Enhanced Performance of Ultra-Microporous Hard Carbon Spheres as Anode in Half /Full Cells for Sodium-ion Batteries through Optimized Carbonate Ester Electrolytes

Symposium:

EN05: Emerging Materials for Electrochemical Energy Storage Devices—Degradation andFailure Characterization—From Composition, Structure and Interfaces to Deployed Systems

Title: Enhanced Performance of Ultra-Microporous Hard Carbon Spheres as Anode in Half /Full Cells for Sodium-ion Batteries through Optimized Carbonate Ester Electrolytes.

Author(s): Nagmani, Sreeraj Puravankara 

Presented @ 2022, MRS Spring Meeting

Abstract:

Sodium-ion batteries (SIBs) draw great attention for promising next-generation stationary energy storage systems. In the last two decades, many novel materials have been proposed as the anode for the application in SIBs.¹ Carbon-based anode materials have played a significant role for all alkali-ion-based batteries, due to low-cost fabrication, the abundance of precursors, and exclusively tunable mechanical and electronic properties.² However, the low working potential of carbon anode leads to unstable solid electrolyte interface (SEI) film and dendrite formation during cycling.³ Also, huge irreversible loss especially during an initial cycle and lower initial faradaic efficiency (IFE) becomes critical to optimize the electrode/electrolyte interface to boost the overall battery performance. SIBs commercialization demands better “3-RC features such as reversible capacity, rate capability, and retention of capacity”. It stimulates to explore electrolytes system to enhance 3-RC features in both half-cell and full-cells configuration using hard carbon based anode.

Herein, we report ultramicroporous hard carbon microspheres (HCMS) derived from sucrose via microwave-assisted solvothermal reaction as anode for SIBs. The HCMS with larger interlayer spacing in graphitic domains and ultra-micropores assists it in delivering excellent 3-RC features yet reported for hard carbons derived from sugar-based carbon precursors through electrolyte optimization of carbonate esters (EC: PC, EC: DEC, EC: DMC).^2,4 The HCMS with 1M NaClO₄ salt in EC: PC electrolyte delivered the best reversible capacity of 385 mAhg^-1 and 265 mAhg^-1 at a current density of 30 mAg^-1 and 300 mAg^-1, respectively. It exhibits the capacity retention of 85.8 % after 100 cycles and 66.3 % after 500 cycles in a half-cell. A full-cell fabricated with HCMS-PC anode and NVP cathode delivered a reversible capacity of 81 mAhg^-1 and 48 mAhg^-1 at a current density of 30 mAg^-1 and 300 mA g^-1, respectively. The high reversible storage capacity with low IIRL, better cyclic stability, with excellent rate performance from 30 mAg^-1 to 3000 mAg^- 1 make HCMS the best sugar-based HC as anode materials for SIBs.

References:

(1)      Zhang, H.; Hasa, I.; Passerini, S. Beyond Insertion for Na-Ion Batteries: Nanostructured Alloying and Conversion Anode Materials. Adv. Energy Mater. 2018, 8 (17). https://doi.org/10.1002/aenm.201702582.

(2)    Nagmani.; Puravankara, S. Insights into the Plateau Capacity Dependence on the Rate Performance and Cycling Stability of a Superior Hard Carbon Microsphere Anode for Sodium-Ion Batteries. ACS Appl. Energy Mater. 2020, 3 (10), 10045–10052. https://doi.org/10.1021/acsaem.0c01750.

(3)      Xu, K. Electrolytes and Interphases in Li-Ion Batteries and Beyond. Chem. Rev. 2014, 114 (23), 11503–11618. https://doi.org/10.1021/cr500003w.

(4)      Subramanyan, K.; Lee, Y. S.; Aravindan, V. Impact of Carbonate-Based Electrolytes on the Electrochemical Activity of Carbon-Coated Na₃V₂(PO₄)₂F₃ Cathode in Full-Cell Assembly with Hard Carbon Anode. Journal of Colloid and Interface Science. 2021, pp 51–59. https://doi.org/10.1016/j.jcis.2020.08.043.