The dendrite growth of Li anodes severely degrades the performance of lithium-oxygen (Li-O₂) batteries. Recently, hybrid solid electrolyte (HSE) has been regarded as one of the most promising routes to tackle this problem. However, before this is realized, the HSE needs to simultaneously satisfy contradictory requirements of high modulus and even, flexible contact with Li anode, while ensuring uniform Li⁺ distribution. To tackle this complex dilemma, here, an HSE with rigid Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) core@ultrathin flexible poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) shell interface has been developed. The introduced large amount of nanometer-sized LAGP cores can not only act as structural enhancer to achieve high Young's modulus but can also construct Li⁺ diffusion network to homogenize Li⁺ distribution. The ultrathin flexible PVDF-HFP shell provides soft and stable contact between the rigid core and Li metal without affecting the Li⁺ distribution, meanwhile suppressing the reduction of LAGP induced by direct contact with Li metal. Thanks to these advantages, this ingenious HSE with ultra-high Young's modulus of 25 GPa endows dendrite-free Li deposition even at a deposition capacity of 23.6 mAh. Moreover, with the successful inhibition of Li dendrites, the HSE-based quasi-solid-state Li-O₂ battery delivers a long cycling stability of 146 cycles, which is more than three times that of gel polymer electrolyte-based Li-O₂ battery. This new insight may serve as a starting point for further designing of HSE in Li-O₂ batteries, and can also be extended to various battery systems such as sodium-oxygen batteries.

A high-performance Na–O₂ battery was achieved using a porous and metallic CoB nanosheet/carbon nanotube composite cathode, synthesised for the first time.