Carbon Anode Research Articles

Engineering interleaved large and small Na4MnV(PO4)3@NC microspheres cathode towards high performance sodium ion batteries

The booming consumption of energy storage devices spontaneously accelerates the urgent development of robust cathode materials for sodium-ion batteries (SIBs). In view of this, the sodium superionic conductor Na4MnV(PO4)3 (NMVP), with considerable energy density of 425 Wh kg−1, has become the focus in SIB research. Despite this, the performance of NMVP is substantially compromised by Jahn-Teller distortion of Mn3+ ions in conjunction with inherently limited electronic conductivity. In order to address this limitation, this study introduces a series of N-doped carbon (NC) coated NMVP materials with interleaved large and small microsphere morphology. Of particular note, the optimized NMVP-NC2 shows the most excellent performance, maintaining a capacity of 65.7 mAh g−1 at 5C over 500 cycles. A full cell configuration employing an NMVP-NC2 cathode and a commercial hard carbon (HC) anode manifests commendable circular stability with a capacity of 80.7 mAh g−1 underneath 100 cycles at 1C, with an impressive 95.3 % capacity preservation. This distinctive architecture imparts the materials with a high tap density and a relatively low surface area, which is beneficial to the industrial employment. In addition, density functional theory (DFT) calculations indicate that the NC regulation significantly narrows the NMVP's bandgap and facilitates electron transfer, thereby accelerating electron/ion transport kinetics. The NC coating approach combined with large-scale spray drying tactic in this work offers a clear strategy to industrialize NMVP cathode towards high-performance SIBs.

Potassium Metal Underpotential Deposition in Crystalline Carbon of Potassium‐Ion Batteries

AbstractCarbon materials, owing to their low cost, high conductivity, and good thermal and chemical stability, have been deemed as a promising anode candidate for potassium‐ion batteries. However, anomalous low‐voltage discharge situations in crystalline carbon materials imply uncertainty in the potassium storage mechanism. Herein, an overlooked scenario, i.e., potassium metal underpotential deposition (PMUPD), is disclosed in crystalline carbon materials for the first time. The study unveils the induction of interlayer pores on desolvation and PMUPD by insights from thermodynamics, kinetics, and experimental analyses. By manipulating the cutoff voltage to utilize partial PMUPD, a novel synergistic mechanism of co‐intercalation and PMUPD is revealed. A remarkable initial coulombic efficiency of 92% and a 65% capacity retention at 30C (80 mAh g−1) are realized in crystalline carbon anode. This work provides a new insight into the potassium storage mechanism of carbon anode and contributes to further research and application of the UPD behavior in other alkaline metal ion batteries.

State change of Na clusters in hard carbon electrodes and increased capacity for Na-ion batteries achieved by heteroatom doping

Although heteroatom doping is an effective method to improve the capacity of hard carbon (HC) anodes in Na-ion batteries (NIBs), the complicated structure of HC leads to uncertainty when understanding the effects of heteroatom doping on sodium storage. This study shows the effects of phosphorus and sulfur doping to HC on sodium storage using solid-state NMR to improve the capacity of HC prepared by the carbonization of resorcinol formaldehyde (RF) resin at 1100 °C. Heteroatom doping increased the battery capacity of the HC, especially the plateau capacity, but the interlayer distance of the carbon layers in the HC did not expand considerably. 23Na solid-state NMR revealed that heteroatom doping facilitates the formation of quasi-metallic sodium clusters, thereby contributing to the plateau capacity increase. The metallicity of the sodium clusters in heteroatom-doped HC samples was controlled by the amount of doped-phosphorous. XPS and 31P NMR detected various phosphorus sites such as phosphine and phosphine oxide in the carbon structure.

