ABSTRACT
Biomass-derived carbon materials are gaining attention for their environmental and economic advantages in waste resource recovery, particularly for their potential as high-energy materials for alkali metal ion storage. However, ensuring the reliability of secondary battery anodes remains a significant hurdle. Here, we report Areca Catechu sheath-inner part derived carbon (referred to as ASIC) as a high-performance anode for both rechargeable Li-ion (LIBs) and Na-ion batteries (SIBs). We explore the microstructure and electrochemical performance of ASIC materials synthesized at various pyrolysis temperatures ranging from 700 to 1400 °C. ASIC-9, pyrolyzed at 900 °C, exhibits multilayer stacked sheets with the highest specific surface area, and the least lateral size and stacking height. ASIC-14, pyrolyzed at 1400 °C, demonstrates the most ordered carbon structure with the least defect concentration and the highest stacking height and an increased lateral size. ASIC-9 achieves the highest capacities (676 mAh/g at 0.134C) and rate performance (94 mAh/g at 13.4C) for hosting Li+ ions, while ASIC-14 exhibits superior electrochemical performance for hosting Na+ ions, maintaining a high specific capacity after 300 cycles with over 99.5% Coulombic efficiency. This comprehensive understanding of structure-property relationships paves the way for the practical utilization of biomass-derived carbon in various battery applications.
ABSTRACT
Hard carbon (HC) is a promising anode candidate for Na-ion batteries (NIBs) because of its excellent Na-storage performance, abundance, and low cost. However, a precise understanding of its Na-storage behavior remains elusive. Herein, based on the D2O/H2SO4-based TMS results collected on charged/discharged state HC electrodes, detailed Na-storage mechanisms (the Na-storage states and active sites in different voltage regions), specific SEI dynamic evolution process (formation, rupture, regeneration and loss), and irreversible capacity contribution (dead Na0, NaH, etc.) were elucidated. Moreover, by employing the online electrochemical mass spectrometry (OEMS) to monitor the gassing behavior of HC-Na half-cell during the overdischarging process, a surprising rehydrogen evolution reaction (re-HER) process at around 0.02 V vs Na+/Na was identified, indicating the occurrence of Na-plating above 0 V vs Na+/Na. Additionally, the typical fluorine ethylene carbonate (FEC) additive was demonstrated to reduce the accumulation of dead Na0 and inhibit the re-HER process triggered by plated Na.
ABSTRACT
The closed pores play a critical role in improving the sodium storage capacity of hard carbon (HC) anode, however, their formation mechanism as well as the efficient modulation strategy at molecular level in the polymer-derived HCs is still lacking. In this work, the steric hindrance effect has been proposed to create closed pores in the polymer-derived HCs for the first time through grafting the aromatic rings within and between the main chains in the precursor. The experimental data and theoretical calculation demonstrate that steric-hindrance effect from the aromatic ring side group can increase backbone rigidity and the internal free volumes in the polymer precursor, which can prevent the over graphitization and facilitate the formation of closed pores during the carbonization process. As a result, the as-prepared HC anode exhibits a remarkably enhanced discharge capacity of 340.3 mAh/g at 0.1 C, improved rate performance (210.7 mAh/g at 5 C) as well as boosted cycling stability (86.4% over 1000 cycles at 2C). This work provides a new insight into the formation mechanisms of closed pores via steric hindrance engineering, which can shed light on the development of high-performance polymer-derived HC anode for sodium-ion batteries.
