Investigation of Heteroatom Doped Graphene Anode for High-Capacity Alkali Metal-Ion Batteries
Authors: Vashishth Surishi , Eswaramoorthy Muthusamy 
Published: February 2024

The drastic growth of Li-ion batteries (LIBs) in global electronic market and low crustal abundance of Li demands for more abundant alternatives such as sodium and potassium having similar electrochemical properties. Sodium-ion battery (SIB) and potassium-ion battery (PIB) can be used “side-by-side” to LIB which can help battery technology progress efficiently. 1Graphite has been a commercial anode in LIB due to its low cost, high abundance, high electrical conductivity, with a theoretical storage capacity (LiC6) of 372 mAh g-1. In contrast the utilization of graphite in SIBs and PIBs is challenging. This is due to the large radius and unstable graphite-intercalation compounds (NaC64) giving very low theoretical capacity of 30 mAh g-1. In PIBs, graphite exhibits a theoretical capacity of 279 mAh g-1 but suffers from poor stability due to huge volume expansion (60%) in fully potassiated state (KC8). Thus, focus is now shifted on to class of amorphous carbon materials such as hard carbon, soft carbon, graphene etc. with variations in micro-structures, larger interlayer spacing, and defect rich sites promoting enhanced capacity and stability even at high current densities. 2

In my presentation I will be discussing about the synthesis of heteroatom doped graphene with high charge storage and stability for LIB, SIB and PIB compared to graphite. The heteroatom doped graphene exhibits nearly 1000 mAh g-1 (LIB), 380 mAh g-1 (SIB) and 379 mAh g-1 (PIB) at a low current density of 25 mAg-1. Additionally, the elastic nature of ultrathin graphene nanosheets aids in attaining long term cyclability at 1 A g-1 with high-capacity retention of 83% for 300 cycles (LIB), 73% for 400 cycles (SIB) and 91% for 600 cycles (PIB). The enhanced stability in case of PIB, is attributed to optimizing solid electrolyte interphase (SEI) components and improving interfacial reaction kinetics at high current densities. Choice of high concentrated electrolyte (HCE) over conventional KPF6 in EC:DEC determines the nature of SEI and thereby helps in achieving cycling stability. The stability in SEI is characterized via voltage profile and understanding chemical composition by ex-situ X-ray photoelectron spectroscopy. Robust SEI in HCE is due to difference in anion structure studied by Raman spectroscopy.

Furthermore, the charge-discharge mechanism, alkali ion diffusion kinetics and structure-activity relationship of electrode materials was investigated using various techniques like cyclic voltammetry profiles at different scan rates and Galvanostatic intermittent titration technique (GITT). Additionally, deeper insights into the fundamental understanding of interfacial and bulk behavior were provided with the help of in-situ Raman spectroscopy and in-situ potentiostatic electrochemical impedance spectroscopy (PEIS) analysis. The investigation of peak area and shift in D (defect) and G (graphitic) band analyzed from in-situ Raman studies helped in understanding the evolution and reversibility of alkali ion storage behavior during charging and discharging. PEIS analysis gave us a thorough understanding of the evolution of stable SEI on charging-discharging and after cycling, which helps us to understand the long-term stability in LIB, SIB and PIB.

References:

Durmus, Y. E. et al. Side by Side Battery Technologies with Lithium-Ion Based Batteries. Adv Energy Mater
10, 2000089 (2020).

Zhang, W. et al. A Cyclized Polyacrylonitrile Anode for Alkali Metal Ion Batteries. Angewandte Chemie
133, 1375–1383 (2021).