Nerea Casado

High performance PEDOT/lignin biopolymer composites for electrochemical supercapacitors

Developing sustainable organic electrode materials for energy storage applications is an urgent task. We present a promising candidate based on the use of lignin, the second most abundant biopolymer in nature. This polymer is combined with a conducting polymer, where lignin as a polyanion can behave both as a dopant and surfactant. The synthesis of PEDOT/Lig biocomposites by both oxidative chemical and electrochemical polymerization of EDOT in the presence of lignin sulfonate is presented. The characterization of PEDOT/Lig was performed by UV-Vis-NIR spectroscopy, FTIR infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, cyclic voltammetry and galvanostatic charge–discharge. PEDOT doped with lignin doubles the specific capacitance (170.4 F g−1) compared to reference PEDOT electrodes (80.4 F g−1). The enhanced energy storage performance is a consequence of the additional pseudocapacitance generated by the quinone moieties in lignin, which give rise to faradaic reactions. Furthermore PEDOT/Lig is a highly stable biocomposite, retaining about 83% of its electroactivity after 1000 charge/discharge cycles. These results illustrate that the redox doping strategy is a facile and straightforward approach to improve the electroactive performance of PEDOT.

Redox-active polyimide–polyether block copolymers as electrode materials for lithium batteries

Redox-active polyimide–polyether multi-block copolymers were synthesized by polycondensation reaction of aromatic dianhydrides with α-ω-diamino poly(ethylene oxide). Polyimide-b-polyether block copolymers showed microphase separation between a hard-polyimide domain and a soft-polyether domain as observed by Atomic Force Microscopy. The block copolymers were investigated as cathodes for polymer/lithium metal batteries. Polymer cathodes were formulated where the block copolymer had a dual role as active material and binder, with a small amount of carbon black (15 wt%). Naphthalene polyimides showed higher discharge voltages, higher specific capacities as well as better cycling performance, compared to pyromellitic polyimides. The longest PEO blocks resulted in a better performance as electrodes. The best performing naphthalene polyimide-b-PEO2000 presented an excellent value of discharge capacity of 170 mA h g−1, stable after 100 cycles at a current density of 1Li+/5 h and considering the polyimide as the active material. The average discharge plateaus were 2.51 V and 2.37 V vs. Li+/Li.

Full-cell quinone/hydroquinone supercapacitors based on partially reduced graphite oxide and lignin/PEDOT electrodes

The development of new, scalable and inexpensive materials for low-cost and sustainable energy storage devices is intensely pursued. The combination of redox active biopolymers with electron conducting polymers has shown enhanced charge storage properties. However, their performance has just been investigated at the electrode level. Herein, we move a step further by assembling full-cell supercapacitors based on natural lignin (Lig) and partially reduced graphite oxide (prGrO) electrode materials. Both materials evidenced that quinone/hydroquinone redox moieties are able to store and release charge reversibly. The redox properties of lignin were improved by combining it with poly(3,4-ethylenedioxythiophene) (PEDOT). Analysis of the capacitive contributions to the charge storage proved that PEDOT enhanced the lignins capacitive contribution to the current by 22%. The capacitive contributions were equal to 66% and 75% in Lig/PEDOT blend and prGrO electrodes, respectively. We also show for the first time that by distributing equally charges in carbon–biopolymer composite electrodes, a higher capacitance retention, up to 79% after 1000 cycles, is achieved.

Electrochemical Behavior of PEDOT/Lignin in Ionic Liquid Electrolytes: Suitable Cathode/Electrolyte System for Sodium Batteries

Biomass-derived polymers, such as lignin, contain quinone/ hydroquinone redox moieties that can be used to store charge. Composites based on the biopolymer lignin and several conjugated polymers have shown good charge-storage properties. However, their performance has been only studied in acidic aqueous media limiting their applications mainly to supercapacitors. Here, we show that PEDOT/lignin (PEDOT: poly(3,4-ethylenedioxythiophene)) biopolymers are electroactive in aprotic ionic liquids (ILs) and we move a step further by assembling sodium full cell batteries using PEDOT/lignin as electrode material and IL electrolytes. Thus, the electrochemical activity and cycling of PEDOT/lignin electrodes was investigated in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BMPyrTFSI), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (BMPyrFSI), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI) and 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMImFSI) IL electrolytes. The effects of water and sodium salt addition to the ILs were investigated to obtain optimum electrolyte systems for sodium batteries. Finally, sodium batteries based on PEDOT/lignin cathode with imidazolium-based IL electrolyte showed higher capacity values than pyrrolidinium ones, reaching 70 mAhg-1 . Our results demonstrate that PEDOT/lignin composites can serve as low cost and sustainable cathode materials for sodium batteries.

Catechol End-Functionalized Polylactide by Organocatalyzed Ring-Opening Polymerization

There is a great interest in incorporating catechol moieties into polymers in a controlled manner due to their interesting properties, such as the promotion of adhesion, redox activity or bioactivity. One possibility is to incorporate the catechol as end-group in a polymer chain using a functional initiator by means of controlled polymerization strategies. Nevertheless, the instability of catechol moieties under oxygen and basic pH requires tedious protection and deprotection steps to perform the polymerization in a controlled fashion. In the present work, we explore the organocatalyzed synthesis of catechol end-functional, semi-telechelic polylactide (PLLA) using non-protected dopamine, catechol molecule containing a primary amine, as initiator. NMR and SEC-IR results showed that in the presence of a weak organic base such as triethylamine, the ring-opening polymerization (ROP) of lactide takes place in a controlled manner without need of protecting the cathechol units. To further confirm the end-group fidelity the catechol containing PLLA was characterized by Cyclic Voltammetry and MALDI-TOF confirming the absence of side reaction during the polymerization. In order to exploit the potential of catechol moieties, catechol end-group of PLLA was oxidized to quinone and further reacted with aliphatic amines. In addition, we also confirmed the ability of catechol functionalized PLLA to reduce metal ions to metal nanoparticles to obtain well distributed silver nanoparticles. It is expected that this new route of preparing catechol-PLLA polymers without protection will increase the accessibility of catechol containing biodegradable polymers by ROP.