ABSTRACT
Lignite, as one of the coal materials, has been considered a promising precursor for hard carbon anodes in sodium-ion batteries (SIBs) owing to its low cost and high carbon yield. Nevertheless, hard carbon directly derived from lignite pyrolysis typically exhibits highly ordered microstructure with narrow interlayer spacing and relatively unreactive interfacial properties, owing to the abundance of polycyclic aromatic hydrocarbons and inert aromatic rings within its molecular composition. Herein, an innovative demineralization activating strategy is established to simultaneously modulate the interfacial properties and the microstructure of lignite-derived carbon for the development of high-performance SIBs. Demineralization process not only creates numerous void spaces in the matrix of lignite precursor to assist aromatic hydrocarbon rearrangement, thereby reducing the ordering and expanding interlayer spacing, but also exposes more interfacial oxygen-containing functional groups to effectively increasing the sodium storage active sites. As a result, the optimal demineralized lignite-derived hard carbon (DLHC 1300) delivers a high reversible capacity of 335.6 mAh g-1 at 30 mA g-1, superior rate performance of 246.3 mAh g-1 at 6 A g-1 and nearly 100 % capacity retention after 1100 cycles at 1A g-1. Furthermore, the optimized DLHC 1300 material functions as an outstanding anode in sodium ion full cells. This work significantly advances the development of low-cost, high-performance commercial hard carbon anodes for SIBs.
ABSTRACT
Hard carbon materials have shown promising potential for sodium-ion storage due to accommodating larger sodium ions. However, as for lithium-ion storage, the challenge lies in tuning the high lithiation plateau capacities, which impacts the overall energy density. Here, hard carbon microspheres (HCM) are prepared by tailoring the cross-linked polysaccharide, establishing a comprehensive methodology to obtain high-performance lithium-ion batteries (LIBs) with long plateau capacities. The "adsorption-intercalation mechanism" for lithium storage is revealed combining in situ Raman characterization and ex situ nuclear magnetic resonance spectroscopy. The optimized HCM possesses reduced defect content, enriched graphitic microcrystalline, and low specific surface area, which is beneficial for fast lithium storage. Therefore, HCM demonstrates a high reversible capacity of 537 mAh g-1 with a significant low-voltage plateau capacity ratio of 55%, high initial Coulombic efficiency, and outstanding rate performance (152 mAh g-1 at 10 A g-1). Moreover, the full cell (HCM||LiCoO2) delivers outstanding fast-charging capability (4 min charge to 80% at 10 C) and impressive energy density of 393 Wh kg-1. Additionally, 80% reversible capacity can be delivered under -40 °C with competitive cycling stability. This work provides in-depth insights into the rational design of hard carbon structures with extended low-voltage plateau capacity for high energy LIBs.
ABSTRACT
Hard carbon (HC) is a promising anode material for sodium-ion batteries. However, the intrinsic relationship between the closed pores/surface groups and sodium storage performance has been unclear, leading to difficulties in targeted regulation. In this study, renewable tannin extracts were used as raw materials to prepare HC anodes with abundant tunable closed pores and carbonyl groups through a pyrolytic modulation strategy. Combining ex situ characterizations reveals that closed pores and carbonyl groups are regulated by the pyrolytic process. Further, it is demonstrated that the plateau region is mainly contributed by the closed pores; highly stable fluorine-rich solid electrolyte interphase compositions are produced through carbonyl-induced interfacial catalysis. The optimized HC anode displays good cycling stability, exhibiting a high reversible capacity (360.96 mAh g-1) at 30 mA g-1 and capacity retention of up to 94% after 500 cycles at 1 A g-1. Moreover, the full battery assembled with Na3V2(PO4)3/C demonstrates a stable cycling performance. These findings provide a fresh knowledge of the structural design of high-performance HC anode materials and the mechanism of sodium storage in HC.
ABSTRACT
Sodium-ion batteries (SIBs) have significant potential for applications in portable electric vehicles and intermittent renewable energy storage due to their relatively low cost. Currently, hard carbon (HC) materials are considered commercially viable anode materials for SIBs due to their advantages, including larger capacity, low cost, low operating voltage, and inimitable microstructure. Among these materials, renewable biomass-derived hard carbon anodes are commonly used in SIBs. However, the reports about biomass hard carbon from basic research to industrial applications are very rare. In this paper, we focus on the research progress of biomass-derived hard carbon materials from the following perspectives: (1) sodium storage mechanisms in hard carbon; (2) optimization strategies for hard carbon materials encompassing design, synthesis, heteroatom doping, material compounding, electrolyte modulation, and presodiation; (3) classification of different biomass-derived hard carbon materials based on precursor source, a comparison of their properties, and a discussion on the effects of different biomass sources on hard carbon material properties; (4) challenges and strategies for practical of biomass-derived hard carbon anode in SIBs; and (5) an overview of the current industrialization of biomass-derived hard carbon anodes. Finally, we present the challenges, strategies, and prospects for the future development of biomass-derived hard carbon materials.