Coordination engineering for iron-based hexacyanoferrate as a high-stability cathode for sodium-ion batteries

Iron-based hexacyanoferrate (Fe-HCF) are promising cathode materials for sodium-ion batteries (SIBs) due to their unique open-channel structure that facilitates fast ion transport and framework stability. However, practical implementation of SIBs has been hindered by low initial Coulombic efficiency (ICE), poor rate performance, and short lifespan. Herein, we report a coordination engineering to synthesize sodium-rich Fe-HCF as cathodes for SIBs through a uniquely designed 10-kg-scale chemical reactor. Our study systematically investigated the relationship between coordination surroundings and the electrochemical behavior. Building on this understanding, the cathode delivered a reversible capacity of 99.3 mAh g-1 at 5 C (1 C = 100 mA g-1), exceptional rate capability (51 mAh g-1 even at 100 C), long lifespan (over 15,000 times at 50 C), and a high ICE of 92.7%. A full cell comprising the Fe-HCF cathode and hard carbon (HC) anode exhibited an impressive cyclic stability with a high-capacity retention rate of 98.3% over 1,000 cycles. Meanwhile, this material can be readily scaled to the practical levels of yield. The findings underscore the potential of Fe-HCF as cathodes for SIBs and highlight the significance of controlling nucleation and morphology through coordination engineering for a sustainable energy storage system.

Modifying lignite-derived hard carbon with micron carbon tubes to improve sodium-ion storage

Lignite is a feasible raw material for the development of hard carbon anodes for sodium-ion batteries because of its high abundance and cheap cost. However, the existence of more defects in lignite-derived carbon, leads to unsatisfactory electrochemical performance as the anode of sodium-ion batteries, such as the initial Coulombic efficiency (ICE) and capacity retention rate. In this work, we introduce a preparation process of lignite-derived hard carbon using carbonized lignite and oleic acid (C9H16O2) as precursors. The micron carbon tubes (MCTs) generation on the hard carbon surface can provide additional Na+ active sites and reduce the defects, which effectively enhances the specific capacity and ICE of the anode. Benefiting the MCT modification, the hard carbon anode has a high reversible capacity of 244.8 mAh g−1 and ICE of 76.72%, which is respectively 30% and 10% higher than that of the bare hard carbon anode, this is of significance for the practical application of coal-based hard carbon in sodium-ion batteries.

Anode of Anthracite Hard Carbon Hybridized by Phenolic Epoxy Resin toward Enhanced Performance for Sodium-Ion Batteries

Anode of Anthracite Hard Carbon Hybridized by Phenolic Epoxy Resin toward Enhanced Performance for Sodium-Ion Batteries

Exploring the Impact of Lanthanum on Sodium Manganese Oxide Cathodes: Insight into Electrochemical Performance

This investigation focuses on nominally La‐doped Na0.67MnO2, exploring its structural, electrochemical, and battery characteristics for Na‐ion batteries. X‐ray diffraction analysis reveals formation of composite materials containing three distinct phases: P2‐Na0.67MnO2, NaMn8O16, and LaMnO3. The bond structures of the powders undergo scrutiny through Fourier‐transform infrared and Raman analyses, revealing dependencies on the NaO, MnO, and LaO structures. X‐ray photoelectron spectroscopy and energy‐dispersive X‐ray dot mapping analyses show that the La ions are unevenly dispersed within the samples, exhibiting a valence state of 3+. Half‐cell tests unveil similarities in redox peaks between the cyclic voltammetry analysis of La‐doped samples and P2‐type Na0.67MnO2, with a reduction in peak intensities as La content increases. Electrochemical impedance spectroscopy model analysis indicates direct influences of La content on the half‐cell's resistive elements values. The synergistic effect of composite material with multiple phases yields promising battery performances for both half and full cells. The highest initial capacity value of 208.7 mAh g−1, with a 57% capacity fade, among others, is observed, and it diminishes with increasing La content. Full cells are constructed using an electrochemically presodiated hard carbon anode, yielding a promising capacity value of 184.5 mAh g−1 for sodium‐ion battery studies.

