Acid-in-clay electrolyte for wide-temperature-range and long-cycle proton batteries

Proton conduction underlies many important electrochemical technologies. We report a series of new proton electrolytes: acid-in-clay electrolyte termed AiCE, prepared by integrating fast proton carriers in a natural phyllosilicate clay network, that can be made into thin-film (tens of microns) fluid-impervious membranes. The chosen example systems (sepiolite-phosphoric acid) rank top among the solid proton conductors in consideration of proton conductivities (15 mS cm−1 at 25 °C, 0.023 mS cm−1 at −82 °C), the stability window (3.35 V), and reduced chemical activity. A solid-state proton battery was assembled using AiCE as the electrolyte to demonstrate the performance of these electrolytes. Benefitting from the wider electrochemical stability window, reduced corrosivity, and excellent ionic selectivity of AiCE, the two main problems (gasification and cyclability) of proton batteries have been successfully solved. This work also draws the attention of elemental cross-over in proton batteries and illustrates a simple “acid-in-clay” approach to synthesize a series of solid proton electrolytes with a superfast proton permeability, outstanding selectivity, and improved stability for many potential applications associated with protons.

Anhydrous Grotthuss mechanism for fast proton transport in a dense oxide-ion array of α-MoO3

Developing high-power battery chemistry is an urgent task to buffer fluctuating renewable energies and achieve a sustainable and flexible power supply. Owing to the small size of proton and its ultrahigh mobility in water via the Grotthuss mechanism, aqueous proton batteries are an attractive candidate for high-power energy storage devices. Although Grotthuss proton transfer usually occurs in hydrogen-bonded networks of water molecules, in this work, we discover anhydrous Grotthuss-type proton transport in a dense oxide-ion array of solid α-MoO3 even without structural water. The fast proton transfer and accumulation that occurs during (de)intercalation in α-MoO3 is unveiled using both experiments and first-principles calculations. Coupled with a zinc anode and a superconcentrated dual-ion Zn2+/H+ electrolyte, the solid-state anhydrous Grotthuss proton transport mechanism realizes an aqueous MoO3-Zn battery with both high energy and power densities.

Alkaline polymers of intrinsic microporosity: high-conduction and low-loss anhydrous proton exchange membranes for energy conversion

Polymers of intrinsic microporosity, with high volume and capillary force, can meet the requirements of PA adsorption and retention for HT-PEMs. The widespread and interconnected microstructure realized state-of-the-art HT-PEMs with fast proton transfer.

Proton transport enabled by a field-induced metallic state in a semiconductor heterostructure

Tuning a semiconductor to function as a fast proton conductor is an emerging strategy in the rapidly developing field of proton ceramic fuel cells (PCFCs). The key challenge for PCFC researchers is to formulate the proton-conducting electrolyte with conductivity above 0.1 siemens per centimeter at low temperatures (300 to 600°C). Here we present a methodology to design an enhanced proton conductor by means of a NaxCoO2/CeO2 semiconductor heterostructure, in which a field-induced metallic state at the interface accelerates proton transport. We developed a PCFC with an ionic conductivity of 0.30 siemens per centimeter and a power output of 1 watt per square centimeter at 520°C. Through our semiconductor heterostructure approach, our results provide insight into the proton transport mechanism, which may also improve ionic transport in other energy applications.