Soft Carbon Research Articles

High-rate soft carbon anode for lithium storage: from modified pitch molecular structure to ordered carbon microcrystals

High-rate soft carbon anode for lithium storage: from modified pitch molecular structure to ordered carbon microcrystals

Biomimetic surface design enables a resilient solid electrolyte interphase for high-performance anodes

Surface coating presents an effective methodology for mitigating the detrimental effects of large volume changes inherent to high-capacity anode materials (e.g. Si, SiOx). However, designs often prioritize the protection of internal active particles, inadvertently neglecting the intricate interplay between the coating layer and the external electrolyte which exhibits profound influences on the solid electrolyte interphases (SEIs). Inspired by the extracellular polymeric substance (EPS) protecting biological cells (e.g. yeast) from predation and chemical damages, we prepare a conducting polymer-based EPS system (CP-EPS) on a surface bilayer comprising soft carbon membranes and compact graphene walls, constructing the biomimetic cellular structure. The CP-EPS chemically interacts with electrolyte catalyzing the symbiosis of integrated LiF-enriched SEIs and physically provide sufficient resilience for SEIs. This resilient SEIs offer excellent reaction kinetics and roughness which protects the structural integrity of the particle and itself from pulverization and excessive SEI thickening. The prepared SiOx anode delivers a superior average coulombic efficiency of 99.4% over 200 cycles at 0.5C and a high reversible capacity of 730 mAh g-1 after 300 cycles at 2C.

Comparative Analysis of Graphitization Characteristics in Bamboo and Oak Charcoals for Secondary Battery Anodes

When compared to natural graphite, artificial graphite has advantages such a longer cycle life, faster charging rates, and better performance. However, the process of producing it, which frequently uses coal, raises questions about the impact on the environment and the depletion of resources. Eco-friendly, wood-based graphite must be developed in order to solve these problems. This study assessed and investigated the characteristics of charcoals derived from bamboo and oak which were utilized to produce graphite. After heating to 1500 °C at 10 K/min, 86.87 wt% of oak charcoal and 88.33 wt% of bamboo charcoal remained, indicating a yield of more than 85% when charcoal was graphitized. Depending on the species of wood, different-sized pores showed different shapes as the graphitization process advanced, as revealed by SEM surface analyses. The carbon atoms seen in the XRD crystal development changed into graphite crystals when heated to 2400 °C, and the isotropic peaks vanished. Bamboo charcoal has a higher degree of crystallinity than other wood-based charcoals, such as oak charcoal, which is made up of turbostratic graphite, according to Raman spectroscopic research. Lithium-ion batteries employ bamboo charcoal as their anode material. At this point, the values for soft carbon were determined to be 196 mAh/g and for hard carbon to be 168 mAh/g at a current density of 0.02 A/g.

Synergistic plasma and platinum catalysts interactions in CO2 reforming of propane at room temperature: The role of supports

This study investigates the synergistic impact of plasma and catalyst in a hybrid non-thermal plasma system integrated with 1 wt% Pt catalysts supported on diverse catalyst supports (γ-Al2O3, SBA-15, HZSM-5, CeO2, TiO2, and multi-wall carbon nanotube (CNT)) at ambient conditions in dry reforming of propane (DRP). To optimize the reaction, the impact of in-situ plasma reduction time was investigated over the Pt/Al2O3 catalyst at varying durations before the DRP reaction. The most favorable catalytic performance was observed at a reduction time of 60 min due to having the highest surface area (284 m2/g), which might result in smaller Pt particle size, and the effective reduction of oxidation states to Pt0. A comparison of reduction sources also revealed that the plasma-reduced catalyst outperformed the other, which was attributed to the agglomeration of Pt active sites during the thermal reduction process. The chemo-physical properties of different catalysts directly affected the plasma characteristics and catalytic performance. Pt/Al2O3 exhibited the highest performance, attributed to having the smallest mean Pt particle size (0.94 nm) and highest discharge power (13.97 W), effective capacitance (1.41 nF), and charge transfer (0.34 μC) during DRP reaction, leading to a 13 % and 15 % increase in CO2 and C3H8 conversions, respectively, compared to plasma-only mode. The catalytic performance showed that the synergy of catalysts with higher basic sites and plasma characteristics, along with smaller Pt particle size, resulted in high reactant conversion and syngas selectivity. Binary HRTEM images also indicated the presence of more soft carbon (coke) in the pore channels of the spent Pt/HZSM-5 catalyst than in spent Pt/Al2O3.

