Potassium-ion batteries (KIBs) have come up as a potential alternative to lithium-ion batteries due to abundant potassium storage in the crust. Red phosphorus is a promising anode material for KIBs with abundant resources and high theoretical capacity. Nevertheless, large volume expansion, low electronic conductivity, and limited K+ charging speed in red phosphorus upon cycling have severely hindered the development of red phosphorus-based anodes. To obtain improved conductivity and structural stability, surface engineering of red phosphorus is required. Poly(3,4-ethylenedioxythiophene) (PEDOT)-coated red phosphorus nanospheres (RPNP@PEDOT) with an average diameter of 60 nm were synthesized via a facile solution-phase approach. PEDOT can relieve the volume change of red phosphorus and promote electron/ion transportation during charge−discharge cycles, which is partially corroborated by our DFT calculations. A specific capacity of 402 mAh g−1 at 0.1 A g−1 after 40 cycles, and a specific capacity of 302 mAh g−1 at 0.5 A g−1 after 275 cycles, were achieved by RPNP@PEDOT anode with a high pseudocapacitive contribution of 62%. The surface–interface engineering for the organic–inorganic composite of RPNP@PEDOT provides a novel perspective for broad applications of red phosphorus-based KIBs in fast charging occasions.
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