2026-10-12T04:57:02Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34024992 2026-09-29T16:04:33Z category_1 category_4 category_7 category_21 category_873 category_734 category_128 category_135 portal_63 item_type_6 month_year_09_2026

Molecular-Level Cleavage and Kinetics Optimization in PVDF Electrolytes for Anode-Lean Ultrastable Solid-State Sodium Batteries Chen Li (54018) Yongbiao Mu (9513581) Tongtong Deng (24139307) Jinlong Hu (3401600) Mingliu Kuang (25137786) Kuiyou Wang (17294480) Yangyang Wang (642852) Qizheng Zheng (11606740) Ronghua Wang (1834945) Chaohe Xu (1582795) Biophysics Biochemistry Medicine Biotechnology Chemical Sciences not elsewhere classified Biological Sciences not elsewhere classified Hematology Computational Biology unstable electrode interfaces theoretical simulations reveal reducing polymer crystallinity raising bulk conductivity low ionic conductivity loading pouch cell facilitates salt dissociation 93 × 10 sup >–</ sup sup >+</ sup optimized electrolyte system 3 –</ sup p simultaneously serves 12 mg cm lean ultrastable solid collectively promoting na 3 </ sub lean solid electrolyte interphase rich solid density solid based solid vinylidene fluoride state batteries solvation structure situ formation releasing f released f reduces f practical potential p remodels nucleophilic p migration barrier level cleavage ion conductor fundamentally constrained function nanofiller desolvation barrier 84 ev 5700 cycles 1000 cycles 100 cycles Polymer-based solid-state electrolytes are promising for safe and high-energy batteries but are fundamentally constrained by low ionic conductivity and unstable electrode interfaces. Here, we propose a molecular-level design using Na₃P as a dual-function nanofiller in poly(vinylidene fluoride) (PVDF) electrolytes. The nucleophilic P^3– selectively cleaves C–F bonds, reducing polymer crystallinity and releasing F^– species, while Na₃P simultaneously serves as a built-in fast-ion conductor. Theoretical simulations reveal that Na₃P remodels the solvation structure, lowers the desolvation barrier from 9.96 to 2.84 eV, facilitates salt dissociation and reduces F^– migration barrier from 4.23 to 3.0 eV, collectively promoting Na⁺ mobility and raising bulk conductivity to 6.93 × 10^–4 S cm^–1. The released F^– promotes in situ formation of a dense, NaF-rich solid-electrolyte interphase, enabling homogeneous Na plating. Consequently, an anode-lean solid-state sodium battery exhibits exceptional stability, with only 0.002% capacity fade per cycle over 1000 cycles at 5C and >5700 cycles at 10C. A high-loading pouch cell (12 mg cm^–2) also maintains stable performance for more than 100 cycles, underscoring the practical potential of this kinetics-optimized electrolyte system for high-energy-density solid-state batteries. 2026-09-29T00:00:00Z Text Journal contribution 10.1021/jacs.6c03378.s001 https://figshare.com/articles/journal_contribution/Molecular-Level_Cleavage_and_Kinetics_Optimization_in_PVDF_Electrolytes_for_Anode-Lean_Ultrastable_Solid-State_Sodium_Batteries/34024992 CC BY-NC 4.0