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Summary: The majority of usable energy generated by humanity is lost as waste heat, but thermogalvanic systems (or thermocells) can address this problem by converting low-grade waste heat directly into electricity using redox chemistry. The concentration of the redox couple is a critical parameter; almost invariably, higher concentrations result in more power. This study exploits the simple synergy between Na+ and K+ counter ions to achieve—to the best of our knowledge—the most concentrated stable aqueous ferricyanide/ferrocyanide thermocell to date, at 1.6 m [Fe(CN)6]3−/4−. Despite increasing the concentration by 400% relative to the standard K3/K4[Fe(CN)6] electrolyte (0.4 m), electrical power production increased only 166%. Pushing the system from conventional salt-in-water electrolytes into the quasi-stable water-in-salt region (up to 2.4 m) resulted in a decrease in power. Detailed characterization highlighted the various physicochemical hurdles introduced by these extremely concentrated electrolytes; the identified issues have direct relevance to other energy systems also seeking to use the highest possible concentration.

Thermogalvanic systems represent a means to convert a temperature gradient into electricity, using only redox chemistry. However, the kinetics of electron transfer and physical mass transport of the redox couples are known limitations. In this study we present self-contained gelled thermogalvanic cells (or thermocells) containing the ferricyanide/ferrocyanide redox couple, which additionally have gold nanoparticles either immobilised at the gel/electrode interface, or distributed throughout the entire gel. Both methods of introducing the gold nanoparticles result in an apparent electrocatalytic improvement, as demonstrated by significant decreases in the electron transfer resistance. However, when used as thermogalvanic cells, only minor improvements were observed in power generation, and relatively rapid dissolution of the gold nanoparticles was observed, to yield passivating gold analogues of Prussian blue. Therefore successful preparation and short-term improvements have been demonstrated, but are offset by long-term stability issues. The relatively surprising instability of the generally inert gold nanoparticles in the presence of ferricyanide/ferrocyanide, particularly under thermogalvanic conditions, is of particular note. Keywords: Thermoelectrochemistry, Thermogalvanic cells, Gold nanoparticles

Thermo-electrochemical cells (known as thermocells) can convert heat energy into electrical power through redox reactions driven by the presence of a temperature gradient. Low-grade heat from the human body can be harvested using thermocells containing a suitable electrolyte, such as the iron(II)/iron(III) chloride redox couple housed in poly (vinyl alcohol) described here. However, conventionally the thermo-electrochemical performance of gelled electrolytes is poor, due to slow ionic transport and high charge transfer resistance. In this report, hydrochloric acid has been found to synergistically decrease the charge transfer resistance of the redox reaction, whilst doubling the tensile properties of the gel housing. Moreover, individual thermocells can be connected in parallel to enhance current output.