Preparation of PDOL-based solid electrolyte by in-situ polymerization and its application in lithium metal batteries

doi:10.19799/j.cnki.2095-4239.2024.0712

Abstract

Abstract:

YPVDF nanofiber membranes coated with yttria-stabilized zirconia (YSZ) nanoparticles on the surface of polyvinylidene fluoride (PVDF) nanofibers were prepared by a coaxial electrospinning process. In this process, 1,3-dioxolane (DOL) was used as the polymer precursor monomer; tris (trifluoromethanesulfonic acid) aluminum (Al(OfT)₃) was used as the initiator; LiTFSI was used as the lithium salt; and FEC was used as the SEI film additive. In situ polymerization was performed on the YPVDF nanofiber base film with a high surface area to generate PDOL. PDOL formed a large number of YSZ/PDOL organic-inorganic rapid-ion-transport interfaces with YSZ on the surface of YPVDF fibers. PDOL@YPVDF-CSE has an ionic conductivity of 0.94 × 10^-4 S/cm at room temperature. The Lewis acid sites (Zr⁴⁺, Y³⁺, and oxygen vacancies) of the YSZ on the YPVDF fibers facilitate the adsorption of anions from LiTFSI, thus promoting the dissociation of Li⁺ from LiTFSI. Therefore, PDOL@YPVDF-CSE YSZ has a lithium ion migration number of 0.78, and the Lewis acid sites provided by YSZ can synergistically promote the ring opening polymerization of DOL with Al (OfT)₃, resulting in a DOL monomer conversion rate of 98.2%. In addition, because of the introduction of YPVDF nanofibers, the heat-resistant decomposition temperature of PDOL@YPVDF-CSE increased to 312 ℃. A symmetric lithium battery assembled as Li| PDOL@YPVDF-CSE |Li was capable of stable cycling for over 1500 h. An assembled LiFeO₄| PDOL@YPVDF-CSE | battery subjected to 800 cycles at a rate of 0.5C had a capacity retention rate of 97.4%, and after 500 cycles at a rate of 2C, the capacity retention rate was 96.8%. Meanwhile, the NCM622 | PDOL @ YPVDF-CSE | Li battery assembled with LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) as the positive electrode had a capacity retention rate of 96.2% after 150 cycles at a rate of 1C.

Key words: coaxial electrospinning, poly(1,3-dioxolane), in situ polymerization, electrochemical performance, composite solid electrolyte

CLC Number:

O 63

Xunchang JIANG, Kelin YU, Daxiang YANG, Minhui LIAO, Yang ZHOU. Preparation of PDOL-based solid electrolyte by in-situ polymerization and its application in lithium metal batteries[J]. Energy Storage Science and Technology, 2025, 14(1): 1-12.

Figures/Tables 10

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