An All-Climate Nonaqueous Hydrogen Gas-Proton Battery.

Rechargeable hydrogen gas batteries, driven by hydrogen evolution and oxidation reactions (HER/HOR), are emerging grid-scale energy storage technologies owing to their low cost and superb cycle life. However, compared with aqueous electrolytes, the HER/HOR activities in nonaqueous electrolytes have rarely been studied. Here, for the first time, we develop a nonaqueous proton electrolyte (NAPE) for a high-performance hydrogen gas-proton battery for all-climate energy storage applications. The advanced nonaqueous hydrogen gas-proton battery (NAHPB) assembled with a representative V2(PO4)3 cathode and H2 anode in a NAPE exhibits a high discharge capacity of 165 mAh g-1 at 1 C at room temperature. It also efficiently operates under all-climate conditions (from -30 to +70 °C) with an excellent electrochemical performance. Our findings offer a new direction for designing nonaqueous proton batteries in a wide temperature range.

Breaking Local Charge Symmetry of Iron Single Atoms for Efficient Electrocatalytic Nitrate Reduction to Ammonia.

The electrochemical conversion of nitrate pollutants into value-added ammonia is a feasible way to achieve artificial nitrogen cycle. However, the development of electrocatalytic nitrate-to-ammonia reduction reaction (NO3 - RR) has been hampered by high overpotential and low Faradaic efficiency. Here we develop an iron single-atom catalyst coordinated with nitrogen and phosphorus on hollow carbon polyhedron (denoted as Fe-N/P-C) as a NO3 - RR electrocatalyst. Owing to the tuning effect of phosphorus atoms on breaking local charge symmetry of the single-Fe-atom catalyst, it facilitates the adsorption of nitrate ions and enrichment of some key reaction intermediates during the NO3 - RR process. The Fe-N/P-C catalyst exhibits 90.3 % ammonia Faradaic efficiency with a yield rate of 17980 µg h-1 mgcat -1 , greatly outperforming the reported Fe-based catalysts. Furthermore, operando SR-FTIR spectroscopy measurements reveal the reaction pathway based on key intermediates observed under different applied potentials and reaction durations. Density functional theory calculations demonstrate that the optimized free energy of NO3 - RR intermediates is ascribed to the asymmetric atomic interface configuration, which achieves the optimal electron density distribution. This work demonstrates the critical role of atomic-level precision modulation by heteroatom doping for the NO3 - RR, providing an effective strategy for improving the catalytic performance of single atom catalysts in different electrochemical reactions.

Anions Regulation Engineering Enables a Highly Reversible and Dendrite-Free Nickel-Metal Anode with Ultrahigh Capacities.

The development of safe and high-energy metal anodes represents a crucial research direction. Here, the achievement of highly reversible, dendrite-free transition metal anodes with ultrahigh capacities by regulating aqueous electrolytes is reported. Using nickel (Ni) as a model, theoretical and experimental evidence demonstrating the beneficial role of chloride ions in inhibiting and disrupting the nickel hydroxide passivation layer on the Ni electrode is provided. As a result, Ni anodes with an ultrahigh areal capacity of 1000 mAh cm-2 (volumetric capacity of ≈6000 mAh cm-3 ), and a Coulombic efficiency of 99.4% on a carbon substrate, surpassing the state-of-the-art metal electrodes by approximately two orders of magnitude, are realized. Furthermore, as a proof-of-concept, a series of full cells based on the Ni anode is developed. The designed Ni-MnO2 full battery exhibits a long lifespan of 2000 cycles, while the Ni-PbO2 full battery achieves a high areal capacity of 200 mAh cm-2 . The findings of this study are important for enlightening a new arena toward the advancement of dendrite-free Ni-metal anodes with ultrahigh capacities and long cycle life for various energy-storage devices.

Ultrafast Electrical Pulse Synthesis of Highly Active Electrocatalysts for Beyond-Industrial-Level Hydrogen Gas Batteries.

The high reliability and proven ultra-longevity make aqueous hydrogen gas (H2 ) batteries ideal for large-scale energy storage. However, the low alkaline hydrogen evolution and oxidation reaction (HER/HOR) activities of expensive platinum catalysts severely hamper their widespread applications in H2 batteries. Here, cost-effective, highly active electrocatalysts, with a model of ruthenium-nickel alloy nanoparticles in ≈3 nm anchored on carbon black (RuNi/C) as an example, are developed by an ultrafast electrical pulse approach for nickel-hydrogen gas (NiH2 ) batteries. Having a competitive low cost of about one fifth of Pt/C benckmark, this ultrafine RuNi/C catalyst displays an ultrahigh HOR mass activity of 2.34 A mg-1 at 50 mV (vs RHE) and an ultralow HER overpotential of 19.5 mV at a current density of 10 mA cm-2 . As a result, the advanced NiH2 battery can efficiently operate under all-climate conditions (from -25 to +50 °C) with excellent durability. Notably, the NiH2 cell stack achieves an energy density up to 183 Wh kg-1 and an estimated cost of ≈49 $ kWh-1 under an ultrahigh cathode Ni(OH)2 loading of 280 mg cm-2 and a low anode Ru loading of ≈62.5 µg cm-2 . The advanced beyond-industrial-level hydrogen gas batteries provide great opportunities for practical grid-scale energy storage applications.

