Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries

Significance Statement

Manganese dioxide (MnO2) – zinc (Zn) batteries have a rich 150 year old history dating back to its initial discovery by the famous French scientist Georges Leclanche. It once held of promise of being a breakthrough battery chemistry because of the theoretical energy density that it could store (>400Wh/L). However, the battery could not be made rechargeable because of the inherent problematic material properties of manganese dioxide. The battery could store the high energy density because of the high capacity of MnO2 (617mAh/g), which it obtained through two electron reactions (This is famously called the 2nd electron capacity). However, in trying to access the 2nd electron capacity the MnO2 would undergo deleterious reactions that would cause a breakdown in its crystal structure, which rendered the battery irreversible(not rechargeable). Hence, the chemistry was relegated to the realm of primary batteries for one time use in small applications like watch batteries, etc. This was a shame because the high energy density of these batteries were capable to be used for much larger and greener applications like electric vehicles, grid-scale storage,etc.

At the Energy Institute, Dr. Gautam G. Yadav and his team solved this 150 year old problem by tailoring the material properties of MnO2 by creating a layered structure called birnessite (δ-MnO2) intercalated with copper ions. This approach led to stabilizing the crystal structure and enhancing its electrochemical properties through its 2 electron reactions and thus, leading to its complete rechargeability with accessing the 2nd electron capacity for thousands of cycles. The promising outcome of this discovery is that this cheap(its raw materials are extremely cheap) and safe(aqueous-based) battery can be used for use large scale applications like grid-scale storage(the utilities market),etc. where the use of Li-ion batteries could be fatal because of its tendency to catch fire. In the paper, Dr. Yadav and his team have shown that very high energy densities >140Wh/L is obtained when paired with a zinc anode at 15% utilization. They also show that with modeling energy densities >250Wh/L is achievable when zinc utilization is increased to 35%.

Dr. Gautam G. Yadav’s discovery is a breakthrough in the field of alkaline batteries and this will enable cheaper, safer and energy dense aqueous-based batteries to be used for grid-scale storage applications.

Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries - Advances in Engineering

About The Author

Dr. Gautam G. Yadav is an expert materials scientist and electrochemist, working as a Senior Research Associate at the Energy Institute, City University of New York. He earned his doctoral degree in chemical engineering at Purdue University, where he specialized in synthesizing one-dimensional complex metal oxide nanowires for thermoelectric applications and lithium-ion batteries. At the Energy Institute, Dr. Yadav has led the advancement of the next generation of highly energy dense aqueous-based batteries based on manganese dioxide and zinc as a replacement for the expensive and dangerous lithium-ion batteries for grid-storage applications.

He solved the 150-year old problem of manganese dioxide irreversibility by intercalating a layered polymorph called birnessite with copper ions, which is a breakthrough in the field of alkaline batteries. This work is published in Nature Communications. The copper intercalated birnessite is able to operate for over thousands of cycles at its complete theoretical second electron capacity. Dr. Yadav has also led the efforts to make the first birnessite/zinc energy dense bipolar battery, create separator/interlayers to block detrimental zinc ions and improve the reversibility and capacity retention of the zinc anode. He is also working on materials development for other battery chemistry’s like aluminium-ion, lithium-ion and magnesium-ion.

A number of major grants have resulted from Dr. Yadav’s research and he has played a vital role in other government funded projects. Some examples are Advanced Research Projects Agency – Energy of the United States Department of Energy (ARPA-E) for GRIDS applications, New York State Energy Research and Development Authority (NYSERDA), Consolidated Edison, Inc. (Con Ed) and Sandia National Laboratories.

Dr. Yadav has authored over 12 referred articles and 13 patents. A number of his patents have been transferred to a New York-based startup company called Urban Electric Power (UEP).

Reference

Gautam G. Yadav, Joshua W. Gallaway, Damon E. Turney, Michael Nyce, Jinchao Huang, Xia Wei & Sanjoy Banerjee. Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries. Nature Communications 8, Article number: 14424 (2017).

The CUNY Energy Institute at the City College of New York, Department of Chemical Engineering, Steinman Hall, 140th Street and 160 Convent Avenue, Room 316, New York, New York 10031, USA.

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