All-solid-state
potassium batteries are promising candidates in
the fields of large-scale energy storage owing to their intrinsic
safety, stability, and cost-effectiveness. However, a suitable solid-state
electrolyte with high ionic conductivity and favorable interfacial
stability is a major challenge for the design and development of these
batteries. Herein, we report the synthesis of new KB3H8·nNH3B3H7 (n = 0.5 and 1) complexes to develop suitable solid-state
K-ion conductors for batteries. Both the complexes undergo a reversible
phase transition below the thermal decomposition temperature. The
optimal KB3H8·NH3B3H7 delivers a solid-state K-ion conductivity of 1.3 ×
10–4 S cm–1 at 55 °C with
an activation energy of 0.44 eV after a transition from a monoclinic
to an orthorhombic phase, which is the highest value of K borohydrides
reported to date and places KB3H8·NH3B3H7 among the leading solid-state K-ion
conductors. Moreover, KB3H8·NH3B3H7 reveals a K-ion transference number of
nearly 0.93, an electrochemical stability window of 1.2 to 3.5 V vs
K+/K, a good capability of K dendrite suppression, and
a remarkable stability against the K metal anode due to the formation
of the stable interface. These performances make KB3H8·NH3B3H7 a promising
electrolyte for all-solid-state potassium batteries.