Liquid bath-assisted combustion activation preparation of nitrogen/sulfur-doped porous carbon for sodium-ion battery applications

A liquid-bath-assisted salt-template combustion activation method has been developed to overcome the shortcomings of the conventional template method, including elaborate processes and environmental pollution. Herein, N/S double-doped porous carbon material (ECSK-15) with high specific surface area (1148.60 m2 g−1) is synthesized through it for sodium-ion batteries (SIBs). Benefitting from this approach, the number of ion diffusion channels and the ion exchange rate of the product are significantly increased. When using ether-based electrolyte, after 1000 cycles at a large current density of 2 A g−1, the reversible capacity could still be maintained at 135.60 mA h g−1. The assembled full cell exhibits a high reversible capacity of 480.49 mAh g−1 at a current rate of 0.5 A g−1. The energy density is calculated to be 204.11 Wh kg−1 at a power density of 160.71 W kg−1. This work provides a porous carbon anode material with good sodium-ion storage capacity and rate performance for application in SIBs.

Effect of Supporting Carbon Fiber Anode by Activated Coconut Carbon in the Microbial Fuel Cell Fed by Molasses Decoction from Yeast Production

A microbial fuel cell (MFC) is a bioelectrochemical system that generates electrical energy using electroactive micro-organisms. These micro-organisms convert chemical energy found in substances like wastewater into electrical energy while simultaneously treating the wastewater. Thus, MFCs serve a dual purpose, generating energy and enhancing wastewater treatment processes. Due to the high construction costs of MFCs, there is an ongoing search for alternative solutions to improve their efficiency and reduce production costs. This study aimed to improvement of MFC operation and minimize MFC costs by using anode material derived from by-products. Therefore, the proton exchange membrane (PEM) was abandoned, and a stainless steel cathode and a carbon anode were used. To improve the cell’s efficiency, a carbon fiber anode supplemented with activated coconut carbon (ACCcfA) was utilized. Micro-organisms were provided with molasses decoction (a by-product of yeast production) to supply the necessary nutrients for optimal functioning. For comparison, an anode made solely of carbon fibers (CFA) and an anode composed of activated carbon grains without carbon fibers (ACCgA) were also tested. The results indicated that the ACCcfA system achieved the highest cell voltage, power density, and COD reduction efficiency (compared to the CFA and ACCgA electrodes). Additionally, the study demonstrated that incorporating activated coconut carbon significantly enhances the performance of the MFC when powered by a by-product of yeast production.

Adding CNTs into Anthracite towards High Performance Anode Materials for Lithium Ion Batteries

AbstractCommercial graphite anodes face the problems of high preparation temperature and limited specific capacity in lithium‐ion batteries (LIBs). Amorphous carbon anode materials are prepared at low temperatures and have abundant sources and modes of preparation. As a low‐cost carbon source material, anthracite has a practical application value in storing lithium as anode electrodes of LIBs. However, the capacity is not enough to meet the present increasing demand. We added CNTs to enhance the performance of anthracite‐based carbon anodes. The addition of CNTs significantly improves the electrical properties of amorphous carbon anode materials due to their good electronic conductivity. This anthracite‐based carbon with CNTs (A−C) anode displays a specific cycling capacity of 360 mAh ⋅ g−1 at the current density of 200 mA ⋅ g−1 after 200 cycles in LIBs. We believe that the work has far‐reaching significance for improving the practicability of amorphous carbon anode materials.

Joule heating for structure reconstruction of hard carbon with superior sodium ion storage performance

Hard carbon anode for sodium ion batteries still remains many challenges including insufficient cycling life and initial Coulombic efficiency (ICE), weak rate capability and poor compatibility in common ester electrolytes. Here, we propose a Joule heating post-treatment including multifield sintering method to reconstruct the structure of hard carbon from thick graphene layers to more disordered vortex layer structure composed of thin and curved graphite-like domains. The molecular dynamics simulation and differential charge density distribution demonstrate the crucial effect of electric field in strengthening the interaction between the polar molecule groups and the graphene layer, leading to the distortion and expanding of graphene layer. This is a universal and highly efficient strategy to modify various hard carbons within minutes. The optimized hard carbon anode exhibits exceptional rate capability and cycling stability with a high retention rate of 88.4% after 15,000 cycles at 10C in ether electrolyte. It also displays remarkably improved reversible capacity, initial Coulombic efficiency ICE of 89.5% and cycling stability in ester electrolyte. It is revealed by in-situ electrochemical impedance spectroscopy and atomic force microscopy that the spontaneous formation of a thin, stable and inorganic substance-rich solid electrolyte interface layer with significantly improved mechanical property is largely responsible for the outstanding sodium-ion transport kinetics and long lifespan.

