Abstract
Oxides composed of an oxygen framework and interstitial cations are promising cathode materials for lithium‐ion batteries. However, the instability of the oxygen framework under harsh operating conditions results in fast battery capacity decay, due to the weak orbital interactions between cations and oxygen (mainly 3
d
–2
p
interaction). Here, a robust and endurable oxygen framework is created by introducing strong 4
s
–2
p
orbital hybridization into the structure using LiNi
0.5
Mn
1.5
O
4
oxide as an example. The modified oxide delivers extraordinarily stable battery performance, achieving 71.4 % capacity retention after 2000 cycles at 1 C. This work shows that an orbital‐level understanding can be leveraged to engineer high structural stability of the anion oxygen framework of oxides. Moreover, the similarity of the oxygen lattice between oxide electrodes makes this approach extendable to other electrodes, with orbital‐focused engineering a new avenue for the fundamental modification of battery materials.
Strong molecular bonding formed by Ge 4
s
and O 2
p
orbitals contributes to a robust and endurable metal–oxygen framework of the spinel oxide structure, which is not achievable via common 3
d
–2
p
orbital hybridization alone, making the oxide cathodes exhibit extraordinarily stable electrochemical performance in lithium‐ion batteries.