Functionalised Poly(Vinyl Alcohol)/Graphene Oxide as Polymer Composite Electrolyte Membranes

[EN] Crosslinked poly(vinyl alcohol) (PVA) based composite films were prepared as polyelectrolyte membranes for low temperature direct ethanol fuel cells (DEFC). The membranes were functionalised by means of the addition of graphene oxide (GO) and sulfonated graphene oxide (SGO) and crosslinked with sulfosuccinic acid (SSA). The chemical structure was corroborated and suitable thermal properties were found. Although the addition of GO and SGO slightly decreased the proton conductivity of the membranes, a significant reduction of the ethanol solution swelling and crossover was encountered, more relevant for those functionalised with SGO. In general, the composite membranes were stable under simulated service conditions. The addition of GO and SGO particles permitted to buffer the loss and almost retain similar proton conductivity than prior to immersion. These membranes are alternative polyelectrolytes, which overcome current concerns of actual commercial membranes such as the high cost or the crossover phenomenon.The authors would like to thank the support of the European Union through the European Regional Development Funds (ERDF). The Spanish Ministry of Economy, Industry and Competitiveness, is thanked for the research project POLYDECARBOCELL (ENE2017-86711-C3-1-R). The Spanish Ministry of Education, Culture and Sports is thanked for the FPU grant for O. Gil-Castell (FPU13/01916).Gil Castell, Ó.; Cerveró, R.; Teruel Juanes, R.; Badia, JD.; Ribes Greus, MD. (2019). Functionalised Poly(Vinyl Alcohol)/Graphene Oxide as Polymer Composite Electrolyte Membranes. Journal of Renewable Materials. 7(7):655-665. https://doi.org/10.32604/jrm.2019.04401S6556657

Functionalised poly (vinyl alcohol)/graphene oxide as polymer composite electrolyte membranes

Crosslinked poly(vinyl alcohol) (PVA) based composite films were prepared as polyelectrolyte membranes for low temperature direct ethanol fuel cells (DEFC). The membranes were functionalised by means of the addition of graphene oxide (GO) and sulfonated graphene oxide (SGO) and crosslinked with sulfosuccinic acid (SSA). The chemical structure was corroborated and suitable thermal properties were found. Although the addition of GO and SGO slightly decreased the proton conductivity of the membranes, a significant reduction of the ethanol solution swelling and crossover was encountered, more relevant for those functionalised with SGO. In general, the composite membranes were stable under simulated service conditions. The addition of GO and SGO particles permitted to buffer the loss and almost retain similar proton conductivity than prior to immersion. These membranes are alternative polyelectrolytes, which overcome current concerns of actual commercial membranes such as the high cost or the crossover phenomenon

Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers

[EN] The macromolecular dynamics of dendronized copolymer membranes (PECHs), obtained by chemical modification of poly(epichlorohydrin) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, was investigated. In response to a thermal treatment during membrane preparation, these copolymers show an ability to change their shape, achieve orientation, and slightly crystallize, which was also observed by CP-MAS NMR, XRD, and DSC. The phenomenon was deeply analyzed by dielectric thermal analysis. The dielectric spectra show the influence of several factors such as the number of dendritic side groups, the orientation, their self-assembling dendrons, and the molecular mobility. The dielectric spectra present a sub-Tg dielectric relaxation, labelled as gamma, associated with the mobility of the benzyloxy substituent of the dendritic group. This mobility is not related to the percentage of these lateral chains but is somewhat hindered by the orientation of the dendritic groups. Unlike other less complex polymers, the crystallization was dismantled before the appearance of the glass transition (alpha(Tg)). Only after that, clearing transition (alpha(Clear)) can be observed. The PECHs were flexible and offered a high free volume, despite presenting a high degree of modifications. However, the molecular mobility is not independent in each phase and the self-assembling dendrons can be eventually fine-tuned according to the percentage of grafted groups.This research was funded by the Spanish Ministry of Science, Innovation and Universities, grant POLYDECARBOCELL (ENE2017-86711-C3-1-R, ENE2017-86711-C3-3-R).Teruel Juanes, R.; Pascual-Jose, B.; Graf, R.; Reina, JA.; Giamberini, M.; Ribes-Greus, A. (2021). Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers. Polymers. 13(12):1-19. https://doi.org/10.3390/polym13121961119131