ABSTRACT
Hard carbon anode demonstrates exceptional potential in sodium-ion batteries due to their cost-effectivenss and superior plateau capacity. However, the proximity of the plateau capacity to the cut-off voltage of battery operation and the premature cut-off voltage response caused by polarization at high rates greatly limit the exploitation of plateau capacities, raising big concerns about inferior rate performance of high-plateau-capacity hard carbon. In this work, a facile pre-oxidation strategy is proposed for fabricating lignin-derived hard carbon. Both high-plateau capacity and sodiation kinetics are significantly enhanced due to the introduction of expanded pseudo-graphitic domains and high-speed closed pores. Impressively, the optimized hard carbon exhibits an increased reversible capacity from 252.1 to 302.0 mAh g-1, alongside superior rate performance (174.7 mAh g-1 at 5 C) and stable cyclability over 500 cycles. This study paves a low-cost and effective pathway to modulate the microstructure of biomass-derived hard carbon materials for facilitating plateau sodium storage kinetics.
ABSTRACT
A cost-effective chemical prelithiation solution, which consists of Li+, polyaromatic hydrocarbon (PAH), and solvent, is developed for a model hard carbon (HC) electrode. Naphthalene and methyl-substituted naphthalene PAHs, namely 2-methylnaphthalene and 1-methylnaphthalene, are first compared. Grafting an electron-donating methyl group onto the benzene ring can decrease electron affinity and thus reduce the redox potential, which is validated by density functional theory calculations. Ethylene glycol dimethyl ether (G1), diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether solvents are then compared. The G1 solution has the highest conductivity and least steric hindrance, and thus the 1-methylnaphthalene/G1 solution shows superior prelithiation capability. In addition, the effects of the interaction time between Li+ and 1-methylnaphthalene in G1 solvent on the electrochemical properties of a prelithiated HC electrode are investigated. Nuclear magnetic resonance data confirm that 10-h aging is needed to achieve a stable solution coordination state and thus optimal prelithiation efficacy. It is also found that appropriate prelithiation creates a more Li+-conducing and robust solid-electrolyte interphase, improving the rate capability and cycling stability of the HC electrode.
ABSTRACT
Given the merits of abundant resource, low cost and high electrochemical activity, hard carbons have been regarded as one of the most commercializable anode material for sodium-ion batteries (SIBs). However, poor rate capability is one of the main obstacles that severely hinder its further development. In addition, the relationships between preparation method, material structure and electrochemical performance have not been clearly elaborated. Herein, a simple but effective strategy is proposed to accurately construct the multiple structural features in hard carbon via adjusting the components of precursors. Through detailed physical characterization of the hard carbons derived from different regulation steps, and further combined with in-situ Raman and galvanostatic intermittent titration technique (GITT) analysis, the network of multiple relationships between preparation method, microstructure, sodium storage behavior and electrochemical performance have been successfully established. Simultaneously, exceptional rate capability about 108.8â mAh g-1 at 8â A g-1 have been achieved from RHC sample with high reversible capacity and desirable initial Coulombic efficiency (ICE). Additionally, the practical applications can be extended to cylindrical battery with excellent cycle behaviors. Such facile approach can provide guidance for large-scale production of high-performance hard carbons and provides the possibility of building practical SIBs with high energy density and durability.