Zn Doping Strategy to Suppress the Jahn-Teller Effect to Stabilize Mn-Based Layered Oxide Cathode toward High-Performance Potassium Ion Batteries.

In the research report of cathode of potassium ion battery, Mn-based layered structural oxides have attracted the researcher's attention because of its good energy density and high specific rate capacity. However, the Jahn-Teller effect is the main limiting factor for their development. It leads to the expansion and deactivation of Mn-based layered metal oxides during cycling for a long time. Therefore, mitigation of the Jahn-Teller effect is considered a useful measure to enhance the electrochemical capability of Mn-based layered oxide. In this paper, an R3m-type K0.4Mn0.7Co0.25Zn0.05O2 cathode material is designed through a Zn doping strategy. X-ray diffraction techniques and electrochemical tests verified that the Jahn-Teller effect is effectively mitigated. High performance is achieved in the rate capacity test with 113 mAh g-1 at 50mA g-1. Comparison with similar materials in recent years has demonstrated its superiority, leading rate performance among Mn-based metal oxides reported in recent years. The practical feasibility is verified in the assembled full cell with soft carbon in anode materials and K0.4Mn0.7Co0.25Zn0.05O2 as cathode. In the full cell rate test, 104.8 mAh g-1 discharging capacity is achieved at 50mA g-1 current density.

Effect of introducing oxygen into ethylene tar pitches on their carbonaceous products

Ethylene tar is a prospective precursor for preparing carbonaceous materials, which is regard-ed as a representative soft carbon material after carbonization. However, the introduction of oxygen can influence the morphology of the final carbonaceous materials. For the introduction of oxygen, dealkylation and dehydrogenation will be promoted and the molecules can be linked more effectively. For the subsequent carbonization, the biphenyl structures caused by the deoxygenation via the elimination of CO2, as well as the reserved aromatic ether bonds, can facilitate the strong cross-linking, which will restrain the movement of the carbon layers and the formation of the graphitic structures. After the graphitization treatment at 2800 oC, the oxidized pitch can lead to short-range ordered and long-range unordered structures, while the sample without oxidation can result in long-range ordered graphitic structures. It can be proved that a simple oxidation-carbonization treatment can transform ethylene tar into hard carbon structures.

Electrochemical Performance of Coal-Based Needle Coke Anode for Lithium Ion Batteries

Lithium-ion capacitors (LICs) with the capability of high energy and high power are considered to be attractive for advanced energy storage applications. However, the design and fabrication of suitable electrode materials with desirab-le properties by a facile approach using cost-effective precursors are still a great challenge. In this work, we have utilized needle cokes, an commercial carbon material with high carbon content and soft carbon structure, as a single carbon source for anode material. A lithium-ion battery fabricated using four kinds of needle cokes exhibits a maximum high energy density of 1357mAhg-1. Systematic characterization analysis demonstrates that unique characteristics of the green coke including large interlayer spacing, turbostratic and disordered microstructures that are composed of surface defects, nanopores or voids, and graphitic domains. That contribute synergistically to the outstanding performance of the needle coke-based LIC. More importantly, anode materials from a single source is an effective way for high value-added utilization of needle coke at the commercial level.

Remarkable performance of Co3O4 anode coated with hard-soft carbon 2D nanosheets prepared from single pavement petroleum asphalt precursor

Incorporating extraneous carbonaceous materials to coat transitional metal oxide (TMO) anodes emerges as a viable strategy to mitigate the pulverization of TMO anode during Li-ion insertion/extraction processes. Herein, hard-soft carbon coated Co3O4 (HC-SC@Co3O4) composites were synthesized by employing a facile NaCl-mediated pyrolysis with Co(NO3)2·6 H2O as the oxide precursor and pavement petroleum asphalt as the single hard-soft carbon source. Microscopic structure characterizations revealed that HC-SC@Co3O4 exhibited a core-shell structure with a fluffy nanoflower-like S/O co-doped carbon shell. Benefiting from its distinctive coating structure, the HC-SC@Co3O4 anode demonstrated remarkable cycling stability and significant initial coulombic efficiency (ICE) of 71 %, after 150 cycles at 100 mA g−1, it still maintained a capacity of 742 mAh g−1. Moreover, introduction of soft carbon delivered outstanding rate capability upon HC-SC@Co3O4 anode, evidenced by discharge capacities of 1108 and 571 mA h g−1 at 100 and 1000 mA g−1, respectively. This study not only presents the potential to effectively solve the challenge of TMO anodes in lithium-ion batteries (LIBs), but also introduces an economically and environmentally approach for the efficient utilization of pavement petroleum asphalt.