Impact of fuel starvation–induced anode carbon corrosion in proton exchange membrane fuel cells on the structure of the membrane electrode assembly and exhaust gas emissions: A quantitative case study

Although the durability of proton exchange membrane fuel cells (PEMFCs) is crucial for their broad commercial applications, current durability assessments do not encompass all operational scenarios. Startup/shut-down (SUSD) are among the most significant degradation factors in the city. To bridge this gap, we examine the phenomenon of fuel starvation, which leads to the rapid and irreversible degradation of PEMFC performance, particularly during SUSD, but has not been independently examined in the context of PEMFC durability. A quantitative methodology is used to analyze anode carbon corrosion and establish correlations with critical parameters under fuel starvation conditions. In particular, we quantify carbon loss based on (i) the composition or amount of the anode outlet gas emitted under such conditions and (ii) changes in the anode thickness at three distinct locations. The corresponding carbon losses due to 10 min of fuel starvation ((i): 212.0 μg cm−2, (ii): 189.6 ± 12.9 μg cm−2) agree well with each other. The largest decrease in the anode thickness (81.3 %) is observed near the outlet. The obtained insights provide guidance for the design of high-performance PEMFCs and the development of protective measures against the detrimental effects of fuel starvation.

Boosting Initial Coulombic Efficiency of Coal-Based Carbon Anodes with Cross-Linked Polymeric Binder for Sodium-Ion Batteries

Boosting Initial Coulombic Efficiency of Coal-Based Carbon Anodes with Cross-Linked Polymeric Binder for Sodium-Ion Batteries

Sub-minute carbonization of polymer/carbon nanotube films by microwave induction heating for ultrafast preparation of hard carbon anodes for sodium-ion batteries

Hard carbons (HCs) are excellent anode materials for sodium-ion batteries (SIBs). However, the carbonization and granulation of HC powders involve complex processes and require considerable energy. Here, we developed a facile method for manufacturing HC anodes for SIBs via a novel microwave induction heating (MIH) process for polymer/single-walled carbon nanotube (SWCNT) films. Numerical simulations solving electromagnetic field and heat transfer problems revealed the MIH mechanism; the electric current induced by the applied microwave enables direct Joule heating of the SWCNT networks in the composite film. Consequently, the composite films could be heated to the target temperatures (800–1400 °C) and free-standing HC/SWCNT anodes could be prepared by applying MIH for only 30 s. Comparative analyses confirmed that ultrafast MIH is a reliable technique for producing HC anodes and can replace conventional carbonization processes which require a high-temperature furnace. Moreover, the HC/SWCNT anodes prepared by the ultrafast MIH were successfully applied to the SIB full cells. Finally, the feasibility of MIH for scalable roll-to-roll production of HC anodes was verified through local heating tests using a circular sheet larger than a resonator.

Heterogeneous carbon coated resin-based hard carbon anode material for high-performance sodium ion batteries

