An In Situ Polymerized Comb-Like PLA/PEG-based Solid Polymer Electrolyte for Lithium Metal Batteries

Abstract

High ionic conductivity is a prerequisite for the application of solid-state polymer electrolyte towards the safe and high energy density electrochemical devices. Here we report the preparation and properties of an in-situ polymerized comb-like copolymer-based SPE (PLA/PEG-SPE) with high ionic conductivity from methyl acrylate functionalized poly(D,L-Lactide) (PLAMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMA). A remarkably high ionic conductivity value of 6.9 × 10−5 S cm−1 at ambient temperature and a maximum ionic conductivity of 4.3 × 10−4 S cm−1 at 60°C were detected, with an activation energy of 0.2 eV and a Li+ transference number (tLi+) of 0.36. The PLA/PEG-SPE exhibits a wide electrochemical stability window up to 4.6 vs. Li/Li+ and very good lithium metal electrode compatibility. Solid-state LiFePO4/SPE/Li cells with integrated cathode and lithium metal deliver superior cycling stability with high discharge capacities (149 mAh g−1 as the initial specific capacity) and high capacity retention (exceeded 82% of its initial specific capacity) at 0.2 C at 60°C. The solid-state cells are also capable of being cycled at room temperature at 0.2 C. This work highlights a facile, in-situ fabrication strategy involving a vinyl-functionalized PLA precursor that yields a high-performance ion-conducting membrane attractive for lithium metal battery applications.

Ionic Liquid Functionalized Gel Polymer Electrolytes for Stable Lithium Metal Batteries

“…Fourier-transform infrared spectra (FT-IR) measurements were conducted to verify the polymerization of F-IL, DPEPA and PEGMA monomers in F-IL-GEL. Thep eaks at % 1633 cm À1 in the DPEPA [19] and PEGMA, [20] and % 3107 cm À1 in the F-IL monomers were assigned to the stretching bands of C=Ca nd CÀH, respectively. [21] Upon polymerization, FT-IR spectrum of the F-IL-GEL showed (Figure 2a)asignificant decrease in the intensity of the C = C stretching band pointing to the successful polymerization.…”

Toward High Resolution 3D Printing of Shape-Conformable Batteries via Vat Photopolymerization: Review and Perspective

“…The spiral-shaped solid polymer electrolyte was shown to greatly reinforce interfacial adhesion. A similar VPP approach could be undoubtedly transposed to other methacrylate-based solid polymer electrolytes, such as the methyl acrylate functionalized poly(D,L-Lactide)/poly(ethylene glycol) methyl ether methacrylate with LiTFSI as lithium salt and Irgacure 1173 as photoinitiator, proposed by Zaheer et al [56]. In this study, the authors obtained a 2D film after the UV illumination step, but 3D complex geometries could theoretically be produced via VPP.…”

One-Pot Synthesis of Polyester-Based Linear and Graft Copolymers for Solid Polymer Electrolytes

“…The graft copolymerization of HEMA and ε-CL via a one-pot method allows for significant ionic conductivity enhancement (more than two orders of magnitude) compared to the PESPE linear . Figure S25 shows the temperature dependence of the ionic conductivity of SPEs based on different graft copolymers ( 44,45 The high t Li + helps to reduce the concentration polarization, 17,26 interaction between the cation and anion in the lithium salt, further promote the transference of lithium ions, and promote the increase of t Li +. 83 Moreover, the brush-shaped structure destroys the regularity of the PCL segment, and the coordination between Li + and the carbonyl group of PCL is improved, thereby increasing the t Li + value.…”

“…It noted to be pointed out that polyester has a similar thermal property and semi-crystallinity to PEO. [43][44][45] Building linear block copolymers or graft copolymers and polymers with various topological structures to destroy the crystallinity of polyester has proved to be a good way to meet the practical application requirements of LIBs. [46][47][48][49][50][51] With the development of polymer synthesis technology, various living polymerizations including atom transfer radical polymerization (ATRP), [52][53][54][55][56] and reversible addition fragmentation chain transfer (RAFT) polymerization, [57][58][59][60] nitroxide-mediated radical polymerization (NMP), [61][62][63][64] and ring-opening polymerization system in the system.…”