Correction for ‘A relaxor ferroelectric polymer with an ultrahigh dielectric constant largely promotes the dissociation of lithium salts to achieve high ionic conductivity’ by Yan-Fei Huang et al. , Energy Environ. Sci. , 2021, 14 , 6021–6029, https://doi.org/10.1039/D1EE02663A.

Restricted by the poor ability of polymers to dissociate lithium salts and transport ions, solid‐state polymer electrolytes (SPEs) show extremely low ionic conductivities (≈10 −7 –10 −5 S cm −1 ) and transference number of lithium ions ( t Li+ ≈0.2–0.4) at 25 °C. Here, a novel polymer matrix of SPEs that simultaneously promotes lithium salt dissociation and ion transportation based on a high dielectric poly(vinylidene fluoride‐trifluoroethylene‐chlorotrifluoroethylene) (TerP) and an all‐ trans conformational poly(vinylidene fluoride‐trifluoroethylene) (CoP), is developed. The high dielectric constant increases the polarity of CH 2 CF 2 polar groups; then, brings a strong electronegative end that dissociates Li + from lithium salts. The all‐ trans conformation assures all fluorine atoms locate on one side of the chain, constructing ion hopping highways. As a result, the TerP/CoP (TC) SPE exhibits a high ionic conductivity (2.37 × 10 −4 S cm −1 ) and a quite large t Li + of 0.61 at 25 °C. The Li/TC SPE/Li symmetric cells cycle stably for more than half a year (>4500 h) and the LiNi 0.8 Co 0.1 Mn 0.1 O 2 /TC SPE/Li cell cycles steadily for 1000 and 600 cycles at 1 C and 2 C at 25 °C, respectively. This work paves a new way to prepare high‐performance SPEs by simultaneously modulating dielectric constants and conformation of polymers.

A unique P(VDF-TrFE) that always shows an all-trans conformation displays a strong polarity to promote the dissociation of lithium salts, increasing the ionic conductivity of solid-state polymer electrolytes to 4.48 × 10−4 S cm−1 at 25 °C.

A unique relaxor ferroelectric P(VDF-TrFE-CTFE) is investigated as a matrix of SPEs. The P(VDF-TrFE-CTFE) with ultrahigh ε r promotes the dissociation of LiTFSI to greatly enhance the ionic conductivity and the transference number of lithium ions.

The extremely low room-temperature ionic conductivity of solid-state polymer electrolytes (SPEs) ranging from 10(-7) to 10(-5) S cm(-1) seriously restricts their practical application in solid-state lithium metal batteries (LMBs). Herein, a unique relaxor ferroelectric (RFE) polymer of poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)] is first investigated as a matrix of SPEs. We find that the P(VDF-TrFE-CTFE) with an ultrahigh dielectric constant (epsilon(r)) of 44 presents a stronger solvation ability towards lithium ions, which promotes the dissociation of LiN(SO2CF3)(2) to form more free charge carriers and enhances their mobility compared to the conventional PVDF with a low epsilon(r) of 9. The P(VDF-TrFE-CTFE) based SPEs show a much higher ionic conductivity of 3.10 x 10(-4) S cm(-1) at 25 degrees C and lower activation energy (0.26 eV) than PVDF based SPEs (1.77 x 10(-5) S cm(-1) and 0.49 eV). The PVDF blended with the P(VDF-TrFE-CTFE) or dielectric fillers such as BaTiO3 further confirm that the hybrid electrolytes with a larger epsilon(r) show a higher ionic conductivity. In addition, very tight interfaces of P(VDF-TrFE-CTFE) based SPEs with both the cathode and Li metal anode are constructed to ensure a stable interfacial resistance during cycling. The LiFePO4/Li and LiNi0.8Co0.1Mo0.1O2/Li batteries using P(VDF-TrFE-CTFE) based SPEs present a stable cycling performance at 25 degrees C. This work proposes a new strategy and opens a new research area to construct SPEs with high ionic conductivity by greatly increasing the epsilon(r) of polymers.