Resin-based hard carbons are promising anode materials for sodium ion batteries (SIBs) due to their high storage capacity and purity. However, the low initial coulombic efficiency (ICE) still hinders their practical application. Crosslinking and high-temperature pyrolysis strategies have been demonstrated to improve ICE effectively, but the complex process and high energy consumption hinder their industrialization. This paper proposes a facile synthesis of resin-based hard carbon with a soft carbon coating strategy to improve ICE. By carbonizing commercial phenolic resin at 1150℃, hard carbon with a reversible capacity of 291.6 mAh g−1 and 82.6 % ICE was obtained. After asphalt-based soft carbon coating, the optimized sample (CHC-1150) with a heterogeneous carbon coating layer of about 8.5 nm displays a high reversible capacity and ICE of 309.8 mAh g−1 and 88.2 %. Moreover, when combined with NaFe1/3Ni1/3Mn1/3O2 cathode, the assembled 18650 cylindrical-type batteries deliver a high ICE of 84.3 %, excellent low-temperature capability and cycling stability. Additionally, the disassembly results after cycling indicate that the soft carbon layer can inhibit the decomposition of electrolytes and avoid sodium plating. These encouraging results suggest that heterogeneous carbon coating should be a promising strategy to promote the electrochemical performance of resin-based hard carbon anode materials for SIBs.

From Powder to Pouch Cell: Setting up a Sodium‐Ion Battery Reference System Based on Na3V2(PO4)3/C and Hard Carbon

At the research level, novel active materials for batteries are synthesised on a small scale, fabricated into electrodes and electrochemically characterised using each group’s established process due to the lack of standards. Recently, eminent researchers have criticised the implementation of e.g. low active material contents/electrode loadings, the use of research‐type battery cell constructions, or the lack of statistically relevant data, resulting in overstated data and thus giving misleading predictions of the key performance indicators of new battery technologies. Here, we report on the establishment of a reference system for the development of sodium‐ion batteries. Electrodes are fabricated under relevant conditions using 9.5 mg/cm² self‐synthesised Na3V2(PO4)3/C cathode active material and 3.6 mg/cm² commercially available hard carbon anode active material. It is found that different types of battery cells are more or less suitable for half‐ and/ or full‐cell testing, resulting in ir/reproducible or underestimated active material capacities. Furthermore, the influence of electrode overhang, which is relevant for upscaling, is evaluated. The demonstrator cell (TRL 4‐5) has been further characterised providing measured data on the power/energy density and thermal behaviour during rate testing up to 15 C and projections are made for its practical limits.

Anchoring Multi‐Coordinated Bismuth Metal Atom Sites on Honeycomb‐Like Carbon Rods Achieving Advanced Potassium Storage

AbstractCarbonaceous materials are recognized for their high conductivity and adaptable structures, making them potential candidates for potassium‐ion batteries (PIBs). Yet, their application has been restricted due to challenges like limited potassium storage and slow kinetics. Addressing these issues, this study presents a novel method by anchoring nitrogen‐oxygen‐coordinated bismuth metal atom sites onto honeycomb‐like carbon rods, termed Bi‐N4‐O2@HCR. This aims to enhance PIB performance by exploiting carbonaceous materials' strengths and mitigating their limitations. Through comprehensive experiments and theoretical simulations, it is found that Bi‐N4‐O2 sites enrich potassium storage and facilitate potassium ion migration, thus improving transport efficiency and reaction kinetics. The resulting anode showcased rapid and durable potassium storage, with a remarkable capacity of 190.7 mAh g−1 at 30 A g−1 and maintaining 192.2 mAh g−1 over 4200 cycles at 5 A g−1, outperforming many existing carbon anodes. Additionally, in full cell tests, it exhibited excellent rate performance and ultra‐long cycle life, sustaining up to 8000 cycles with a stable capacity of 88.9 mAh g−1 at 5 A g−1. This research underscores the significance of incorporating unique metal sites on carbon substrates to advance battery technology.

Effect of Presodiation Additive on Structural and Interfacial Stability of Hard Carbon | P2‐Na0.66Mn0.75Ni0.2Mg0.05O2 Full Cell

The compatibility between a corncob‐derived hard carbon anode and a layered oxide cathode (Na0.66Mn0.75Ni0.2Mg0.05O2), as well as the effect of presodiation via cathode additive (Na2C4O4), are investigated in a sodium‐ion full cell. Extensive physicochemical and electrochemical characterizations are performed to deeply investigate the structural and interfacial evolution of the materials in the presodiated cell, either within the single cycle or upon long‐term cycling. The use of sacrificial cathode additives is generally regarded as a method to improve full cell performance, especially when using sodium‐deficient materials. However, undesired effects upon decomposition of the sacrificial salt may arise due to the complexity of the system. In this study, it is evidenced that the presodiation changes the properties of the electrodes causing a worsening of the electrochemical performance of the cell during long‐term cycling. The surface morphology of the cathode is negatively affected by the formation of holes/cracks, while redox processes associated with structural transformations are suppressed in the voltage window of interest, with partial structural deformations occurring during activation cycles. The SEI and CEI are also affected by the formation of insulating organic species, which lead to an increased thickness and interphase resistance hampering the charge transfer kinetics of the cell.

