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Copyright © 2020 American Chemical Society.The Na2UF8 complex is an important intermediate compound in the purification of UF6 by the adsorption-desorption process during fluoride volatility of the spent nuclear fuel, and its decomposition is seriously affected by temperature and atmosphere. In this study, the thermal stability of Na2UF8 in the argon atmosphere was investigated by the in situ Raman spectroscopy. The decomposition products of Na2UF8 at different temperatures were systematically determined by X-ray diffraction spectroscop