Al ₂ ö ₃与KF的到的AlF不同摩尔比系统₃分别的AlF ₆ ^3-，的AlF ₅ ^2-，的AlF ₄ ^-，AL ₂ OF ₄，AL ₂ OF ₈ ^4-， Al ₂ OF ₆ ²⁻和Al ₂ O ₂ F ₄²⁻。考虑到抗衡离子K ⁺，Al ₂ OF ₄表现出D _2d点群对称性，因此优化了Al ₂ OF ₄，Al ₂ OF ₈ ^4-，Al ₂ OF ₆ ^2-和Al ₂ O ₂ F ₄ ^{2-的结构。}，K ₄ Al ₂ OF ₈和K ₂ Al ₂ OF ₆表现出C _2v点群对称性，而K ₂ Al ₂ O₂ F ₄具有C _2h点群对称性。Al的实验主要拉曼频带₂的₈ ^4-，AL ₂ OF ₆ ^2-，和Al ₂ ö ₂ ˚F ₄ ^2-均在495厘米^-1，465厘米^-1，和410厘米^-1分别，后比较他们的理论拉曼光谱。系统中含氧络合物离子的形式和含量与KF与AlF ₃的摩尔比以及氧化铝的浓度有关。AlF ₆ ³⁻，AlF ₅ ²⁻，的AlF ₄ ^- ，和Al ₂ OF ₄在熔融KF-的AlF发现₃ -Al ₂ ö ₃与KF到的AlF系统₃的1.22摩尔比的KF-的AlF的1003 K的温度下₃在1273 K的温度下，KF与AlF _3的摩尔比为2的-Al ₂ O ₃系统，当氧化铝浓度小于或等于10 wt％时，包含AlF ₆ ^3-和AlF ₅ ^2-，的AlF ₄ ^-，AL ₂ OF ₄和Al ₂ OF_在图8 ^4-中，当氧化铝浓度达到12重量％时，出现Al ₂ OF ₆ ^2-和Al ₂ O ₂ F ₄ ^2-。在1273 K的温度下KF与AlF ₃摩尔比为3的KF-AlF ₃ -Al ₂ O ₃系统中，当氧化铝浓度小于或等于10 wt％时，系统包含AlF ₆ ^3-，的AlF ₅ ^2-，的AlF ₄ ^-，AL ₂ OF ₄和Al ₂ OF ₈ ^4-。当氧化铝的浓度增加至14质量％，Al ₂ OF ₆ ^2-和Al ₂ ö ₂ ˚F ₄ ^2-开始出现，但的AlF ₄ ^-消失了。随着氧化铝浓度的增加，Al ₂ OF ₆ ^2-和Al ₂ O ₂ F ₄ ^2-的含量增加。获得了形成各种含氧络合物的离子反应。这些化学反应的发生与体系中KF与AlF ₃的摩尔比和氧化铝浓度有关。当KF-AlF ₃使用KF与AlF ₃摩尔比为1.22、2和3的-Al ₂ O ₃熔融体系作为铝电解质，在阳极处释放的离子为Al ₂ OF ₈ ^4-（具有KF的体系除外） -to-的AlF ₃的1.22，其中Al的摩尔比₂的₄在阳极排出），并且离子在阴极为Al排出₂ OF ₄根据波函数的分析。