Engineering mesoporous Na4Mn0.9Ni0.1V(PO4)3@NC microspheres cathode towards advanced sodium ion batteries

Currently, the exploitation of robust cathode materials for sodium-ion batteries (SIBs) is of critical urgency. Sodium superionic conductor (NASICON) Na4MnV(PO4)3 (NMVP) owns a decent energy density of 425 Wh kg−1 which has been regarded as a research hotspot in SIBs. Nonetheless, the performance of NMVP is greatly hindered by structural degradation due to Jahn-Teller distortions of Mn3+ and intrinsically limited electronic conductivity. In view of this, a series of Na4Mn1-xNixV(PO4)3@NC (x = 0.04, 0.1 or 0.12) denoted as NMVP, 0.04Ni-NMVP, 0.1Ni-NMVP and 0.12Ni-NMVP are facilely envisaged via the scalable spray-drying approach in this work. Notably, the optimized mesoporous 0.1Ni-NMVP reveals the most excellent cycling durability at high current rate (a capacity of 67.8 mAh g−1 at 5C over 1500 cycles with a capacity retention ratio of 73.7 %). Especially, the full cell based on 0.1Ni-NMVP cathode and commercial hard carbon (HC) anode manifests a satisfied energy density of 295 Wh kg−1 at the power density of 105.6 W kg−1. It is proved that the appropriate Ni-doping could extremely mitigate the Jahn-Teller distortion in MnO6 during cycling and significantly favor the electron/ion transportation. Besides, the N-doped carbon coating could also avoid the aggregation of NMVP microspheres and ameliorate the electronic conductivity. A reversible structural evolution including two-phase and solid-solution reactions during cycling are validated for the 0.1Ni-NMVP upon (de)sodiation based on the in-situ XRD patterns. Furthermore, density functional theory (DFT) calculations suggest the Ni-modification for NMVP leads to the reduced bandgap and boosted electron transfer, which is much beneficial to the expedited electron/ion transportation. This innovative Ni-modification protocol serves an explicit direction for engineering advanced NMVP cathode in SIBs.

Unraveling the intercorrelation between pseudo-graphitic phase and Li+/Na+ migration behavior in semicoke-based carbon anodes

Microstructural engineering is regarded as a promising option for fabricating high-performance carbon anodes. Hence, a facile solvothermal-assisted low-temperature calcination strategy was employed to modulate the microstructure of semicoke-derived carbon anodes. Owing to the effective pseudo-graphite phase modulation, the modified carbon anode exhibited a significant increase in capacity, cycling stability and ion kinetics in both lithium-ion batteries and sodium-ion batteries. Kinetic analysis and in-situ X-ray diffraction confirmed the “adsorption and intercalation” energy storage mechanism of the obtained carbon electrodes. In addition, by investigating the energy storage mechanism, we found that increasing the pseudo-graphite phase proportion played different roles in lithium and sodium ions storage. For lithium-ion storage, the pseudo-graphitic phase preferentially promotes lithium-ion transport kinetics. Conversely, during sodium-ion storage, this particular structure markedly augments the embedding capacity of sodium. Theoretical calculations demonstrate that different patterns of variation in the activation energy with the carbon layer spacing of lithium/sodium intercalation compounds lead to differences in performance enhancement. This study not only offers a low-cost approach for preparing carbon anodes enriched with a pseudo-graphitic phase, but also provides new insight into the discrepancy between lithium ion and sodium ion storage.