ABSTRACT
Phenolic resin (PF) is considered a promising precursor of hard carbon (HC) for advanced-performance anodes in sodium-ion batteries (SIBs) because of its facile designability and high residual carbon yield. However, understanding how the structure of PF precursors influences sodium storage in their derived HC remains a significant challenge. Herein, the microstructure of HC is controlled by the degree of cross-linking of resorcinol-benzaldehyde (RB) resin. We reveal that robust molecular cross-linking in RB resin induced by hydrothermal treatment promotes closed-pore formation in the derived HC. The mechanism is devised for the decomposition of a highly cross-linked RB three-dimensional network into randomly stacked short-range graphitic microcrystals during high-temperature carbonization, contributing to the abundant closed pores in the derived HC. In addition, the high cross-linking degree of RB resin endows its derived HC with a small-sized spherical morphology and large interlayer spacing, which improves the rate performance of HC. Consequently, the optimized hydrothermal treatment HC anode shows a higher specific capacity of 372.7 mAh g-1 and better rate performance than the HC anode without hydrothermal treatment (276.0 mAh g-1). This strategy can provide feasible molecular cross-linking engineering for the development of closed pores in PF-based HC toward enhanced sodium storage.
ABSTRACT
Sodium-ion batteries (SIBs) are emerging as a viable alternative to lithium-ion batteries, reducing the reliance on scarce transition metals. Converting agricultural biomass into SIB anodes can remarkably enhance sustainability in both the agriculture and battery industries. However, the complex and costly synthesis and unsatisfactory electrochemical performance of biomass-derived hard carbon have hindered its further development. Herein, we employed a hydrothermally assisted carbonization process that converts switchgrass to battery-grade hard carbon capable of efficient Na-ion storage. The hydrothermal pretreatment effectively removed hemicellulose and impurities (e.g., lipids and ashes), creating thermally stable precursors suitable to produce hard carbon via carbonization. The elimination of hemicellulose and impurities contributes to a reduced surface area and lower oxygen content. With the modifications, the initial Coulombic efficiency (ICE) and cycling stability are improved concurrently. The optimized hard carbon showcased a high reversible specific capacity of 313.4 mAh g-1 at 100 mA g-1, a commendable ICE of 84.8%, and excellent cycling stability with a capacity retention of 308.4 mAh g-1 after 100 cycles. In short, this research introduces a cost-effective method for producing anode materials for SIBs and highlights a sustainable pathway for biomass utilization, underscoring mutual benefits for the energy and agricultural sectors.
ABSTRACT
Cellulose nanocrystals (CNCs) are currently of great interest for many applications, such as energy storage and nanocomposites, because of their natural abundance. A number of carbonization studies have reported abnormal graphitization behavior of CNCs, although cellulose is generally known as a precursor for hard carbon (nongraphitizable carbon). Herein, we report a spray-freeze-drying (SFD) method for CNCs and a subsequent carbonization study to ascertain the difference in the structural development between the amorphous and crystalline phases. The morphological observation by high-resolution transmission electron microscopy of the carbonized SFD-CNC clearly shows that the amorphous and crystalline phases of CNC are attributed to the formation of hard and soft carbon, respectively. The results of a reactive molecular dynamics (RMD) study also show that the amorphous cellulose phase leads to the formation of fewer carbon ring structures, indicative of hard carbon. In contrast, the pristine crystalline cellulose phase has a higher density and thermal stability, resulting in limited molecular relaxation and the formation of a highly crystalline graphitic structure (soft carbon).
ABSTRACT
A sodium bis(fluorosulfonyl)imide (NaFSI)-based multifunctional electrolyte is developed by partially replacing NaPF6 salt in the electrolyte to improve the wide temperature range working capability of NaNi1/3Fe1/3Mn1/3O2/hard carbon (NNFM111/HC) sodium-ion batteries (SIBs). The capacity retention of the SIBs with NaFSI-NaPF6 dual salt electrolyte increases from 47.2 % to 75.5 % after 250 cycles at 25 °C, and from 51.0 % to 82.3 % after 80 cycles at 45 °C, and the 1â C discharge capacity retention at the low temperature of -20 °C also increases 26.8 %. In the single salt system, NaPF6 effectively passivate the aluminum foil and NaFSI passivate the electrode/electrolyte interface. The synergistic effect of NaPF6 and NaFSI greatly improves the battery performance in a wide temperature range. This NaFSI-based dual salt electrolyte also effectively overcomes the flaws when the SIBs using NaFSI or NaPF6 independently, and makes it more suitable for SIBs, indicating promising prospects in the commercial application of NNFM111/HC SIBs.
