Regulated electrochemical performance of manganese oxide cathode for potassium-ion batteries: A combined experimental and first-principles density functional theory (DFT) investigation

Bidhan Pandit; Sachin R Rondiya; Shoyebmohamad F Shaikh; Mohd Ubaidullah; Ricardo Amaral; Nelson Y Dzade; Emad S Goda; Abu Ul Hassan Sarwar Rana; Harjot Singh Gill; Tokeer Ahmad

doi:10.1016/j.jcis.2022.11.070

Regulated electrochemical performance of manganese oxide cathode for potassium-ion batteries: A combined experimental and first-principles density functional theory (DFT) investigation

J Colloid Interface Sci. 2023 Mar:633:886-896. doi: 10.1016/j.jcis.2022.11.070. Epub 2022 Nov 15.

Authors

Affiliations

¹ Department of Materials Science and Engineering and Chemical Engineering, Universidad Carlos III de Madrid, Avenida de la Universidad 30, 28911 Leganés, Madrid, Spain. Electronic address: bpandit@ing.uc3m.es.
² School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, UK; Department of Materials Engineering, Indian Institute of Science (IISc), Bengaluru 560012, Karnataka, India.
³ Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia.
⁴ Department of Energy and Mineral Engineering, Pennsylvania State University, University Park, PA 16802, United States.
⁵ School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, Wales, UK; Department of Energy and Mineral Engineering, Pennsylvania State University, University Park, PA 16802, United States.
⁶ Organic Nanomaterials Lab, Department of Chemistry, Hannam University, Daejeon 34054, Republic of Korea; Fire Protection Laboratory, National Institute of Standards, 136, Giza 12211, Egypt.
⁷ Department of Electrical and Electronic Engineering, The University of Melbourne, Parkville VIC 3010, Australia.
⁸ University Centre for Research & Development, Mechanical Department, Chandigarh University, Gharuan, Mohali, Punjab, India.
⁹ Nanochemistry Laboratory, Department of Chemistry, Jamia Millia Islamia, New Delhi 110025, India.

PMID: 36495810
DOI: 10.1016/j.jcis.2022.11.070

Abstract

Potassium-ion batteries (KIBs) are promising energy storage devices owing to their low cost, environmental-friendly, and excellent K⁺ diffusion properties as a consequence of the small Stoke's radius. The evaluation of cathode materials for KIBs, which are perhaps the most favorable substitutes to lithium-ion batteries, is of exceptional importance. Manganese dioxide (α-MnO₂) is distinguished by its tunnel structures and plenty of electroactive sites, which can host cations without causing fundamental structural breakdown. As a result of the satisfactory redox kinetics and diffusion pathways of K⁺ in the structure, α-MnO₂ nanorods cathode prepared through hydrothermal method, reversibly stores K⁺ at a fast rate with a high capacity and stability. It has a first discharge capacity of 142 mAh/g at C/20, excellent rate execution up to 5C, and a long cycling performance with a demonstration of moderate capacity retention up to 100 cycles. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) simulations confirm that the K⁺ intercalation/deintercalation occurs through 0.46 K movement between Mn^IV/Mn^III redox pairs. First-principles density functional theory (DFT) calculations predict a diffusion barrier of 0.31 eV for K⁺ through the 1D tunnel of α-MnO₂ electrode, which is low enough to promote faster electrochemical kinetics. The nanorod structure of α-MnO₂ facilitates electron conductive connection and provides a strong electrode-electrolyte interface for the cathode, resulting in a very consistent and prevalent execution cathode material for KIBs.

Keywords: Cathode; Density functional theory; Manganese oxide; Nanorods; Potassium-ion battery.