Xylose-and Nucleoside-Based Polymers via Thiol−ene Polymerization toward Sugar-Derived Solid Polymer Electrolytes

Sep 21, 2026

A series of copolymers were prepared via thiol−ene polymerization of bioderived α,ω-unsaturated diene monomers with dithiols to form solid polymer electrolytes (SPEs) for Li+-ion conduction. Amorphous polyesters and polyethers with low Tg’s (−31 to −11 °C) were synthesized from xylose-based monomers and EDT, and trifunctional crosslinking improved ionic transport. Ionic conductivity reached 2.2 × 10−5 S cm−1 at 60 °C with electrochemical stability up to 5.08 V. Nucleoside-bearing copolymers enabled flexible, transparent, reprocessable films with conductivity up to 1.5 × 10−4 S cm−1, hydrolytic degradability, and potential self-healing.

LanguageEnglish

CategoryResearch & Report

FormatPDF

Pages11

Reading Time28 min

AccessFree to download

Introduction

Motivation: sustainability and safety of electrolytes

Sugar-derived and bioderived polymer electrolyte approaches

Solid polymer electrolytes and thiol−ene crosslinking context

This article is licensed under CC-BY 4.0 [pubs.acs.org/acsapm](pubs.acs.org/acsapm) Article Xylose-and Nucleoside-Based Polymers via Thiol−ene Polymerization toward Sugar-Derived Solid Polymer Electrolytes Matthew Oshinowo, Marco Piccini, Gabriele Kociok-Köhn, Frank Marken, and Antoine Buchard * Cite This: ACS Appl. Polym. Mater. 2024, 6, 1622−1632 Read Online | | | | | | | | --- | --- | --- | --- | --- | --- | | ACCESS | Metrics & More | | Article Recommendations | | *sı Supporting Information | ABSTRACT: A series of copolymers have been prepared via thiol−ene polymerization of bioderived α,ω-unsaturated diene monomers with dithiols toward application as solid polymer electrolytes (SPEs) for Li+-ion conduction. Amorphous polyestersand polyethers with low Tg’s (−31 to −11 °C) were first prepared from xylose-based monomers (with varying lengths of fatty acid moiety) and 2,2′-(ethylenedioxy)diethanethiol (EDT) . Crosslinking by incorporation of a trifunctional monomer also produced a series of SPEs with ionic conductivities up to 2.2 × 10−5 S cm−1 at 60 °C and electrochemical stability up to 5.08 V, a significant improvement over previous xylose-derived materials. Furthermore, a series of copolymers bearing nucleoside moieties were prepared to exploit the complementary base-pairing interaction of nucleobases. Flexible, transparent, and reprocessable SPE films were thus prepared with improved ionic conductivity (up to 1.5 × 10−4 S cm−1 at 60 °C), hydrolytic degradability, and potential self-healing capabilities. KEYWORDS: sugars, xylose, fatty acids, nucleosides, base-pairing, self-healing, polymer electrolytes, lithium-ion conduction ■ INTRODUCTION Lithium-ion batteries (LIBs) are a continually evolving yet wellestablished technology essential for the transition of society to amore sustainable future. According to a 2019 Global Battery Alliance report for the World Economic Forum, it is predicted that the global demand for LIBs will have increased 14-fold from 184 GWh in 2018 to 2623 GWh by 2030.1 This will be primarily driven by our transition to electric vehicles and also by our continually increasing capacity to store renewable energy for the grid. However, the current use of liquid electrolyte components in LIBs poses a myriad of safety and performance issues. Various alternative electrolyte materials are being investigated to address these issues, among which polymer electrolytes are promising contenders. However, while many high-performance polymer electrolytes have been reported in the literature, the majority are derived from fossil fuel feedstocks and therefore do little to address the environmental and sustainability concerns surrounding petrochemically derived polymers. To this regard, there have been recent examples of polymer electrolytes featuring polysaccharides or carbohydrate-derived synthetic polymers, due to the merits of sugars as renewable polymer building blocks, such as their low cost, high abundance, high oxygen content, and high functionalization potential. For example, in 2022, Chen and co-workers exploited the high functionality of the natural polysaccharide chitosan to form cross-linked organogel polymer electrolyte networks with high room temperature ionic conductivity (1.1 × 10−3 S cm−1) and © 2024 The Authors. Published by American Chemical Society lithium-ion transport number (0.82).2 In a different approach, we also recently reported an organogel polyether electrolyte derived from D-xylose (a renewable sugar), which was crosslinked with boronic acid groups to achieve even higher room temperature ionic conductivity (3.7 × 10−3 S cm−1) and lithium transference numbers (t+ = 0.88−0.92), as well as a wide electrochemical stability window of +4.51 V.3 However, solid polymer electrolytes (SPEs) are also promising contenders that offer the potential of improved safety and electrochemical, mechanical, and thermal stability (and thus compatibility with Li metal a

FAQs

What polymer chemistry is used to prepare the solid polymer electrolytes?

The study prepares copolymers via thiol−ene polymerization of bioderived α,ω-unsaturated diene monomers with dithiols, using EDT and incorporating a trifunctional monomer for crosslinking.

How do the xylose-derived materials perform as SPEs?

Amorphous xylose-derived polyesters and polyethers show low Tg’s and, after crosslinking, achieve ionic conductivity up to 2.2 × 10−5 S cm−1 at 60 °C and electrochemical stability up to 5.08 V.

What additional design is used in nucleoside-bearing copolymers?

Nucleoside moieties are introduced to leverage complementary base-pairing interactions, enabling flexible, transparent, reprocessable SPE films with improved ionic conductivity and hydrolytic degradability, plus potential self-healing capabilities.

Sep 21, 2026

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