Long-term continuous ammonia electrosynthesis

Abstract

Ammonia is crucial as a fertilizer and in the chemical industry and is considered to be a carbon-free fuel¹. Ammonia electrosynthesis from nitrogen under ambient conditions offers an attractive alternative to the Haber-Bosch process^2,3, and lithium-mediated nitrogen reduction represents a promising approach to continuous-flow ammonia electrosynthesis, coupling nitrogen reduction with hydrogen oxidation⁴. However, tetrahydrofuran, which is commonly used as a solvent, impedes long-term ammonia production owing to polymerization and volatility problems. Here we show that a chain-ether-based electrolyte enables long-term continuous ammonia synthesis. We find that a chain-ether-based solvent exhibits non-polymerization properties and a high boiling point (162 °C) and forms a compact solid-electrolyte interphase layer on the gas diffusion electrode, facilitating ammonia release in the gas phase and ensuring electrolyte stability. We demonstrate 300 h of continuous operation in a flow electrolyser with a 25 cm² electrode at 1 bar pressure and room temperature, and achieve a current-to-ammonia efficiency of 64 ± 1% with a gas-phase ammonia content of approximately 98%. Our results highlight the crucial role of the solvent in long-term continuous ammonia synthesis.