ABSTRACT
The phenol-formaldehyde (PF) resin is an economical precursor for spherical hard carbon (HC) anodes for sodium-ion batteries (SIBs). However, achieving precise molecular-level control of PF-based HC microspheres, particularly for optimizing ion transport microstructure, is challenging. Here, a sodium linoleate (SL)-assisted strategy is proposed to enable molecular-level engineering of PF-based HC microspheres. PF microspheres are synthesized through the polymerization of 3-aminophenol and formaldehyde, initially forming oxazine rings and then undergoing ring-opening polymerization to create a macromolecular network. SL functions as both a surfactant to control microsphere size and a catalyst to enhance ring-opening polymerization and increase polymerization of PF resin. These modifications lead to reduced microsphere diameter, increased interlayer spacing, enhanced graphitization, and significantly improved electron and ion transfer. The synthesized HC microspheres exhibit a remarkable reversible capacity of 337 mAh/g, maintaining 96.9 mAh/g even at a high current density of 5.0 A/g. Furthermore, the full cell demonstrates a high capacity of 150 mAh/g, an energy density of 125.3 Wh kg-1, an impressive initial coulombic efficiency (ICE) of 930.3% at 1 A/g, and remarkable long-term stability over 3000 cycles. This study highlights the potential of surfactant-assisted molecular-level engineering in customizing HC microspheres for advanced SIBs.
ABSTRACT
Resin-derived hard carbons have shown great advantages in serving as promising anode materials for sodium-ion batteries due to their flexible microstructure tunability. However, it remains a daunting challenge to rationally regulate the pseudo-graphitic crystallite and defect of hard carbon toward advanced sodium storage performance. Herein, a molecular engineering strategy is demonstrated to modulate the cross-linking degree of phenolic resin and thus optimize the microstructure of hard carbon. Remarkably, the resorcinol endows resin with a moderate cross-linking degree, which can finely tune the pseudo-graphitic structure with enlarged interlayer spacing and restricted surface defects. As a consequence, the optimal hard carbon delivers a notable reversible capacity of 334.3 mAh g-1 at 0.02 A g-1, a high initial Coulombic efficiency of 82.1%, superior rate performance of 103.7 mAh g-1 at 2 A g-1, and excellent cycling durability over 5000 cycles. Furthermore, kinetic analysis and in situ Raman spectroscopy are performed to reveal the electrochemical advantage and sodium storage mechanism. This study fundamentally sheds light on the molecular design of resin-based hard carbons to advance sodium energy for scale-up applications.
ABSTRACT
Biomass-derived porous carbon materials are meaningful to employ as a hard carbon precursor for anode materials of sodium-ion batteries (SIBs) from a sustainability perspective. Here, a straightforward approach is proposed to develop rich closed pores in pinenut-derived carbon, with the aim of improving Na+ plateau storage by adjusting the pyrolysis temperature. The optimized sample, namely the pinenut-derived carbon at 1300 °C, demonstrates remarkable reversible specific capacity of 278 mAh g-1, along with a high initial Coulomb efficiency of 85% and robust cycling stability (with a capacity retention of 89% after 800 cycles at 0.2 A g-1). In situ and ex situ analyses unveil that the developed closed pores play a significant role in enhancing the plateau capacity, providing compelling evidence for the "adsorption-filling" mechanism. Moreover, the corresponding full-cell achieves a high energy density of 245.7 Wh kg-1 (based on the total weight of both electrode active materials) and exhibits outstanding rate capability (191.4 mAh g-1 at 3 A g-1).