A Review of Carbon Anode Materials for Sodium-Ion Batteries: Key Materials, Sodium-Storage Mechanisms, Applications, and Large-Scale Design Principles.

Sodium-ion batteries (SIBs) have been proposed as a potential substitute for commercial lithium-ion batteries due to their excellent storage performance and cost-effectiveness. However, due to the substantial radius of sodium ions, there is an urgent need to develop anode materials with exemplary electrochemical characteristics, thereby enabling the fabrication of sodium-ion batteries with high energy density and rapid dynamics. Carbon materials are highly valued in the energy-storage field due to their diverse structures, low cost, and high reliability. This review comprehensively summarizes the typical structure; energy-storage mechanisms; and current development status of various carbon-based anode materials for SIBs, such as hard carbon, soft carbon, graphite, graphene, carbon nanotubes (CNTs), and porous carbon materials. This review also provides an overview of the current status and future development of related companies for sodium-ion batteries. Furthermore, it offers a summary and outlook on the challenges and opportunities associated with the design principles and large-scale production of carbon materials with high-energy-density requirements. This review offers an avenue for exploring outstanding improvement strategies for carbon materials, which can provide guidance for future application and research.

Carbon coating engineering enhances the stability of graphite anode in potassium ion batteries

Graphite forms reversible potassium-graphite intercalation compounds electrochemically. Graphite anode possesses a high reversible specific capacity (279 mAh g−1) and an optimal low potential platform, rendering it an ideal anode material for potassium-ion batteries. However, the intercalation of K+ ions in graphite causes a bulk volume expansion of up to 61%, resulting in irreversible damage to the structure of graphite, which leads to inferior cycling stability. In this paper, surface-oxidized graphite (OG) with reduced particle size and increased defect densities was obtained by mechanical ball milling and chemical oxidation. Composites of soft carbon-coated OG (OG@PC) were prepared by soft carbon coating. The soft carbon coating can alleviate the bulk expansion caused by K+ intercalation/deintercalation in OG, thus slowing down the destruction of the crystalline structure of graphite after multiple charging/discharging cycles. OG@PC exhibits increased reversible specific capacity from 267 mAh g−1 to 314 mAh g−1 compared with pristine graphite at a current density of 0.05 A g−1. Moreover, at a high current density of 0.5 A g−1, a reversible specific capacity of 213 mAh g−1 was achieved after 200 cycles. This work investigates simple surface carbon coating strategies to improve the cycling stability of a graphite anode of potassium-ion batteries.

Validation of dual-energy CT-based composition analysis using fresh animal tissues and composition-optimized tissue equivalent samples

Objective. Proton therapy allows for highly conformal dose deposition, but is sensitive to range uncertainties. Several approaches currently under development measure composition-dependent secondary radiation to monitor the delivered proton range in-vivo. To fully utilize these methods, an estimate of the elemental composition of the patient’s tissue is often needed. Approach. A published dual-energy computed tomography (DECT)-based composition-extraction algorithm was validated against reference compositions obtained with two independent methods. For this purpose, a set of phantoms containing either fresh porcine tissue or tissue-mimicking samples with known, realistic compositions were imaged with a CT scanner at two different energies. Then, the prompt gamma-ray (PG) signal during proton irradiation was measured with a PG detector prototype. The PG workflow used pre-calculated Monte Carlo simulations to obtain an optimized estimate of the sample’s carbon and oxygen contents. The compositions were also assessed with chemical combustion analysis (CCA), and the stopping-power ratio (SPR) was measured with a multi-layer ionization chamber. The DECT images were used to calculate SPR-, density- and elemental composition maps, and to assign voxel-wise compositions from a selection of human tissues. For a more comprehensive set of reference compositions, the original selection was extended by 135 additional tissues, corresponding to spongiosa, high-density bones and low-density tissues. Results. The root-mean-square error for the soft tissue carbon and oxygen content was 8.5 wt% and 9.5 wt% relative to the CCA result and 2.1 wt% and 10.3 wt% relative to the PG result. The phosphorous and calcium content were predicted within 0.4 wt% and 1.1 wt% of the CCA results, respectively. The largest discrepancies were encountered in samples whose composition deviated the most from tabulated compositions or that were more inhomogeneous. Significance. Overall, DECT-based composition estimations of relevant elements were in equal or better agreement with the ground truth than the established SECT-approach and could contribute to in-vivo dose verification measurements.

