All Publications


  • Rechargeable Na/Cl2 and Li/Cl2 batteries. Nature Zhu, G., Tian, X., Tai, H., Li, Y., Li, J., Sun, H., Liang, P., Angell, M., Huang, C., Ku, C., Hung, W., Jiang, S., Meng, Y., Chen, H., Lin, M., Hwang, B., Dai, H. 2021; 596 (7873): 525-530

    Abstract

    Lithium-ion batteries (LIBs) are widely used in applications ranging from electric vehicles to wearable devices. Before the invention of secondary LIBs, the primary lithium-thionyl chloride (Li-SOCl2) battery was developed in the 1970s using SOCl2 as the catholyte, lithium metal as the anode and amorphous carbon as the cathode1-7. This battery discharges by lithium oxidation and catholyte reduction to sulfur, sulfur dioxide and lithium chloride, is well known for its high energy density and is widely used in real-world applications; however, it has not been made rechargeable since its invention8-13. Here we show that with a highly microporous carbon positive electrode, a starting electrolyte composed of aluminium chloride in SOCl2 with fluoride-based additives, and either sodium or lithium as the negative electrode, we can produce a rechargeable Na/Cl2 or Li/Cl2 battery operating via redox between mainly Cl2/Cl- in the micropores of carbon and Na/Na+ or Li/Li+ redox on the sodium or lithium metal. The reversible Cl2/NaCl or Cl2/LiCl redox in the microporous carbon affords rechargeability at the positive electrodeside and the thin alkali-fluoride-doped alkali-chloride solid electrolyte interfacestabilizesthe negative electrode, both are critical to secondary alkali-metal/Cl2 batteries.

    View details for DOI 10.1038/s41586-021-03757-z

    View details for PubMedID 34433941

  • Selective and High Current CO2 Electro-Reduction to Multicarbon Products in Near-Neutral KCl Electrolytes. Journal of the American Chemical Society Zhang, X., Li, J., Li, Y., Jung, Y., Kuang, Y., Zhu, G., Liang, Y., Dai, H. 2021

    Abstract

    Reducing CO2 to value-added multicarbon (C2+) fuels and chemicals using renewable energy is a viable way to circumvent CO2 buildup in the atmosphere and facilitate closing the carbon cycle. To date it remains a challenge to achieve high product selectivity and long-term stability of electrocatalytic carbon dioxide reduction reaction (CO2RR) especially at practically relevant high current levels >100 mA cm-2. Here, we report a simple electrodeposited Cu electrocatalyst on a hydrophobic porous gas-diffusion layer (GDL) electrode affording stable and selective CO2RR to C2+ products in near-neutral KCl electrolytes. By directing the CO2 stream to fully submerged hydrophobic GDLs in a H-cell, high C2+ partial current densities near 100 mA cm-2 were achieved. In a flow-cell setup, the Cu/GDL cathode in 2 M KCl afforded stable CO2RR superior to that in widely used KOH electrolytes. We found that Cu etching/corrosion associated with trace oxygen played a role in the catalyst instability in alkaline media under cathodic CO2RR conditions, a problem largely suppressed in near-neutral electrolyte. A two-electrode CO2 electrolyzer was constructed with a Cu/GDL cathode in KCl catholyte and an anode comprised of nickel-iron hydroxide on nickel foam (NiFe/NF) in a KOH anolyte separated by Nafion membrane. By periodically adding HCl to the KCl catholyte to compensate the increasing pH and remove accumulated (bi)carbonates, we observed little decay over 30 h in flow-cell CO2RR activity and selectivity at 150 mA cm-2 with a high Faradaic efficiency (FE) of 75% and energy efficiency of 40% for C2+ products.

