Tunable Polymer Nanoreactors from RAFT Polymerization-Induced Self-Assembly: Fabrication of Nanostructured Carbon-Coated Anatase as Battery Anode Materials with Variable Morphology and Porosity

Yen Theng Cheng; Qingbo Xia; Hongwei Liu; Marcello B Solomon; Emma R L Brisson; Lewis D Blackman; Chris D Ling; Markus Müllner

doi:10.1021/acsami.2c18928

Tunable Polymer Nanoreactors from RAFT Polymerization-Induced Self-Assembly: Fabrication of Nanostructured Carbon-Coated Anatase as Battery Anode Materials with Variable Morphology and Porosity

ACS Appl Mater Interfaces. 2023 Mar 8;15(9):12261-12272. doi: 10.1021/acsami.2c18928. Epub 2023 Feb 23.

Authors

Yen Theng Cheng^{1

2}, Qingbo Xia^{3

2}, Hongwei Liu⁴, Marcello B Solomon³, Emma R L Brisson¹, Lewis D Blackman⁵, Chris D Ling^{3

2}, Markus Müllner^{1

2}

Affiliations

¹ Key Centre for Polymers and Colloids, School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia.
² The University of Sydney Nano Institute (Sydney Nano), Sydney, NSW 2006, Australia.
³ School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia.
⁴ Sydney Microscopy & Microanalysis, The University of Sydney node of Microscopy Australia, Sydney, NSW 2006, Australia.
⁵ CSIRO Manufacturing Business Unit, Research Way, Clayton, VIC 3168, Australia.

PMID: 36821625
DOI: 10.1021/acsami.2c18928

Abstract

We demonstrate a modular synthesis approach to yield mesoporous carbon-coated anatase (denoted as TiO₂/C) nanostructures. Combining polymerization-induced self-assembly (PISA) and reversible addition-fragmentation chain-transfer (RAFT) dispersion polymerization enabled the fabrication of uniform core-shell polymeric nanoreactors with tunable morphologies. The nanoreactors comprised of a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) shell and a poly(benzyl methacrylate) (PBzMA) core. We selected worm-like and vesicular morphologies to guide the nanostructuring of a TiO₂ precursor, namely, titanium(IV) bis(ammonium lactato)dihydroxide (TALH). Subsequent carbonization yielded nanocrystalline anatase and simultaneously introduced a porous carbon framework, which also suppressed the crystal growth (∼5 nm crystallites). The as-prepared TiO₂/C materials comprised of a porous structure, with large specific surface areas (>85 m²/g) and various carbon contents (20-30 wt %). As anode components in lithium-ion batteries, our TiO₂/C nanomaterials improved the cycling stability, facilitated high overall capacities, and minimized the capacity loss compared to both their sans carbon and commercial anatase analogues.

Keywords: RAFT polymerization; block copolymers; nanocomposites; nanocrystalline TiO2; polymer templating.