ABSTRACT
Lithium oxides (Li2O) possess a considerable theoretical capacity, rendering them highly promising as cathodic pre-lithiation additives. However, its decomposition voltage exceeds the charging cut-off voltage of most cathode materials, hindering its direct use as a cathode sacrificial additive. Herein, we design a facile and safe method to reduce the decomposition energy of Li2O at room temperature to offset the irreversible capacity loss by using a core-shell structured Li2O-reduced graphene oxide (rGO)-polyethylene glycol (PEG) composite (denoted as Li2O-rGO-PEG). The graphene oxide (GO) was heat-treated to remove oxygen functional groups to synthesize rGO, and then reacted with Li2O to form a Li2O-rGO composite. According to the DFT calculations, the density of states at the Fermi level of Li2O-rGO becomes continuous and features a metallic nature, which significantly improves the electrical conductivity of Li2O and facilitates electron conduction that modify the delithiation potential of Li2O. PEG was used to enhance the cohesive force between rGO and Li2O and to protect Li2O from atmospheric contamination. Moreover, in order to demonstrate the excellent pre-lithiation ability of Li2O-rGO-PEG composite, hard carbon (HC) with low initial coulombic efficiency (ICE) was used as the anode. In the application of LFP (Li2O)/HC full cell, Li2O was decomposed to Li+ to effectively improve the initial charge capacity from 149.7 to 200 mAh/g and discharge capacity from 104.2 to 147.5 mAh/g, which are 33.6 % and 41.6 % higher than those of the pristine LFP/HC full cell, respectively. The cathode pre-lithiation method proposed in this work is simple and environmentally friendly. The successful utilization of Li2O as a pre-lithiation additive effectively addressed the issue of low initial coulombic efficiency of the HC, indicating excellent prospects for practical applications.
ABSTRACT
Closed pores play a crucial role in improving the low-voltage (<0.1 V) plateau capacity of hard carbon anodes for sodium-ion batteries (SIBs). However, the lack of simple and effective closed-pore construction strategies, as well as the unclear closed-pore formation mechanism, has severely hindered the development of high plateau capacity hard carbon anodes. Herein, we present an effective closed-pore construction strategy by one-step pyrolysis of zinc gluconate (ZG) and elucidate the corresponding mechanism of closed-pore formation. The closed-pore formation mechanism during the pyrolysis of ZG mainly involves (i) the precipitation of ZnO nanoparticles and the ZnO etching on carbon under 1100 °C to generate open pores of 0.45-4 nm and (ii) the development of graphitic domains and the shrinkage of the partial open pores at 1100-1500 °C to convert the open pores to closed pores. Benefiting from the considerable closed-pore content and suitable microstructure, the optimized hard carbon achieves an ultrahigh reversible specific capacity of 481.5 mA h g-1 and an extraordinary plateau capacity of 389 mA h g-1 for use as the anode of SIBs. Additionally, some in situ and ex situ characterizations demonstrate that the high-voltage slope capacity and the low-voltage plateau capacity stem from the adsorption of Na+ at the defect sites and Na-cluster formation in closed pores, respectively.
ABSTRACT
Hard carbon as a negative electrode material for sodium-ion batteries (SIBs) has great commercial potential and has been widely studied. The sodium-ion intercalation in graphite domains and the filling of closed pores in the low voltage platform region still remain a subject of controversy. We have successfully constructed hard carbon materials with a pseudo-graphitic structure by using polymerizable p-phenylenediamine and dichloromethane as carbon sources. This was achieved by a halogenated amination reaction and oxidative polymerization. It was found that the capacity of hard carbon materials mainly originates from intercalation into graphite domains. The study found that the prepared hard carbon could store 339.33 mAh g-1 of sodium in a reversible way at a current density of 25 mA g-1, and it had an initial coulomb efficiency of 80.23%. It even maintained a reversible sodium storage capacity of 125.53 mAh g-1 at a high current density of 12.8 A g-1. Based on the analysis of hard carbon structure and electrochemical performance, it was shown that the materials conform with an "adsorption-intercalation" mechanism for sodium storage.