The neutron powder diffraction technique has been used for structural studies of Rb2UBr6 solid electrolyte as a function of temperature. The low-, room-, and high-temperature structures have been determined. At the temperature range of 4.2–80 K, the compound crystallizes in a monoclinic unit cell in the P21/c space group. At 80 K and 853 K, the compound crystallizes in a tetragonal unit cell in the P4/mnc space group. At 300 K, the lattice constants are a = b = 7.745(1) and c = 11.064(1) Å. At the temperature range of 853–960 K, a trigonal phase is observed in the P–3ml space group.
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