    View details for DOI 10.1021/jacs.0c13427

    View details for PubMedID 33617245

  • A high-performance potassium metal battery using safe ionic liquid electrolyte. Proceedings of the National Academy of Sciences of the United States of America Sun, H., Liang, P., Zhu, G., Hung, W. H., Li, Y., Tai, H., Huang, C., Li, J., Meng, Y., Angell, M., Wang, C., Dai, H. 2020

    Abstract

    Potassium secondary batteries are contenders of next-generation energy storage devices owing to the much higher abundance of potassium than lithium. However, safety issues and poor cycle life of K metal battery have been key bottlenecks. Here we report an ionic liquid electrolyte comprising 1-ethyl-3-methylimidazolium chloride/AlCl3/KCl/potassium bis(fluorosulfonyl) imide for safe and high-performance batteries. The electrolyte is nonflammable and exhibits a high ionic conductivity of 13.1 mS cm-1 at room temperature. A 3.6-V battery with K anode and Prussian blue/reduced graphene oxide cathode delivers a high energy and power density of 381 and 1,350 W kg-1, respectively. The battery shows an excellent cycling stability over 820 cycles, retaining 89% of the original capacity with high Coulombic efficiencies of 99.9%. High cyclability is also achieved at elevated temperatures up to 60 °C. Uniquely, robust K, Al, F, and Cl-containing passivating interphases are afforded with this electrolyte, which is key to superior battery cycling performances.

    View details for DOI 10.1073/pnas.2012716117

    View details for PubMedID 33106405

  • High-Safety and High-Energy-Density Lithium Metal Batteries in a Novel Ionic-Liquid Electrolyte. Advanced materials (Deerfield Beach, Fla.) Sun, H., Zhu, G., Zhu, Y., Lin, M., Chen, H., Li, Y., Hung, W. H., Zhou, B., Wang, X., Bai, Y., Gu, M., Huang, C., Tai, H., Xu, X., Angell, M., Shyue, J., Dai, H. 2020: e2001741

    Abstract

    Rechargeable lithium metal batteries are next generation energy storage devices with high energy density, but face challenges in achieving high energy density, high safety, and long cycle life. Here, lithium metal batteries in a novel nonflammable ionic-liquid (IL) electrolyte composed of 1-ethyl-3-methylimidazolium (EMIm) cations and high-concentration bis(fluorosulfonyl)imide (FSI) anions, with sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a key additive are reported. The Na ion participates in the formation of hybrid passivation interphases and contributes to dendrite-free Li deposition and reversible cathode electrochemistry. The electrolyte of low viscosity allows practically useful cathode mass loading up to 16 mg cm-2 . Li anodes paired with lithium cobalt oxide (LiCoO2 ) and lithium nickel cobalt manganese oxide (LiNi0.8 Co0.1 Mn0.1 O2 , NCM 811) cathodes exhibit 99.6-99.9% Coulombic efficiencies, high discharge voltages up to 4.4 V, high specific capacity and energy density up to 199 mAh g-1 and 765 Wh kg-1 respectively, with impressive cycling performances over up to 1200 cycles. Highly stable passivation interphases formed on both electrodes in the novel IL electrolyte are the key to highly reversible lithium metal batteries, especially for Li-NMC 811 full batteries.

    View details for DOI 10.1002/adma.202001741

    View details for PubMedID 32449260

  • Electroreduction of CO2 to Formate on a Copper-Based Electrocatalyst at High Pressures with High Energy Conversion Efficiency. Journal of the American Chemical Society Li, J. n., Kuang, Y. n., Meng, Y. n., Tian, X. n., Hung, W. H., Zhang, X. n., Li, A. n., Xu, M. n., Zhou, W. n., Ku, C. S., Chiang, C. Y., Zhu, G. n., Guo, J. n., Sun, X. n., Dai, H. n. 2020

    Abstract

    Electrocatalytic CO2 reduction (CO2RR) to valuable fuels is a promising approach to mitigate energy and environmental problems, but controlling the reaction pathways and products remains challenging. Here a novel Cu2O nanoparticle film was synthesized by square-wave (SW) electrochemical redox cycling of high-purity Cu foils. The cathode afforded up to 98% Faradaic efficiency for electroreduction of CO2 to nearly pure formate under ≥45 atm CO2 in bicarbonate catholytes. When this cathode was paired with a newly developed NiFe hydroxide carbonate anode in KOH/borate anolyte, the resulting two-electrode high-pressure electrolysis cell achieved high energy conversion efficiencies of up to 55.8% stably for long-term formate production. While the high-pressure conditions drastically increased the solubility of CO2 to enhance CO2 reduction and suppress hydrogen evolution, the (111)-oriented Cu2O film was found to be important to afford nearly 100% CO2 reduction to formate. The results have implications for CO2 reduction to a single liquid product with high energy conversion efficiency.

