Maria Strømme

All-polymer and paper-based energy storage devices have significant inherent advantages in comparison with many currently employed batteries and supercapacitors regarding environmental friendliness, flexibility, cost and versatility. The research within this field is currently undergoing an exciting development as new polymers, composites and paper-based devices are being developed. In this report, we review recent progress concerning the development of flexible energy storage devices based on electronically conducting polymers and cellulose containing composites with particular emphasis on paper-based batteries and supercapacitors. We discuss recent progress in the development of the most commonly used electronically conducting polymers used in flexible device prototypes, the advantages and disadvantages of this type of energy storage devices, as well as the two main approaches used in the manufacturing of paper-based charge storage devices.

Conducting polymers for battery applications have been subject to numerous investigations during the last two decades. However, the functional charging rates and the cycling stabilities have so far been found to be insufficient for practical applications. These shortcomings can, at least partially, be explained by the fact that thick layers of the conducting polymers have been used to obtain sufficient capacities of the batteries. In the present letter, we introduce a novel nanostructured high-surface area electrode material for energy storage applications composed of cellulose fibers of algal origin individually coated with a 50 nm thin layer of polypyrrole. Our results show the hitherto highest reported charge capacities and charging rates for an all polymer paper-based battery. The composite conductive paper material is shown to have a specific surface area of 80 m(2) g(-1) and batteries based on this material can be charged with currents as high as 600 mA cm(-2) with only 6% loss in capacity over 100 subsequent charge and discharge cycles. The aqueous-based batteries, which are entirely based on cellulose and polypyrrole and exhibit charge capacities between 25 and 33 mAh g(-1) or 38-50 mAh g(-1) per weight of the active material, open up new possibilities for the production of environmentally friendly, cost efficient, up-scalable and lightweight energy storage systems.

Conductive metal–organic frameworks (c-MOFs) show great potential in electrochemical energy storage thanks to their high electrical conductivity and highly accessible surface areas. However, there are significant challenges in processing c-MOFs for practical applications. Here, we report on the fabrication of c-MOF nanolayers on cellulose nanofibers (CNFs) with formation of nanofibrillar CNF@c-MOF by interfacial synthesis, in which CNFs serve as substrates for growth of c-MOF nanolayers. The obtained hybrid nanofibers of CNF@c-MOF can be easily assembled into freestanding nanopapers, demonstrating high electrical conductivity of up to 100 S cm–1, hierarchical micromesoporosity, and excellent mechanical properties. Given these advantages, the nanopapers are tested as electrodes in a flexible and foldable supercapacitor. The high conductivity and hierarchical porous structure of the electrodes endow fast charge transfer and efficient electrolyte transport, respectively. Furthermore, the assembled supercapacitor shows extremely high cycle stability with capacitance retentions of >99% after 10000 continuous charge–discharge cycles. This work provides a pathway to develop flexible energy storage devices based on sustainable cellulose and MOFs.

Rechargeable batteries that use organic matter as the capacity-carrying material have previously been considered a technology for the future. Earlier batteries in which both the anode and cathode consisted of organic material required significant amounts of conductive additives and were often based on metal-ion electrolytes containing Li+ or Na+. However, we have used conducting poly(3,4-ethylenedioxythiophene) (PEDOT), functionalized with anthraquinone (PEDOT-AQ) or benzonquinone (PEDOT-BQ) pendant groups as the negative and positive electrode materials, respectively, to make an all-organic proton battery devoid of metals. The electrolyte consists of a proton donor and acceptor slurry containing substituted pyridinium triflates and the corresponding pyridine base. This slurry allows the 2e–/2H+ quinone/hydroquinone redox reactions while suppressing proton reduction in the battery cell. By using strong (acidic) proton donors, the formal potential of the quinone redox reactions is tuned into the potential region in which the PEDOT backbone is conductive, thus eliminating the need for conducting additives. In this all-organic proton battery cell, PEDOT-AQ and PEDOT-BQ deliver 103 and 120 mAh g–1, which correspond to 78% and 75%, respectively, of the theoretical specific capacity of the materials at an average cell potential of 0.5 V. We show that PEDOT-BQ determines the cycling stability of the device while PEDOT-AQ provides excellent reversibility for at least 1000 cycles. This proof-of-concept shows the feasibility of assembling all-organic proton batteries which require no conductive additives and also reveals where the challenges and opportunities lie on the path to producing plastic batteries.