Enabling highly stable lithium metal batteries by using dual-function additive catalyzed in-built quasi-solid-state polymer electrolytes

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: Results and Discussionmentioning

confidence: 99%

Section: Characterization Of Materials and In Situ Polymerizationmentioning

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

Interdisciplinary Materials

“…The utilization of GPE in both S|Li and LiFePO 4 |Li batteries delivered excellent cycling performance for 1000 and 700 cycles, respectively (Figure 2C). In addition to DME, [33][34][35][36] carbonates such as ethylene carbonate (EC), [37] fluoroethylene carbonate (FEC), [38][39][40] and methyl ethyl carbonate [41] have also been studied as cosolvents for DOL in PDOL-based GPEs. Compared with ether solvents, carbonates possess stable thermodynamic properties, high dielectric constant, and low volatility which enable high safety and better anode reversibility.…”

Section: Ethersmentioning

confidence: 99%

Progress and perspectives of in situ polymerization method for lithium‐based batteries

Xiao

Hao

Bai

et al. 2023

The application of lithium-based batteries is challenged by the safety issues of leakage and flammability of liquid electrolytes. Polymer electrolytes (PEs) can address issues to promote the practical use of lithium metal batteries.However, the traditional preparation of PEs such as the solution-casting method requires a complicated preparation process, especially resulting in side solvents evaporation issues. The large thickness of traditional PEs reduces the energy density of the battery and increases the transport bottlenecks of lithium-ion. Meanwhile, it is difficult to fill the voids of electrodes to achieve good contact between electrolyte and electrode. In situ polymerization appears as a facile method to prepare PEs possessing excellent interfacial compatibility with electrodes. Thus, thin and uniform electrolytes can be obtained. The interfacial impedance can be reduced, and the lithium-ion transport throughput at the interface can be increased. The typical in situ polymerization process is to implant a precursor solution containing monomers into the cell and then in situ solidify the precursor under specific initiating conditions, and has been widely applied for the preparation of PEs and battery assembly. In this review, we focus on the preparation and application of in situ polymerization method in gel polymer electrolytes, solid polymer electrolytes, and composite polymer electrolytes, in which different kinds of monomers and reactions for in situ polymerization are discussed. In addition, the various compositions and structures of inorganic fillers, and their effects on the electrochemical properties are summarized. Finally, challenges and perspectives for the practical application of in situ polymerization methods in solidstate lithium-based batteries are reviewed.

“…Other initiators, such as lithium difluoro (oxalato)borate (LiDFOB), [42] tin trifluoromethanesulfonate (Sn(OTf) 2 ), [43] magnesium trifuoromethanesulfonate (Mg(OTf) 2 ), [44] and tris-(1,1,1,3,3,3-hexafluoroisopropyl) (HFiP) [45] have also been developed. Besides, a small amount of LiDFOB with 2 M lithium bis(trifuoromethylsulfonyl)imide (LiTFSI) was applied to construct a dual-salt polyDOL-based GPE.…”

Section: Ring-opening Polymerization Of Cyclic Ethermentioning

confidence: 99%

“…Similarly, Mg(OTf) 2 was reduced to Mg metal and distributed uniformly on the Li metal surface while initiating the polymerization of DOL. [44] Trace Mg element in SEI layer could adjust space charge distribution and inhibit dendrite growth on Li metal surface. After initiating DOL polymerization, HFiP decomposed into the À CF 3 functional groups and formed a dense CEI layer to improve the battery lifetime (Figure 10c).…”

Section: Ring-opening Polymerization Of Cyclic Ethermentioning

confidence: 99%

In situ Synthesis of Gel Polymer Electrolytes for Lithium Batteries

Cheng

Jiang

et al. 2023

Batteries & Supercaps

Gel polymer electrolytes (GPEs) are considered as a promising solution to replace organic liquid electrolytes for safer lithium (Li) batteries due to their high ionic conductivity comparable to liquid electrolytes, no risk of leakage, and high flexibility. However, poor interfacial contact between electrodes and GPEs leads to high interfacial impedance and unsatisfactory electrochemical performance. The emerging in situ synthesized GPEs can fully infiltrate into porous electrodes and form intimate interfaces, improving interfacial contact and electrochemical performance. This perspective covers recent advances of in situ GPEs in design, synthesis, and applications in lithium (Li) batteries. Polyester and polyether-based GPEs are mainly discussed followed by a brief introduction of GPEs with other polymer matrices, such as poly(ionic liquid)s, cyanoethyl polyvinyl alcohol, poly(vinyl acetal) and single-ion conductors. Then, the recent progress in Li batteries using in situ GPEs are summarized, including Li-ion battery, Li-metal battery, Li-sulfur battery, and Li-air battery. Finally, the remaining challenges and future perspectives of in situ GPEs are discussed. We hope this perspective can offer guidance for in situ synthesis of GPEs and facilitate their applications in high-performance Li batteries.