Elucidating the Lithium-Ion Storage Mechanism in Insertion-Available Hard Carbon with Abundant Closed Porosity: Toward a Practical Material for Batteries

Abstract

Traditionally, standard lithium-ion batteries (LIBs) are composed of a positive electrode made of metal oxides and a negative electrode made of highly crystallized graphite materials. Graphite materials, with a theoretical capacity of 372 mAh g-1, are chosen as the negative electrode because lithium-ion storage in graphite materials involves lithium-ion intercalation/de-intercalation between graphitic interlayers, a characteristic of faradaic reactions. During galvanostatic charge/discharge (GCD), long plateau regions at low voltages (e.g., 0-0.1 V (vs. Li+/Li)) resulting from multi-staged ion intercalation/de-intercalation are achieved. The low voltage of this intercalation/de-intercalation reaction contributes to enhancing the nominal voltage of LIBs, leading to a higher energy density of the battery.On the other hand, sodium-ion batteries (SIBs) have been extensively researched over the past 10 years as alternative to LIBs to compensate for the gradual scarcity of lithium metal resources. Hard carbon (HC) materials, also known as amorphous non-graphitizable carbons, were introduced to be the negative electrode material for SIBs, since most HCs exhibit very similar electrochemical responses in sodium-ion storage as lithium-ion storage in graphite materials.However, when examining the application of HC materials in lithium-ion storage, it becomes apparent that the development has been significantly limited over the past 20 years. Recent research primarily focuses on biomass-derived HCs and heteroatom-doping on these carbons. This type of HC is abundant in heteroatoms (e.g., N, P, and S) inherited from the intrinsic properties of biomass precursors. While high capacities and excellent rate capabilities are claimed for these biomass-derived HCs, the electrochemical responses of lithium-ion storage in these HCs often exhibit capacitive reactions with a completely sloping region on their GCD curves. Consequently, the miscalculation of capacities can be induced by assessing reversible capacities beyond excessively high voltages (> 1.5 V), even reaching 3 V. The appropriate working voltage window for HCs should be lower than 1.5 V to match with the positive electrodes. Thus, if reevaluating these HCs in a normal voltage window, the obtained reversible capacities are relatively small, due to the deficiency of faradaic reactions signified by the plateau region at low voltages on GCD curves. Additionally, very low initial coulombic efficiencies are often obtained for these highly defected and heteroatom-doped HCs, attributed to the vigorous consumption of electrolyte during the SEI layer formation on their defective sites. As a result, in this work, we introduce a straightforward method to fabricate hard carbon microbeads with tunable microporous structures by carbonizing cross-linked phenolic-formaldehyde (PF) resin spheres, produced through microwave-assisted suspension polymerization. The ultimate goal is to transform HC into a practical battery material for the negative electrode in LIBs, which must possess several abilities similar to graphite (i.e., reversible faradaic reactions with an obvious plateau region at low voltages on GCD curves, low surface area to suppress SEI formation, and good cycling stability). Additionally, the lithium-ion storage mechanism in HCs with varying open/closed porosity is carefully elucidated. By probing the porosity of HC with multiple gas (N2, O2, and CO2) adsorptions, a solid correlation between porous properties and electrochemical responses has been successfully established. As displayed in Figure 1, the results indicate that carbon porosity can change with carbonization temperature. With increasing temperatures, open pores are initially transformed into closed pores, and ultimately, non-porous properties are detected. The electrochemical behaviors in these HCs with distinct porosity differ significantly as demonstrated by GCD curves in Figure 2.It has been found that ultra-micro closed pores (<0.7 nm) are capable of providing confined spaces for lithium ions to be inserted/extracted, characterized as faradaic reactions. Therefore, a plateau region at low voltages can be acquired, leading to additional reversible capacities. Unlike some reported methods, such as holding at a constant voltage, charging/discharging at a very small current density, or overcharging to negative voltage regions, these faradaic reactions are easily unlocked at a current density of 50 mA g-1 in a safe voltage window of 0-0.12 V. As a result, the optimized HC delivers a total reversible capacity of 550 mAh g-1 at 50 mA g-1 in the voltage range of 0-1.5 V. The excellent rate capability and cycling stability of optimized HC are also confirmed. Furthermore, by the post-treatment with hydrogen-assisted reduction, the performance is further enhanced, achieving a reversible capacity of 574 mAh g-1 and an initial coulombic efficiency of 75%. These breakthrough outcomes provide valuable insights for the rational design of hard carbon materials. The optimized hard carbon could be a promising candidate for replacing traditional graphite materials in next-generation LIBs. Figure 1