Thermoelectric materials, which can generate electricity from waste heat or be used as solid-state Peltier coolers, could play an important role in a global sustainable energy solution. Such a development is contingent on identifying materials with higher thermoelectric efficiency than available at present, which is a challenge owing to the conflicting combination of material traits that are required. Nevertheless, because of modern synthesis and characterization techniques, particularly for nanoscale materials, a new era of complex thermoelectric materials is approaching. We review recent advances in the field, highlighting the strategies used to improve the thermopower and reduce the thermal conductivity.

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Complex thermoelectric materials.

Fuel cells convert chemical energy directly into electrical energy with high efficiency and low emission of pollutants. However, before fuel-cell technology can gain a significant share of the electrical power market, important issues have to be addressed. These issues include optimal choice of fuel, and the development of alternative materials in the fuel-cell stack. Present fuel-cell prototypes often use materials selected more than 25 years ago. Commercialization aspects, including cost and durability, have revealed inadequacies in some of these materials. Here we summarize recent progress in the search and development of innovative alternative materials.

Materials for fuel-cell technologies

1. Introduction 46372. Theoretical Methodologies and Simulation Tools 46402.1. Ab Initio Quantum Chemistry 46412.2. Molecular Dynamics 46422.2.1. Classical Molecular Dynamics and MonteCarlo Simulations46432.2.2. Empirical Valence Bond Models 46442.2.3. Ab Initio Molecular Dynamics (AIMD) 46452.3. Poisson−Boltzmann Theory 46452.4. Nonequilibrium Statistical Mechanical IonTransport Modeling46462.5. Dielectric Saturation 46473. Transport Mechanisms 46483.1. Proton Conduction Mechanisms 46483.1.1. Homogeneous Media 46483.1.2. Heterogeneous Systems (ConfinementEffects)46553.2. Mechanisms of Parasitic Transport 46613.2.1. Solvated Acidic Polymers 46613.2.2. Oxides 46654. Phenomenology of Transport inProton-Conducting Materials for Fuel-CellApplications46664.1. Hydrated Acidic Polymers 46664.2. PBI−H

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Transport in proton conductors for fuel-cell applications: simulations, elementary reactions, and phenomenology.

The state-of-the-art of polymer electrolyte membrane fuel cell (PEMFC) technology is based on perfluorosulfonic acid (PFSA) polymer membranes operating at a typical temperature of 80 °C. Some of the key issues and shortcomings of the PFSA-based PEMFC technology are briefly discussed. These include water management, CO poisoning, hydrogen, reformate and methanol as fuels, cooling, and heat recovery. As a means to solve these shortcomings, high-temperature polymer electrolyte membranes for operation above 100 °C are under active development. This treatise is devoted to a review of the area encompassing modified PFSA membranes, alternative sulfonated polymer and their composite membranes, and acid−base complex membranes. PFSA membranes have been modified by swelling with nonvolatile solvents and preparing composites with hydrophilic oxides and solid proton conductors. DMFC and H2/O2(air) cells based on modified PFSA membranes have been successfully operated at temperatures up to 120 °C under ambient pressure...

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Approaches and Recent Development of Polymer Electrolyte Membranes for Fuel Cells Operating above 100 °C

