Graphical Abstract
![](https://wqketang.oss-cn-beijing.aliyuncs.com/zip-unzip/zip-d4b01a55-7982-41de-8fed-2eea429fa941/EMD-2023-0016/files/EMD-2023-0016-revise-final-Abstract.jpg?Expires=1725755544&OSSAccessKeyId=STS.NTb4DXU4JD36Bm7sCfLXpJ6m3&Signature=1t21mks7k%2BwXL%2BcSXpkhudI5CCg%3D&security-token=CAISywJ1q6Ft5B2yfSjIr5fXf%2F7suOtr8%2FHdQEuGl0MzQNdcpfPG0Tz2IHtKenhsBOsbtfk1mG5W5%2FgZlqJ9SptIAEfJa9d99MznDrFDltCT1fau5Jko1beHewHKeTOZsebWZ%2BLmNqC%2FHt6md1HDkAJq3LL%2Bbk%2FMdle5MJqP%2B%2FUFB5ZtKWveVzddA8pMLQZPsdITMWCrVcygKRn3mGHdfiEK00he8TouufTinpHMskGA1Aell7Mvyt6vcsT%2BXa5FJ4xiVtq55utye5fa3TRYgxowr%2Fwo0v0YpGya5YzHXwcPskvdKZbo78UqLQlla6w%2BGqFJqvPxr%2Fp8t%2Fx5fWJKAezhVgs8cVM8JOjIqKOscIsi5g%2Fq6gWPcD1LXoQ6vH1ZZ5%2FAzVZaVWUEMpNqcRxTMldXaQqhSZT8m3upKXzOJeX7ls9%2Fv%2FV7p7UvocvUTzDnGoABCKEw5zeqVEFt1P1tLtZPWFgqoxMOwG7QFDd16KVAW84FGRPy%2BnneCrZe0HYm786BcWDP3XmPmuNohvQFG%2FYf9X49aXiJQs6eJFt93A5NT8dSRXVX3d0gsHp4aPRQxBXChZPaPyC91ZpQadlfhy79dcqC4544nSt5yl%2BptAu%2FCNkgAA%3D%3D)
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Polymer matrices have limited abilities to dissociate lithium salts and transport ions, thus making most solid-state polymer electrolytes (SPEs) have extremely low ionic conductivities (10−7–10−5 S/cm) at 25 ℃. In this work, a high-energy electron-beam (e-beam) irradiation is applied to a poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] SPE to improve the ionic conductivity. P(VDF-TrFE) easily shows pure all-trans (TTTT) conformation with all fluorine atoms located on one side of the carbon chain to provide an ion transport highway. E-beam irradiation keeps large amounts of TTTT conformation of P(VDF-TrFE) and produces –CF3 side groups, where the latter expands the interchain distance to split the large ferroelectric domains into nanosize to induce a unique relaxor ferroelectric behavior. This enhances the dielectric constant of the irradiated P(VDF-TrFE) from 15 to 20 and thus facilitates lithium salt dissociation. As a consequence, the ionic conductivity of the irradiated P(VDF-TrFE) SPE is increased from 5.8 × 10−5 to 1.6 × 10−4 S cm−1 at 25 ℃. The solid-state Li//Li symmetrical cell cycles for more than 3000 h at 25 ℃ without a short circuit. Furthermore, the solid-state LFP//Li cell cycles stably for more than 350 cycles with a capacity retention of around 91.3% at 1 C and 25 ℃. This study paves a new way to prepare high-performance SPEs by inducing high dielectric constants and abundant TTTT conformations through e-beam irradiation.
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