Solid polymer electrolytes with high ionic conductivity have been prepared from a microphase separated fluorinated copolymer bearing cyclocarbonate side groups.

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SET-LRP is used for the controlled copolymerisation of 2,2,6,6-tetramethylpiperidin-4-yl methacrylate (TMPM) with 3-azidopropyl methacrylate (AzPMA), followed by the oxidation of TMPM to produce electroactive poly(TEMPO methacrylate) (PTMA).

Electro-active polymer gels are prepared via one-pot Cu(0)-mediated radical polymerization and click chemistry.

polymer for application as suspension electrode. Indeed, PTMA is able to undergo stable and reversible redox reactions upon electrochemical stimuli. [6] Moreover, it displays high power density with an ultra-fast electron transfer process of 10 −1 cm s −1. [7] Thus, it is also classified as a pseudocapacitive component. This allows PTMA to be widely used as cathode materials in organic radical batteries (ORB). [8,9] Schubert et al. have synthesized water-soluble statistical copolymers containing PTMA and hydrophilic comonomers [10] and have studied their electrochemical properties in water-based and in organic carbonatebased redox flow batteries. [11] While the organic carbonates are widely used due to their good stabilities, the water-based systems reveal better performances as well as positive environmental impact. Furthermore, Schubert and coworkers were able to design a full organic water-based redox flow battery by using water-soluble redox polymers both as catholyte and anolyte. [12] One of the main challenges related to redox polymer-based electrodes remains the relatively low concentration of redoxactive material that can be dissolved while keeping a sufficiently low viscosity to allow the pumping of the liquid electrode in the main electrochemical cell. Decreasing the molar mass of the polymer is not an appropriate option because the redox polymer should not pass through the semi-permeable membrane which is located in the main electrochemical cell. [12] One solution, that allows the dispersion of a high amount of redox polymer without reaching a too high viscosity, consists in tethering the redox polymer chains in a micellar design. Basically, the redox polymer chains could be incorporated into two different compartments of the micellar cargo: the micellar core or the micellar corona. In a previous work, we have designed micellar nano-objects comprising PTMA coronal chains tethered onto a polystyrene (PS) core. These objects were synthesized from PTMA-b-PS diblock copolymers containing a major PTMA block dissolved in carbonate solvents that are selective solvents for the PTMA blocks. [13] The accordingly obtained micelles were successfully tested as catholytes in redox flow batteries. [14] Such a design has the advantage of a good accessibility of the redox-active PTMA chains for redox reactions since they are located in the micellar corona. However, this design has the drawback of being limited to organic solvents for the preparation of the liquid electrodes since both PTMA and PS are hydrophobic groups. The aim of this work is to synthesize micellar nano-objects in aqueous medium containing the redox PTMA polymer. The target is to elaborate an amphiphilic block copolymer containing Redox Polymer Nanoparticles Poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl-methacrylate) (PTMA) redox polymer-based nano-objects are synthesized by polymerization-induced self-assembly with poly[oligo(ethylene glycol) methyl ether methacrylate] and poly[(4-methacryloyloxy)-2,2,6,6-tetramethylpiperidinium chloride] as hydrophili...

Solid polymer electrolytes (SPEs) are prepared by mixing poly(2‐oxo‐1,3‐dioxolan‐4‐yl)methyl acrylate‐random‐n‐butylacrylate) [P(cyCA‐r‐nBA)] statistical copolymers with bis(trifluoromethane)sulfonimide lithium salt. The P(cyCA‐r‐nBA) copolymers are synthesized by reversible addition‐fragmentation chain transfer polymerization and different molar masses as well as copolymer composition are targeted in order to study the influence of the molecular parameters on the thermal, mechanical, and electrochemical properties of the SPEs obtained after mixing the copolymers with lithium salts. In the investigated experimental window, it is shown that the thermal and mechanical properties of the SPEs mainly depend on the composition of the copolymer and are poorly influenced by the molar mass. In sharp contrast, the ionic conductivities are more deeply influenced by the molar mass than by the composition of the copolymers. In this respect ionic conductivity values ranging from 4.2 × 10−6 S cm−1 for the lower molar mass sample to 8 × 10−8 S cm−1 for the higher molar mass one are measured at room temperature for the investigated SPEs.

Redox-active polymer networks based on stable nitroxide radicals are a very promising class of materials to be used in the so-called organic radical batteries. In order to obtain fast-charging and high power electrodes, however, excellent ionic conductivity inside the electrode material is required to allow easy diffusion of ions and fast redox reactions. In this contribution, we investigated redox-active poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) chains cross-linked through ionic liquid-like 1,2,3-triazolium groups. Different networks were prepared in which the amount of cross-linker and the counter-anion associated to the 1,2,3-triazolium group were varied. The ionic conductivities of the different polymer networks were first measured in the solid state by electrochemical impedance spectroscopy at different temperatures, and an increased ionic conductivity was measured when 1,2,3-triazolium groups were present in the network. The effects of the chemical nature of the counterions associated to the 1,2,3-triazolium groups and of the crosslinking density were then studied. The best ionic conductivities were obtained when bis (trifluoromethane)sulfonamide (TFSI) counter-anions were used, and when the crosslinking density of the TFSI-containing gel was higher. Finally, those ion-conducting gels were loaded with free LiTFSI and the transference number of lithium ions was accordingly measured. The good ionic conductivities and lithium ions transference numbers measured for the investigated redox-active gels make them ideal candidates for application as electrode materials for either organic radical batteries or pseudo-capacitors energy storage devices.