Effect of graphene nanoplatelets on the dielectric permittivity and segmental motions of electrospun poly(ethylene-co-vinyl alcohol) nanofibers

The influence of the addition of graphene nanoplatelets (GNPs) on the intra/inter – molecular segmental motions of poly(ethylene-co-vinyl alcohol) (EVOH) was assessed by means of dielectric thermal analysis (DETA). The relaxation spectra were studied in terms of the dielectric permittivity (ε′) and the dielectric loss tangent (tan δ) at wide ranges of frequency (from 10−2 to 107 Hz) and temperature (from -150 to 140 °C). Two relaxation zones were disthinguished. Below the glass transition temperature (Tg), two β-relaxations were observed, which are characteristic local modes of mobility of the EVOH side groups, and related to the influence of the different surroundings of ethylene or vinyl alcohol units. At higher temperatures, the dielectric α-relaxation in the vicinities of the glass transition of EVOH was determined. The thermal activation of the β-relaxations was explained by an Arrhenius model, and showed activation energies (Ea) around 55 and 80 kJ·mol−1. The α-relaxation was explained by the Vogel-Fulcher-Tammann-Hesse (VFTH) model. The study of the segmental dynamics showed an increase in the dynamic fragility parameters with the addition of GNPs. The permittivity was increased at preferential concentrations of GNPs. In particular, the addition of GNPs up to 0.5 wt% increased the dielectric permittivity of the electrospun EVOH/GNPs nanocomposite fibers, specially at low frequencies.The authors would like to thank the European Regional Development Funds (ERDF) and the Spanish Ministry of Science, Innovation, and Universities (MICIU) for the concession of the Research Projects ENE2017-86711-C3-1-R and RTI2018-097249-B-C21. The UPV authors would also like to thank the Chilean Economic Development Agency (CORFO) the economic support in the frame of the project 13CEI2-21839. This research was also funded by the EU H2020 YPACK (773872) and USABLE (BBI-JTI-2018-836884) projects. Torres-Giner is a recipient of a Juan de la Cierva—Incorporación contract (IJCI-2016-29675) from MICIU. Universitat Politècnica de València is acknowledged for the post-doctoral aid for R. Teruel-Juanes, under the PAID-10-19 SUB.1 SP20190049 scholarship.Peer reviewe

Crosslinked chitosan/poly(vinyl alcohol)-based polyelectrolytes for proton exchange membranes

The preparation of polyelectrolytes based on crosslinked poly(vinyl alcohol) (PVA) and chitosan (CS) was considered as a feasible alternative to develop highly functionalised, cost-effective and eco-friendly membranes for proton exchange fuel cell technologies. CS/PVA-based membranes were combined with sulfosuccinic acid (SSA) as crosslinking and sulfonating agent, and glycerol (GL) to promote flexibility and favour their manageability. The chemical structure, the thermo-oxidative behaviour, the ethanol uptake, the electric, the proton conductivity, and the performance in direct ethanol fuel cell (DEFC) were assessed. In general, all the CS/PVA-based polyelectrolytes showed a synergetic increase of thermo-oxidative stability, appropriate absorption and diffusion of ethanol and good proton conductivity, suitable for the typical service conditions of fuel cells. The GL in the membranes reacted with SSA, reduced the ethanol absorption, the diffusion coefficient and the proton conductivity, but acted as a plasticiser that increased the ductile manageability of the polyelectrolytes to be mounted on the membrane-electrode assembly (MEA). Higher presence of CS and higher proportion of GL in the polyelectrolyte, improved the material performance in the DEFC. In particular, the crosslinked polyelectrolyte 40CS/PVA/SSA/20GLwith a 40%wt. of CS referred to PVA, and a 20%wt. of GL referred to CS, showed a suitable behaviour in the DEFC test, with a maximum value of power density of 746 mW\ub7cm 122