Solid-Liquid-Gas Management for Low-Cost Hydrogen Gas Batteries.

Aqueous nickel-hydrogen gas (Ni-H2) batteries with excellent durability (>10,000 cycles) are important candidates for grid-scale energy storage but are hampered by the high-cost Pt electrode with limited performance. Herein, we report a low-cost nickel-molybdenum (NiMo) alloy as an efficient bifunctional hydrogen evolution and oxidation reaction (HER/HOR) catalyst for Ni-H2 batteries in alkaline electrolytes. The NiMo alloy demonstrates a high HOR mass-specific kinetic current of 28.8 mA mg-1 at 50 mV as well as a low HER overpotential of 45 mV at a current density of 10 mA cm-2, which is better than most nonprecious metal catalysts. Furthermore, we apply a solid-liquid-gas management strategy to constitute a conductive, hydrophobic network of NiMo using multiwalled carbon nanotubes (NiMo-hydrophobic MWCNT) in the electrode to accelerate HER/HOR activities for much improved Ni-H2 battery performance. As a result, Ni-H2 cells based on the NiMo-hydrophobic MWCNT electrode show a high energy density of 118 Wh kg-1 and a low cost of only 67.5 $ kWh-1. With the low cost, high energy density, excellent durability, and improved energy efficiency, the Ni-H2 cells show great potential for practical grid-scale energy storage.

pH-Universal Decoupled Water Electrolysis Enabled by Electrocatalytic Hydrogen Gas Capacitive Chemistry.

In conventional water electrolysis (CWE), the H2 and O2 evolution reactions (HER/OER) are tightly coupled, making the generated H2 and O2 difficult to separate, thus resulting in complex separation technology and potential safety issues. Previous efforts on the design of decoupled water electrolysis mainly concentrated on multi-electrode or multi-cell configurations; however, these strategies have the limitation of involving complicated operations. Here, we propose and demonstrate a pH-universal, two-electrode capacitive decoupled water electrolyzer (referred to as all-pH-CDWE) in a single-cell configuration by utilizing a low-cost capacitive electrode and a bifunctional HER/OER electrode to separate H2 and O2 generation for decoupling water electrolysis. In the all-pH-CDWE, high-purity H2 and O2 generation alternately occur at the electrocatalytic gas electrode only by reversing the current polarity. The designed all-pH-CDWE can maintain a continuous round-trip water electrolysis for over 800 consecutive cycles with an electrolyte utilization ratio of nearly 100%. As compared to CWE, the all-pH-CDWE achieves energy efficiencies of 94% in acidic electrolytes and 97% in alkaline electrolytes at a current density of 5 mA cm-2. Further, the designed all-pH-CDWE can be scaled up to a capacity of 720 C in a high current of 1 A for each cycle with a stable HER average voltage of 0.99 V. This work provides a new strategy toward the mass production of H2 in a facilely rechargeable process with high efficiency, good robustness, and large-scale applications.

Reversible, Dendrite-Free, High-Capacity Aluminum Metal Anode Enabled by Aluminophilic Interface Layer.

Aluminum (Al) metal is an attractive anode material for next-generation rechargeable batteries, because of its low cost and high capacities. However, it brings some fundamental issues such as dendrites, low Coulombic efficiency (CE), and low utilization. Here, we propose a strategy for constructing an ultrathin aluminophilic interface layer (AIL) to regulate the Al nucleation and growth behaviors, which enables highly reversible and dendrite-free Al plating/stripping under high areal capacity. Metallic Al can maintain stable plating/stripping on the Pt-AIL@Ti for over 2000 h at 10 mAh cm-2 with an average CE of 99.9%. The Pt-AIL also enables reversible Al plating/stripping at a record high areal capacity of 50 mAh cm-2, which is 1-2 orders of magnitude higher than the previous studies. This work provides a valuable direction for further construction of high-performance rechargeable Al metal batteries.

Ultralow-Temperature Aqueous Conductive Polymer-Hydrogen Gas Battery.

