Influence of Backbone on the Performance of Pendant Polymer Electrode Materials in Li-ion Batteries.

Pendant polymers are a promising class of electrode materials due to their synthetic simplicity, derivation from sustainable feedstocks, and potentially benign synthesis. These materials consist of a redox-active pendant tethered to a polymer backbone, which mitigates dissolution during electrode cycling. To date, an extensive number of pendant groups have been studied within the context of metal-ion batteries. However, the choice of the polymer backbone and its impact on the electrode performance have been relatively understudied. In this work, we use a postpolymerization modification approach to synthesize a series of viologen-bearing redox-active pendant polymers with similar molecular weights but three distinct chemical backbones, namely, polyacrylamide, polymethacrylamide, and polystyryl. By evaluating the polymers in lithium-ion batteries, we show that the polymer backbone has a significant influence on electrode performance and behavior. Specifically, the polymethacrylamide displays slower kinetics than the other two polymers, resulting in lower capacities, particularly at high cycling rates. Furthermore, the charge storage mechanism is dependent on the nature of the backbone: the polyacrylamide shows a significant capacitive contribution to charge storage, while the polystyryl does not. The difference in performance between the polymer electrode materials is ascribed to a difference in chain mobility and packing within the electrode films. Overall, this work shows that the fundamental properties of the polymer backbone are critical to the design of high-performance polymer electrodes.

High Active Material Loading in Organic Electrodes Enabled by a Multifunctional Binder.

Organic electrodes are promising candidates for next-generation lithium-ion batteries due to their low cost and sustainable nature; however, they often suffer from very low conductivity and active material loadings. The conventional binder used in organic-based Li-ion batteries is poly(vinylidene fluoride) (PVDF), yet it is electrochemically inactive and thus occupies volume and mass without storing energy. Here, we report an organic mixed ionic-electronic conducting polymer, poly[norbornene-1,2-bis(C(O)OPEDOT)]25-b-[norbornene-1,2-bis-(C(O)PEG12)]25 denoted PEDOT-b-PEG for simplicity, as a cathode binder to address the aforementioned issues. The polymer contains a poly(3,4-ethylenedioxythiophene) (PEDOT) functionality to provide electronic conductivity, as well as poly(ethylene glycol) (PEG) chains to impart ionic conductivity to the cathode composite. We compare electrodes containing a perylene diimide (PDI) active material, conductive carbon, and a polymeric binder (either PVDF or PEDOT-b-PEG) with different weight ratios to study the impact of active material loading and type of binder on the performance of the cell. The lithium-ion cells prepared with the PEDOT-b-PEG polymer binder result in higher capacities and decreased impedance at all active material loadings compared to cathodes prepared with the PVDF-containing electrodes, demonstrating potential as a new binder to achieve higher active material loadings in organic electrodes. The strategy of preparing these polymers should be broadly applicable to other classes of mixed polymer conductors.

Synthesis and optoelectronic properties of radical conjugated polyfluorenes.

A novel redox-active fluorene monomer is synthesized and copolymerized with 9,9-dioctylfluorene and benzo[c][1,2,5]thiadiazole via Suzuki cross-coupling to produce alternating and tertiary copolymers. Electrochemical and chemical reduction of the copolymers generates organic polymeric radical anions. Electrochemical, spectroscopic, and photophysical characterization grant insight into the structure-property relationship for open-shell conjugated polymers.

Aqueous zinc batteries: Design principles toward organic cathodes for grid applications.

The development of low-cost and sustainable grid energy storage is urgently needed to accommodate the growing proportion of intermittent renewables in the global energy mix. Aqueous zinc-ion batteries are promising candidates to provide grid storage due to their inherent safety, scalability, and economic viability. Organic cathode materials are especially advantageous for use in zinc-ion batteries as they can be synthesized using scalable processes from inexpensive starting materials and have potential for biodegradation at their end of life. Strategies for designing organic cathode materials for rechargeable zinc-ion batteries targeting grid applications will be discussed in detail. Specifically, we emphasize the importance of cost analysis, synthetic simplicity, end-of-life scenarios, areal loading of active material, and long-term stability to materials design. We highlight the strengths and challenges of present zinc-organic research in the context of our design principles, and provide opportunities and considerations for future electrode design.