    View details for DOI 10.1021/jacs.0c00122

    View details for PubMedID 32250611

  • Ionic Liquid Analogs of AlCl3 with Urea Derivatives as Electrolytes for Aluminum Batteries ADVANCED FUNCTIONAL MATERIALS Angell, M., Zhu, G., Lin, M., Rong, Y., Dai, H. 2019
  • A safe and non-flammable sodium metal battery based on an ionic liquid electrolyte. Nature communications Sun, H., Zhu, G., Xu, X., Liao, M., Li, Y., Angell, M., Gu, M., Zhu, Y., Hung, W. H., Li, J., Kuang, Y., Meng, Y., Lin, M., Peng, H., Dai, H. 2019; 10 (1): 3302

    Abstract

    Rechargeable sodium metal batteries with high energy density could be important to a wide range of energy applications in modern society. The pursuit of higher energy density should ideally come with high safety, a goal difficult for electrolytes based on organic solvents. Here we report a chloroaluminate ionic liquid electrolyte comprised of aluminium chloride/1-methyl-3-ethylimidazolium chloride/sodium chloride ionic liquid spiked with two important additives, ethylaluminum dichloride and 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide. This leads to the first chloroaluminate based ionic liquid electrolyte for rechargeable sodium metal battery. The obtained batteries reached voltages up to ~4V, high Coulombic efficiency up to 99.9%, and high energy and power density of ~420Whkg-1 and ~1766 W kg-1, respectively. The batteries retained over 90% of the original capacity after 700 cycles, suggesting an effective approach to sodium metal batteries with high energy/high power density, long cycle life and high safety.

    View details for DOI 10.1038/s41467-019-11102-2

    View details for PubMedID 31341162

  • An electrodeposition approach to metal/metal oxide heterostructures for active hydrogen evolution catalysts in near-neutral electrolytes NANO RESEARCH Kenney, M. J., Huang, J., Zhu, Y., Meng, Y., Xu, M., Zhu, G., Hung, W., Kuang, Y., Lin, M., Sun, X., Zhou, W., Dai, H. 2019; 12 (6): 1431–35
  • Rechargeable aluminum batteries: effects of cations in ionic liquid electrolytes RSC ADVANCES Zhu, G., Angell, M., Pan, C., Lin, M., Chen, H., Huang, C., Lin, J., Achazi, A. J., Kaghazchi, P., Hwang, B., Dai, H. 2019; 9 (20): 11322–30

    View details for DOI 10.1039/c9ra00765b

    View details for Web of Science ID 000466756100035

  • An operando X-ray diffraction study of chloroaluminate anion-graphite intercalation in aluminum batteries PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA Pan, C., Yuan, C., Zhu, G., Zhang, Q., Huang, C., Lin, M., Angell, M., Hwang, B., Kaghazchi, P., Dai, H. 2018; 115 (22): 5670–75

    Abstract

    We investigated rechargeable aluminum (Al) batteries composed of an Al negative electrode, a graphite positive electrode, and an ionic liquid (IL) electrolyte at temperatures down to -40 °C. The reversible battery discharge capacity at low temperatures could be superior to that at room temperature. In situ/operando electrochemical and synchrotron X-ray diffraction experiments combined with theoretical modeling revealed stable AlCl4-/graphite intercalation up to stage 3 at low temperatures, whereas intercalation was reversible up to stage 4 at room temperature (RT). The higher-degree anion/graphite intercalation at low temperatures affords rechargeable Al battery with higher discharge voltage (up to 2.5 V, a record for Al battery) and energy density. A remarkable cycle life of >20,000 cycles at a rate of 6C (10 minutes charge time) was achievable for Al battery operating at low temperatures, corresponding to a >50-year battery life if charged/discharged once daily.

    View details for PubMedID 29760096