Ameliorating structural and electrochemical properties of traditional poly-dioxolane electrolytes via integrated design of ultra-stable network for solid-state batteries

Huang

ACS Appl. Energy Mater.

et al. 2023

The poor interfacial contact between solid-state electrolytes (SSEs) and electrodes, which hinders the applications of solid-state batteries (SSBs), could be improved by in situ polymerization. However, the limited electrochemical window and insufficient mechanical strength of in situ-polymerized electrolytes make them unable to match high-voltage cathodes and inhibit lithium dendrites. Here, a layered organic–inorganic composite solid-state electrolyte structure is designed by introducing a Li1.3Al0.3Ti1.7(PO4)3 (LATP)-coated polyethylene separator and fluoroethylene carbonate (FEC) into in situ-polymerized 1,3-dioxolane (DOL). The high-voltage stable fluoride-rich cathode–electrolyte interface formed in situ by FEC widens the electrochemical window of the composite solid-state electrolyte. In addition, the LATP coating layer inhibits the growth of lithium dendrites and increases the Li-ion conductivity by reacting with FEC to generate FEC derivatives. The Li/LiCoO2 battery exhibits good cycling and rate performance with a cutoff voltage of 4.3 V at room temperature. It provides a simple and practical solution to improve the performance of high-voltage lithium metal batteries based on in situ polymerization.

Section: Introductionmentioning

confidence: 99%

Layer-Structured Composite Solid-State Electrolyte with a Li_1.3Al_0.3Ti_1.7(PO₄)₃-Coated Separator for High-Voltage Lithium Metal Batteries by In Situ Polymerization

Huang

ACS Appl. Energy Mater.

et al. 2023

ACS Appl. Mater. Interfaces

“…Obviously, the thermal stability of the polymerized long chain PDOL is greatly improved compared with the small-molecule DOL. 44,45 Note that there is a mild weight loss of CPET2 in the original heating period, probably attributed to the presence of a small amount of unpolymerized DOL monomers in the PDOL matrix. After heating to 600 °C, the residual amount of CPET2 and GPE-20% SN was 56.1 and 15.2%, respectively, indicating the ultrahigh thermal stability of CPET2 with the porous 3D LATP framework.…”

Section: Resultsmentioning

confidence: 99%

In Situ Gelation of a 1,3-Dioxolane Dual-Permeable Porous Tandem Framework with Excellent Interfacial Stability to Power Long-Cycling Solid-State Lithium Metal Batteries

Song

Zheng

et al. 2023

Ceramic Li1.3Al0.3Ti1.7(PO4)3 (LATP) with high ionic conductivity and stability in ambient atmosphere is considered to be potent as a solid-state electrolyte of solid-state lithium metal batteries (SSLMBs), but its huge interfacial impedance with electrodes and the unwanted Ti4+-mediated reduction reaction caused by the lithium (Li) metal anode greatly limit its application in LMBs. Herein, a composite polymer electrolyte (CPET) was integrated by in situ gelation of dual-permeable 1, 3-dioxolane (DOL) in the tandem framework composed of the commercial cellulose membrane TF4030 and a porous three-dimensional (3D) skeleton-structured LATP. The in situ gelled DOL anchored in the tandem framework ensured nice interfacial contact between the as-prepared CPET and electrodes. The introduction of the porous 3D LATP endowed CPET the increased lithium-ion migration number (tLi+ ) of 0.70, a wide electrochemical stability window (ESW) of 4.86 V, and a high ionic conductivity of 1.16 × 10–4 S cm–1 at room temperature (RT). Meanwhile, the side reaction of the LATP/Li metal was adequately restrained by inserting TF4030 between the porous LATP and Li anode. Profiting from the superb interfacial stability and the enhanced ionic transport capacity of CPET, Li/Li batteries based on the optimal CPET (CPET2) cycled over 2000 h at 20∼30 °C smoothly. Moreover, solid-state LiFePO4 (LFP)/Li with CPET2 exhibited excellent electrochemical performance with a capacity retention ratio of 72.2% after 400 cycles at 0.5C. This work offers an integrated strategy to guide the fabrication of a highly conductive solid electrolyte and a stable interface design for high-performance SSLMBs.

“…Although in situ polymerization of the DOL monomer has made significant progress in improving interfacial contact and cycling life of low-voltage Li||LFP cells, high-voltage tolerance and interfacial stability are still challenging. 23,[30][31][32] To be specific, the poor oxidative stability of the DOL solvent has prevented the resulting P-DOL PEs from being applied as high-voltage cathodes, and their compatibility with Li-metal remains to be improved.…”

Section: Design Rationale and Fabrication Of P-dox Pesmentioning

confidence: 99%

In situ polymerization of 1,3-dioxane as a highly compatible polymer electrolyte to enable the stable operation of 4.5 V Li-metal batteries

Liu,

Zou,

Huang

et al. 2023

Energy Environ. Sci.