Natural biopolymers, such as DNA and proteins, have uniform microstructures with defined molecular weight, precise monomer sequence, and stereoregularity along the polymer main chain that affords them unique biological functions. To reproduce such structurally perfect polymers and understand the mechanism of specific functions through chemical approaches, researchers have proposed using synthetic polymers as an alternative due to their broad chemical diversity and relatively simple manipulation. Herein, we report a new methodology to prepare sequence-controlled and stereospecific oligomers using alternating radical chain growth and sequential photoinduced RAFT single unit monomer insertion (photo-RAFT SUMI). Two families of cyclic monomers, the indenes and the N-substituted maleimides, can be alternatively inserted into RAFT agents, one unit at a time, allowing the monomer sequence to be controlled through sequential and alternating monomer addition. Importantly, the stereochemistry of cyclic monomer insertion into the RAFT agents is found to be trans-selective along the main chains due to steric hindrance from the repeating monomer units. All investigated cyclic monomers provide such trans-selectivity, but analogous acyclic monomers give a mixed cis- and trans-insertion.

The Ni-rich LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode has attracted great interest owing to its low cost, high capacity, and energy density. Nevertheless, rapid capacity fading is a critical problem because of direct contact of NCM811 with electrolytes and hence restrains its wide applications. To prevent the direct contact, the surface inert layer coating becomes a feasible strategy to tackle this problem. However, to achieve a homogeneous surface coating is very challenging. Considering the bonding effect between NCM811, polyvinylpyrrolidone (PVP), and polyaniline (PANI), in this work, we use PVP as an inductive agent to controllably coat a uniform conductive PANI layer on NCM811 (NCM811@PANI–PVP). The coated PANI layer not only serves as a rapid channel for electron conduction, but also prohibits direct contact of the electrode with the electrolyte to effectively hinder side reaction. NCM811@PANI–PVP thus exhibits excellent cyclability (88.7% after 100 cycles at 200 mA g–1) and great rate performance (152 mA h g–1 at 1000 mA g–1). In situ X-ray diffraction and in situ Raman are performed to investigate the charge–discharge mechanism and the cyclability of NCM811@PANI–PVP upon electrochemical reaction. This surfactant-modulated surface uniform coating strategy offers a new modification approach to stabilize Ni-rich cathode materials for lithium-ion batteries.

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In this communication, we report a catalyst-free methodology for single unit monomer insertion (SUMI) into reversible addition–fragmentation chain transfer (RAFT) agents initiated by low intensity visible light.