Effect of lattice volume and strain on the conductivity of BaCeY-oxide ceramic proton conductors

In-situ electrochemical impedance spectroscopy was used to study the effect of lattice volume and strain on the proton conductivity of the yttrium-doped barium cerate proton conductor by applying the hydrostatic pressure up to 1.25 GPa. An increase from 0.62 eV to 0.73 eV in the activation energy of the bulk conductivity was found with increasing pressure during a unit cell volume change of 0.7%, confirming a previously suggested correlation between lattice volume and proton diffusivity in the crystal lattice. One strategy worth trying in the future development of the ceramic proton conductors could be to expand the lattice and potentially lower the activation energy under tensile strain

New multifunctional sulfonato-containing metal phosphonates proton conductors

Anchoring of acidic functional groups to organic linkers acting as ligands in metal phosphonates has been demonstrate to be a valid strategy to develop new proton conductor materials, which exhibit tunable properties and are potentially applicable to proton exchange membranes, such as those used in PEMFCs [1,2]. In this work, the structural and proton conductivity properties of several families of divalent and trivalent metal amino-sulfophosphonates are presented. The chosen ligand, (H2O3PCH2)2-N-(CH2)2-SO3H, was reacted with the appropriate metal salt using highthrough-put screening and/or microwave-assisted synthesis. Different crystal structures haven been solved displaying a variety of metal ligand coordination modes, in whose frameworks acidic groups contribute to create strong H-bond networks; together with lattice and bound water molecules. Proton conductivity values oscillate between 10-4 and 10-2 S.cm-1, at 80 ºC and 95 % relative humidity, most of them showing activation energies characteristic of a Grotthuss-type proton transport mechanism.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. MINECO: MAT2016-77648-R Junta de Andalucía: P-12-FQM-1656 y FQM-11

Proton conductivity of multifunctional metal phosphonate frameworks

Metal phosphonates exhibit attractive characteristics for proton conductivity, such as tunable functionality, chemical and thermal stability and the existence of H-bond networks with acidic protons within their structure.1 In the present work, we examine the relationship between crystal structure and proton conductivity for several metal (mono-, di- and tri-valent) phosphonates containing rigid: (5-(dihydroxyphosphoryl)isophthalic acid, PiPhtA and 2-hydroxyphosphonoacetic acid, HPAA) or flexible: (hexa- or octamethylenediamine-N,N,N′,N′-tetrakis(methylenephosphonic acid, H8HDTMP or H8ODTMP) multifunctional ligands. The crystalline hybrid derivatives prepared show a great structural diversity, from 1D to 3D open-frameworks possessing hydrogen-bonded water molecules and phosphonic and carboxylic acid groups. The rigid 3D framework of Ca-PiPhtA, that exhibits a proton conductivity of 5.7•10-4 S/cm as synthesized, transforms into a layered compound upon exposure to ammonia vapors2 with increased proton conductivity (6.6•10-3 S/cm). The flexible frameworks of magnesium or lanthanide phosphonates, with 1D channels, present conductivities higher than 10-3 S/cm. Their activation energies fall in the range corresponding to a Grotthuss mechanism.3,4 For M(I)-HPAA solids conductivities up to 5.6•10-3 S/cm were measured. References 1. P. Ramaswamy, N.E. Wong, G.K.H. Shimizu, Chem. Soc. Rev. 43 (2014) 5913. 2. M. Bazaga-García, R.M.P. Colodrero, M. Papadaki, P. Garczarek, J. Zoń, P. Olivera-Pastor, E.R. Losilla, L. León-Reina, M.A.G. Aranda, D. Choquesillo-Lazarte, K.D. Demadis, A. Cabeza, J. Amer. Chem. Soc. 136 (2014) 5731. 3. R.M.P. Colodrero, P. Olivera-Pastor, E.R. Losilla, D. Hernández-Alonso, M.A.G. Aranda, L. Leon-Reina, J. Rius, K.D. Demadis, B. Moreau, D. Villemin, M. Palomino, F. Rey, A. Cabeza, Inorg. Chem. 51 (2012) 7689. 4. R.M.P. Colodrero, P. Olivera-Pastor, E.R. Losilla, M.A.G. Aranda, L. Leon-Reina, M. Papadaki, A.C. McKinlay, R.E. Morris, K.D. Demadis, A. Cabeza, Dalton Trans. 41 (2012) 4045.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. Junta de Andalucía, Proyecto Excelencia FQM-1656. Ministerio de Economía y Competitividad, MAT2013-41836-