Fuel cell materials and components

Fuel cells are attractive alternatives to combustion engines for electrical power generation because of their very high efficiencies and low pollution levels. Polymer electrolyte membrane fuel cells are generally considered to be the most viable approach for mobile applications. However, these membranes require humid operating conditions, which limit the temperature of operation to less than 100 degrees C; they are also permeable to methanol and hydrogen, which lowers fuel efficiency. Solid, inorganic, acid compounds (or simply, solid acids) such as CsHSO4 and Rb3H(SeO4)2 have been widely studied because of their high proton conductivities and phase-transition behaviour. For fuel-cell applications they offer the advantages of anhydrous proton transport and high-temperature stability (up to 250 degrees C). Until now, however, solid acids have not been considered viable fuel-cell electrolyte alternatives owing to their solubility in water and extreme ductility at raised temperatures (above approximately 125 degrees C). Here we show that a cell made of a CsHSO4 electrolyte membrane (about 1.5 mm thick) operating at 150-160 degrees C in a H2/O2 configuration exhibits promising electrochemical performances: open circuit voltages of 1.11 V and current densities of 44 mA cm-2 at short circuit. Moreover, the solid-acid properties were not affected by exposure to humid atmospheres. Although these initial results show promise for applications, the use of solid acids in fuel cells will require the development of fabrication techniques to reduce electrolyte thickness, and an assessment of possible sulphur reduction following prolonged exposure to hydrogen.

Solid acids as fuel cell electrolytes

Although they hold the promise of clean energy, state-of-the-art fuel cells based on polymer electrolyte membrane fuel cells are inoperable above 100°C, require cumbersome humidification systems, and suffer from fuel permeation. These difficulties all arise from the hydrated nature of the electrolyte. In contrast, “solid acids” exhibit anhydrous proton transport and high-temperature stability. We demonstrate continuous, stable power generation for both H_2/O_2 and direct methanol fuel cells operated at ∼250°C using a humidity-stabilized solid acid CsH_2PO_4 electrolyte.

https://science.sciencemag.org/content/sci/303/5654/68.full.pdf

High-Performance Solid Acid Fuel Cells Through Humidity Stabilization

The compound CsH2PO4 has emerged as a viable electrolyte for intermediate temperature (200–300 °C) fuel cells. In order to settle the question of the high temperature behavior of this material, conductivity measurements were performed by two-point AC impedance spectroscopy under humidified conditions (p[H2O] = 0.4 atm). A transition to a stable, high conductivity phase was observed at 230 °C, with the conductivity rising to a value of 2.2 × 10−2 S cm−1 at 240 °C and the activation energy of proton transport dropping to 0.42 eV. In the absence of active humidification, dehydration of CsH2PO4 does indeed occur, but, in contradiction to some suggestions in the literature, the dehydration process is not responsible for the high conductivity at this temperature. Electrochemical characterization by galvanostatic current interrupt (GCI) methods and three-point AC impedance spectroscopy (under uniform, humidified gases) of CsH2PO4 based fuel cells, in which a composite mixture of the electrolyte, Pt supported on carbon, Pt black and carbon black served as the electrodes, showed that the overpotential for hydrogen electrooxidation was virtually immeasurable. The overpotential for oxygen electroreduction, however, was found to be on the order of 100 mV at 100 mA cm−2. Thus, for fuel cells in which the supported electrolyte membrane was only 25 μm in thickness and in which a peak power density of 415 mW cm−2 was achieved, the majority of the overpotential was found to be due to the slow rate of oxygen electrocatalysis. While the much faster kinetics at the anode over those at the cathode are not surprising, the result indicates that enhancing power output beyond the present levels will require improving cathode properties rather than further lowering the electrolyte thickness. In addition to the characterization of the transport and electrochemical properties of CsH2PO4, a discussion of the entropy of the superprotonic transition and the implications for proton transport is presented.

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Solid acid proton conductors: from laboratory curiosities to fuel cell electrolytes

Superprotonic behavior of Cs2(HSO4)(H2PO4) – a new solid acid in the CsHSO4–CsH2PO4 system

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.

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Calum R. I. Chisholm

Papers

Solid acids as fuel cell electrolytes

High-Performance Solid Acid Fuel Cells Through Humidity Stabilization

Solid acid proton conductors: from laboratory curiosities to fuel cell electrolytes

Superprotonic behavior of Cs2(HSO4)(H2PO4) – a new solid acid in the CsHSO4–CsH2PO4 system

Polymer Solid Acid Composite Membranes for Fuel‐Cell Applications