For the first time, we introduce hollandite-type K0.17TiO2, in which potassium ions are located at
the center of a (2 × 2) tunnel structure, as a potential cathode material for potassium-ion batteries.
Density functional theory calculation predicts the possibility of K+ insertion into the hollanditetype
tunnel structure via a single-phase reaction. Operando X-ray diffraction and X-ray absorption
spectroscopy analyses verify that potassium ions are de-/intercalated from/into the crystal structure
of K0.17TiO2, accompanied by a Ti4+/Ti3+ redox reaction. The single-phase reaction is sustainable
for long-term cycling, with exceptionally high operation voltage over 3 V. The hollandite-type
K0.17TiO2 cathode delivers a reversible capacity of 60 mAh g−1 at 5 C (1.55 A g−1), with excellent
capacity retention of over 98 % of the initial capacity for 1000 cycles. This performance is related
to the single-phase reaction with good structural stability. This work presents a facile approach
that enables the use of a cathode with stable tunnel structure for potassium-ion batteries.