Polymer solid acid composite membranes for fuel-cell applications

A systematic study of the conductivity of polyvinylidene fluoride (PVDF) and CsHSO4 composites, containing 0 to 100% CsHSO4, has been carried out. The polymer, with its good mechanical properties, served as a supporting matrix for the high proton conductivity inorganic phase. The conductivity of composites exhibited a sharp increase with temperature at 142°C, characteristic of the superprotonic phase transition of CsHSO4. At high temperature (160°C), the dependence of conductivity on vol % CsHSO4 was monotonic and revealed a percolation threshold of ~10 vol %. At low temperature (100°C), a maximum in the conductivity at ~80 vol % CsHSO4 was observed. Results of preliminary fuel cell measurements are presented

Tunable crystal structure and proton conductivity of lanthanide nitrilotrismethylphosphonates

Metal phosphonates are multifunctional solids with remarkable stability and proton conducting properties owing to their structure is usually composed of extended hydrogen-bond networks that favor proton transfer pathways [1]. Moreover, these properties can be enhanced by appropriate modification of the synthesis conditions [2, 3]. In this communication, a new family of isostructural 2D layered compounds based on lanthanide nitrilotris-methylphosphonates is reported. These compounds have been isolated at room temperature and have the general formula Ln[N(CH2)3(PO3H2)2(PO3H)(H2O)]SO4·2H2O (Ln= Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Yb). The coordination environment of Ln3+ is composed by eight oxygen atoms from three different ligands and two oxygens from bound waters. This connectivity creates positive charged layers connected to sulfate ions through hydrogen-bonds. These compounds show promising proton conductivity with values ranging between 7.6·10-2 and 3.8·10-2 S·cm-1 at 80 °C and 95% RH and low activation energy corresponding to Grotthuss-type proton transfer mechanism. In addition, a structural transformation occurs at T > 70 °C accompanied by a remarkable enhanced conductivity. Studies on the structure-properties relationships will be discussed.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. MINECO: MAT2016-77648-R Junta Andalucía: P12-FQM-1656 y FQM-11

Proton conductivity and luminiscence properties of lanthanide aminotriphosphonates

Metal phosphonates are multifunctional solids with tunable properties, such as internal H-bond networks, and high chemical and thermal stability [1]. In the present work, we describe the synthesis, structural characterization, luminescent properties and proton conduction performance of a new family of isostructural cationic compounds with general formula [Ln(H4NMP)(H2O)2]Cl·2H2O [Ln = La3+, Pr3+, Sm3+, Gd3+, Tb3+, Dy3+, Ho3+, H6NMP = nitrilotris(methylphosphonic acid)]. These solids are formed by positively charge layers, which consist of isolated LnO8 polyhedra and bridge chelating NMP2- ligands, held apart by chloride ions and water molecules. This arrangement result in extended interlayer hydrogen networks with possible proton transfer pathways. The proton conductivity of Gd3+ sample, selected as prototype of the series, was measured. In the range between range 25º and 80 ºC, the conductivity increase with the temperature up to a maximum value of 3.10-4 S·cm-1, at relative humidity of 95 %. The activation energy obtained from the Arrhenius plot (Figure 1) is in the range corresponding to a Grotthuss transfer mechanism.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. FQM-1656; MAT2013-41836-R

Some Peculiarities of Proton Transport in Quasi-One-Dimensional Hydrogen-Bonded Chains

The protonic conductivity in the hydrogen bonded chains is investigated theoretically in the framework of the two-stage transport model. The strong interactions with optical phonon stretching mode are considered. We obtain the transition from the insulator to the metal-type state from the temperature dependencies of the hopping conductivity and analyze the influence of the specific Grotthuss mechanism on the transition character. We investigate also the main peculiarities in the frequency dependencies of the band and hopping conductivity parts which appear due to above-mentioned two-stage process of the proton migration along the chain.Comment: 21 pages, RevTeX, 9 eps figure

Synthesis and proton conduction properties of lanthanide amino-sulfophosphonates

Crystalline acid-functionalized metal phosphonates are potential candidates as proton conducting electrolytes. Their frameworks can be chemically modified to contain proton carriers such as acidic groups (P-OH; -SO3H, -COOH,…) and guest molecules (H2O, NH3,…) that generates hydrogen bond networks stable in a wide range of temperature [1,2]. In this work, focus is laid on properties derived from the combination of lanthanide ions with the amino-sulfophosphonate ligand (H2O3PCH2)2-N-(CH2)2-SO3H. Hightrough-put screening was followed to reach the optimal synthesis conditions under solvothermal conditions at 140 ºC. Isolated polycrystalline solids, Ln[(O3PCH2)2-NH-(CH2)2-SO3H].2H2O (Ln= La, Pr and Sm), crystallize in the monoclinic (La) and orthorhombic (Pr and Sm) systems with unit cell volume of ~2548 Å3. Preliminary proton conductivity measurements for Sm derivative have been carried out between 25º and 80 ºC at relative humidity (RH) values of 70 % and 95 %. The sample exhibits enhanced conductivity at high RH and T (Figure 1) and constant activation energies of 0.4 eV, typical of a Grothuss mechanism of proton.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech. FQM-1656; MAT2013-41836-