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.

[1]  O. Inganäs,et al.  Spectroelectrochemical investigation of redox states in a polypyrrole/lignin composite electrode material , 2015 .

[2]  G. Cui,et al.  Biomass-derived materials for electrochemical energy storages , 2015 .

[3]  G. Wallace,et al.  Poly(3,4-ethylenedioxythiophene):dextran sulfate (PEDOT:DS) - a highly processable conductive organic biopolymer. , 2015, Acta biomaterialia.

[4]  G. Hadziioannou,et al.  Preparation of water-free PEDOT dispersions in the presence of reactive polyisoprene stabilizers. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[5]  Young Jo Kim,et al.  Catechol‐Mediated Reversible Binding of Multivalent Cations in Eumelanin Half‐Cells , 2014, Advanced materials.

[6]  Sang Bok Lee,et al.  Superior pseudocapacitive behavior of confined lignin nanocrystals for renewable energy-storage materials. , 2014, ChemSusChem.

[7]  Michael P. Marshak,et al.  A metal-free organic–inorganic aqueous flow battery , 2014, Nature.

[8]  G. Boschloo,et al.  Neutral, polaron, and bipolaron states in PEDOT prepared by photoelectrochemical polymerization and the effect on charge generation mechanism in the solid-state dye-sensitized solar cell , 2013 .

[9]  M. Nowicki,et al.  Carbon nanotubes/kraft lignin composite: Characterization and charge storage properties , 2013 .

[10]  Roland Lee,et al.  UV-Vis as quantification tool for solubilized lignin following a single-shot steam process. , 2013, Bioresource technology.

[11]  R. B. Lima,et al.  Direct lignin fuel cell for power generation , 2013 .

[12]  Grzegorz Milczarek,et al.  Renewable Cathode Materials from Biopolymer/Conjugated Polymer Interpenetrating Networks , 2012, Science.

[13]  Y. Ge,et al.  Extraction of lignin from sugar cane bagasse and its modification into a high performance dispersant for pesticide formulations , 2011 .

[14]  J. Heinze,et al.  Electrochemistry of conducting polymers--persistent models and new concepts. , 2010, Chemical reviews.

[15]  Hidenori Okuzaki,et al.  Electromechanical properties of poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonate) films. , 2009, The journal of physical chemistry. B.

[16]  Chao Yang,et al.  Water-Dispersed Conductive Polypyrroles Doped with Lignosulfonate and the Weak Temperature Dependence of Electrical Conductivity , 2009 .

[17]  G. Milczarek.  Lignosulfonate-modified electrodes: electrochemical properties and electrocatalysis of NADH oxidation. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[18]  Yunhong Zhou,et al.  PEDOT: Cathode active material with high specific capacity in novel electrolyte system , 2008 .

[19]  Diane K. Smith,et al.  Voltammetry of quinones in unbuffered aqueous solution: reassessing the roles of proton transfer and hydrogen bonding in the aqueous electrochemistry of quinones. , 2007, Journal of the American Chemical Society.

[20]  S. Kirchmeyer,et al.  Scientific importance, properties and growing applications of poly(3,4-ethylenedioxythiophene) , 2005 .

[21]  Jean Manca,et al.  PEDOT/PSS: synthesis, characterization, properties and applications , 2003 .

[22]  L. Samuelson,et al.  Biomimetic synthesis of a water soluble conducting molecular complex of polyaniline and lignosulfonate. , 2002, Biomacromolecules.

[23]  J. Brédas,et al.  Optical and redox properties of a series of 3,4-ethylenedioxythiophene oligomers. , 2002, Chemistry.

[24]  O. Inganäs,et al.  Electrochemical Characterization of Poly(3,4‐ethylene dioxythiophene) Based Conducting Hydrogel Networks , 2000 .

[25]  J. Reynolds,et al.  Poly(3,4‐ethylenedioxythiophene) and Its Derivatives: Past, Present, and Future , 2000 .

[26]  Helmut Neugebauer,et al.  Vibrational signatures of electrochemical p- and n-doping of poly(3,4-ethylenedioxythiophene) films: an in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) study☆ , 2000 .

[27]  O. Inganäs,et al.  Conducting Polymer Hydrogels as 3D Electrodes: Applications for Supercapacitors , 1999 .

[28]  P. Novák,et al.  Electrochemically Active Polymers for Rechargeable Batteries. , 1997, Chemical reviews.

[29]  Henrik Olsson,et al.  Self-discharge in positively charged polypyrrole-cellulose composite electrodes , 2015 .

[30]  O. Inganäs,et al.  Networks of electron-conducting polymer in matrices of ion-conducting polymers. Applications to fast electrodes , 1999 .