Hydrogen gas batteries are regarded as one of the most promising rechargeable battery systems for large-scale energy storage applications due to their advantages of high rates and long-term cycle lives. However, the development of cost-effective and low-temperature-tolerant hydrogen gas batteries is highly desirable yet very challenging. Herein, we report a novel conductive polymer-hydrogen gas battery that is suitable for ultralow-temperature energy storage applications and consists of a hydrogen gas anode, a conductive polymer cathode using polyaniline (PANI) or polypyrrole as examples, and protonic acidic electrolytes. The PANI-H2 battery using 1 M H2SO4 as the electrolyte exhibits a capacity of 67 mA h/g, a remarkable rate up to 15 A/g, a Coulombic efficiency around 100%, and an ultra-long life of 10,000 cycles. Using the anti-freezing 9 M H3PO4 electrolyte, the PANI-H2 battery can operate well at temperatures down to -70 °C, which maintains ∼70% of the capacity at room temperature and shows an excellent cycle stability under -60 °C. Benefiting from the fast redox kinetics of both electrodes, this work demonstrates excellent rate performance and low-temperature feasibility of conductive polymer-H2 batteries, providing a new avenue for further development of low-cost and reliable polymer-H2 batteries for large-scale energy storage.

Production of a hybrid capacitive storage device via hydrogen gas and carbon electrodes coupling.

Conventional electric double-layer capacitors are energy storage devices with a high specific power and extended cycle life. However, the low energy content of this class of devices acts as a stumbling block to widespread adoption in the energy storage field. To circumvent the low-energy drawback of electric double-layer capacitors, here we report the assembly and testing of a hybrid device called electrocatalytic hydrogen gas capacitor containing a hydrogen gas negative electrode and a carbon-based positive electrode. This device operates using pH-universal aqueous electrolyte solutions (i.e., from 0 to 14) in a wide temperature range (i.e., from - 70 °C to 60 °C). In particular, we report specific energy and power of 45 Wh kg-1 and 458 W kg-1 (both values based on the electrodes' active materials mass), respectively, at 1 A g-1 and 25 °C with 9 M H3PO4 electrolyte solution. The device also enables capacitance retention of 85% (final capacitance of about 114 F g-1) after 100,000 cycles at 10 A g-1 and 25 °C with 1 M phosphate buffer electrolyte solution.

Facile Fabrication of Bifunctional Hydrogen Catalytic Electrodes for Long-Life Nickel-Hydrogen Gas Batteries.

The renaissance of long-lasting nickel-hydrogen gas (Ni-H2) battery by developing efficient, robust, and affordable hydrogen anode to replace Pt is particularly attractive for large-scale energy storage applications. Here, we demonstrate an extremely facile corrosion induced fabrication approach to achieve a self-supporting hydrogen evolution/oxidation reaction (HER/HOR) bifunctional nanosheet array electrode for Ni-H2 battery. The electrode is constituted by ultrafine Ru nanoparticles on Ni(OH)2 nanosheets grown on nickel foam. Experimental and theoretical calculation results reveal that the electrode with optimized geometric and electronic structures ensures the efficient and robust catalytic hydrogen activities. The fabricated Ni-H2 battery using the Ru-Ni(OH)2/NF anode with an industrial scale areal capacity of 16 mAh cm-2 demonstrates a high energy density, good rate capability and excellent durability without capacity decay over 1800 h. This study casts light on the development of low manufacturing cost and high performance bifunctional hydrogen catalytic electrodes for future hydrogen energy applications.

An Ultrafast and Ultra-Low-Temperature Hydrogen Gas-Proton Battery.

Aqueous proton batteries are regarded as one of the most promising energy technologies for next-generation grid storage due to the distinctive merits of H+ charge carriers with small ionic radius and light weight. Various materials have been explored for aqueous proton batteries; however, their full batteries show undesirable electrochemical performance with limited rate capability and cycling stability. Here we introduce a novel aqueous proton full battery that shows remarkable rate capability, cycling stability, and ultralow temperature performance, which is driven by a hydrogen gas anode and a Prussian blue analogue cathode in a concentrated phosphoric acid electrolyte. Its operation involves hydrogen evolution/oxidation redox reactions on the anode and H+ insertion/extraction reactions on the cathode, in parallel with the ideal transfer of only H+ between these two electrodes. The fabricated aqueous hydrogen gas-proton battery exhibits an unprecedented charge/discharge capability of up to 960 C with a superior power density of 36.5 kW kg-1, along with an ultralong cycle life of over 0.35 million cycles. Furthermore, this hydrogen gas-proton battery is able to work well at an ultralow temperature of -80 °C with 54% of its room-temperature capacity and under -60 °C with a stable cycle life of 1150 cycles. This work provides new opportunities to construct aqueous proton batteries with high performance in extreme conditions for large-scale energy storage.