Graphical Abstract
![](https://wqketang.oss-cn-beijing.aliyuncs.com/unzip/large-zip/zip-c3274b65-a8c2-46f2-9de5-e1265010cafa/6065/files/6065-TOC.jpg?Expires=1725757501&OSSAccessKeyId=STS.NT5eViCkqzTYdbfdqxMkjpyyq&Signature=HHavoIaTz8XdnooZfE9OgK9sIdQ%3D&security-token=CAISywJ1q6Ft5B2yfSjIr5eALuzdrrRQzZayZkTXgHEtQeRGn7zSkzz2IHtKenhsBOsbtfk1mG5W5%2FgZlqJ9SptIAEfJa9d99MzUP%2FpFltCT1fau5Jko1beHewHKeTOZsebWZ%2BLmNqC%2FHt6md1HDkAJq3LL%2Bbk%2FMdle5MJqP%2B%2FUFB5ZtKWveVzddA8pMLQZPsdITMWCrVcygKRn3mGHdfiEK00he8TouufTinpHMskGA1Aell7Mvyt6vcsT%2BXa5FJ4xiVtq55utye5fa3TRYgxowr%2Fwo0v0YpGya5YzHXwcPskvdKZbo78UqLQlla6w%2BGqFJqvPxr%2Fp8t%2Fx5fWJKAezhVgs8cVM8JOjIqKOscIsiJsO71SmqFV55c8Fdm%2BgUooJVgIMhTnduUfAPJAGOxzJitP%2BUVGGphr60TEnBL4rB5MUctfzRp75SXVPUTzDnGoABjuNLcf76FQN6p3t%2BSlCg%2FxR5C72RIk78k%2BUi44L9ZBmFT6F8GV7aXA52D1Ps56knKF6PAnhRivwyTxgsolycBfvccb3t5jGJ24SgY0aYosAECutxAo7sJhSwlwZvGwGDZJsop1vGiZ8eN1MbtZeRRuMeaZ2I%2BQo%2BnVP6Cf%2F0pDsgAA%3D%3D)
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In order to enhance the ionic conductivity of solid polymer electrolytes (SPEs) and their structural rigidity against lithium dendrite during lithium-ion battery (LIB) cycling, we propose porous garnet Li6.4La3Zr2Al0.2O12 (LLZO), as the filler to SPEs. The porous LLZO with interlinked grains was synthesized via a resol-assisted cationic coordinative co-assembly approach. The porous structure of LLZO with high specific surface area facilitates the interaction between polymer and filler and provides sufficient entrance for Li+ migration into the LLZO phase. Furthermore, the interconnection of LLZO grains forms continuous inorganic pathways for fast Li+ migration, which avoid the multiple diffusion for Li+ in interface. As a result, the SPEs with porous LLZO (SPE-PL) show a high ionic conductive of 0.73 mS·cm−1 at 30 °C and lithium-ion transference number of 0.40. The porous LLZO with uniformly dispersed pores also acts as an ion distributor to regulate ionic flux. The lithium-symmetrical batteries assembled with SPE-PL show a highly stable Li plating/stripping cycling for nearly 3000 h at 0.1 mA·cm−2. The corresponding Li/LiFePO4 batteries also exhibit excellent cyclic performance with capacity retention of 75% after nearly 500 cycles. This work brings new insights into the design of conductive fillers and the optimization of SPEs.
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