Combining water electrolysis and rechargeable battery technologies into a single system holds great promise for the co-production of hydrogen (H2) and electricity. However, the design and development of such systems is still in its infancy. Herein, an integrated hydrogen-oxygen (O2)-electricity co-production system featuring a bipolar membrane-assisted decoupled electrolyzer and a Na-Zn ion battery was established with sodium nickelhexacyanoferrate (NaNiHCF) and Zn2+/Zn as dual redox electrodes. The decoupled electrolyzer enables to produce H2 and O2 in different time and space with almost 100% Faradic efficiency at 100 mA cm−2. Then, the charged NaNiHCF and Zn electrodes after the electrolysis processes formed a Na-Zn ion battery, which can generate electricity with an average cell voltage of 1.75 V at 10 mA cm−2. By connecting Si photovoltaics with the modular electrochemical device, a well-matched solar driven system was built to convert the intermittent solar energy into hydrogen and electric energy with a solar to hydrogen-electricity efficiency of 16.7%, demonstrating the flexible storage and conversion of renewables.
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