Developing high-performance Ni cathodes and understanding the relationship between electron states of Ni 3d orbital and energy storage mechanism from an atomic-orbital perspective are crucial yet challenging for alkal...Developing high-performance Ni cathodes and understanding the relationship between electron states of Ni 3d orbital and energy storage mechanism from an atomic-orbital perspective are crucial yet challenging for alkaline nickel-zinc batteries.Herein,we innovatively design P-NiMoO_(4)/NiSe_(2)heterostructures with rich oxygen vacancy via a selective component segregation.The P substitution in NiMoO_(4)activate Ni atoms,leading to the spin-state transition of Ni-3d orbitals from high-spin to low-spin,which promote the uniform and rapid nucleation of NiSe_(2)on the surface of NiMoO_(4)during subsequent selenization process.After selenization,the in situ formed P-NiMoO_(4)/NiSe_(2)heterostructures exhibits continuous increased unoccupied states of Ni 3d-orbitals and higher Ni valence state.The synergistic effect of P doping and selenization modulate the d-band center(ɛd)level of Ni 3d,thereby promoting d-p orbital hybridization between Ni 3d and O 2p of OH−as well as OH−adsorption ability.Consequently,the P-NiMoO_(4)/NiSe_(2)exhibits a top-level specific capacity of 390.7 mA h g^(−1)at 1 A g^(−1),2.8-fold higher than that of pristine NiMoO_(4),accompanied by remarkable rate capability and structural stability.Moreover,the assembled pouch-type battery and flexible devices demonstrate the practical application potential.This work provides fundamental insights into orbital-level engineering of battery materials for enhanced redox kinetics and cycling stability.展开更多
基金supported by the National Natural Science Foundation of China (Grant no. 22209083)
文摘Developing high-performance Ni cathodes and understanding the relationship between electron states of Ni 3d orbital and energy storage mechanism from an atomic-orbital perspective are crucial yet challenging for alkaline nickel-zinc batteries.Herein,we innovatively design P-NiMoO_(4)/NiSe_(2)heterostructures with rich oxygen vacancy via a selective component segregation.The P substitution in NiMoO_(4)activate Ni atoms,leading to the spin-state transition of Ni-3d orbitals from high-spin to low-spin,which promote the uniform and rapid nucleation of NiSe_(2)on the surface of NiMoO_(4)during subsequent selenization process.After selenization,the in situ formed P-NiMoO_(4)/NiSe_(2)heterostructures exhibits continuous increased unoccupied states of Ni 3d-orbitals and higher Ni valence state.The synergistic effect of P doping and selenization modulate the d-band center(ɛd)level of Ni 3d,thereby promoting d-p orbital hybridization between Ni 3d and O 2p of OH−as well as OH−adsorption ability.Consequently,the P-NiMoO_(4)/NiSe_(2)exhibits a top-level specific capacity of 390.7 mA h g^(−1)at 1 A g^(−1),2.8-fold higher than that of pristine NiMoO_(4),accompanied by remarkable rate capability and structural stability.Moreover,the assembled pouch-type battery and flexible devices demonstrate the practical application potential.This work provides fundamental insights into orbital-level engineering of battery materials for enhanced redox kinetics and cycling stability.