Cesium-doped manganese-based Prussian blue analogue as a high-efficiency cathode material for potassium-ion batteries

Prussian blue analogues (PBAs) are regarded as promising cathode materials for potassium-ion batteries (PIBs) owing to their low cost and high reversible capacity. Compared to other PBAs, potassium manganese hexacyanoferrate (KMnHCF) stands out for its superior capacity and operating voltage. However, Jahn-Teller effect of Mn3+ and the structural collapse caused by potassium ion insertion/extraction still affect the structural stability and electrochemical performance of this material. Herein, a green and efficient synthesis method is adopted to substitute potassium ions in KMnHCF with an appropriate amount of cesium ions to form a column effect. Cesium-doped KMnHCF (Cs-KMnHCF) mitigates the irreversible structural damage caused by potassiation/depotassiation and the Jahn-Teller effect, thereby improving the cycling stability. In addition, it widens the lattice channels, reduces the diffusion barrier of potassium ions, and optimizes the diffusion kinetics. By rationally controlling the doping amount of Cs+, the obtained K1.71Cs0.05Mn[Fe(CN)6]0.95·0.05·0.88H2O exhibits remarkable electrochemical performance, with an initial discharge capacity of 137.6 mA h g−1 at a current density of 20 mA g−1 and a capacity retention of 89.6% after 600 cycles at 200 mA g−1. More importantly, when assembled with a pitch-derived soft carbon anode, the full cell manifests excellent cycle stability and rate performance. This work is expected to provide a highly efficient cathode material for the practical application of PIBs.

Soft carbon filled in expanded graphite layer pores for superior fast-charging lithium-ion batteries

The slow kinetics and lithium deposition of graphite anode are considered the key limitations of fast-charging lithium-ion batteries. Expanded graphite has shown tremendous potential for the improvement of rate performance due to its massive active sites released and lifted lithium storage platform. However, the risk of structural collapse caused by fast charging will reduce the cycling life of the expanded graphite anode. Herein, this study designed a stable structure of expanded graphite by filling its layer pores with pitch-derived soft carbon (EGC). The honeycomb-like EGC is a great fast-charging candidate material with rich active sites, enlarged ion transport channels, and efficient ion transport interfaces. As the experimental and simulation results, the EGC electrode demonstrated significantly fast lithium-ions storage kinetics and durable long cycle life, compared to commercial fast-charging graphite anode. Notably, the EGC//LiNi0.8Co0.1Mn0.1O2 full cell delivered a superior fast-charging and stability performance (near 20 min charging for 80 % State of Charge). The simple multifunctional modification strategy for graphite anode in this work provides a new approach for superior fast-charging lithium-ion batteries.

Effect of carbonization methods on graphitization of soft and hard carbons

Pressurized carbonization is known to improve carbon content and create textural changes in resultant carbon compared to conventional (atmospheric) carbonization. However, further studies investigating the impact of these carbonization methods on the graphitic quality of the carbon precursors have not been explored extensively. This study investigates the influence of carbonization methods on the graphitization behavior of soft and hard carbons using a three-model system: phenolic resole (hard carbon), polyvinyl chloride (PVC) (soft carbon), and a 50:50 blend of resole and PVC. Carbonization was conducted under autogenic pressure (AGP) and atmospheric pressure (APP) at 500 °C for 5 h, followed by high-temperature treatment at varying temperatures. Various techniques, including X-ray diffraction and Raman spectroscopy showed hard carbon precursors exhibited improved properties under AGP carbonization such as larger crystallite size, sharp crystalline peaks, lower ID/IG ratio, and narrow G-full width half-maximum, an indication of improved crystallinity by lowering amorphous phase at high temperature. For soft carbon precursors, the method of carbonization did not impact the graphitization level. The most significant finding was the enhanced crystalline nature observed in hard carbon under AGP conditions, without the need for any catalyst. It shows the influence of pressure on improving the crystallinity of hard carbon precursors.

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.

Insight into the configuration of hard-soft carbon composites for high performance sodium-ion batteries

Hard carbon materials are considered suitable anode materials for sodium-ion batteries due to their abundant defect sites and large interlayer distance, which are respectively beneficial to the adsorption/desorption and insertion/extraction behaviors of Na+ during the electrochemical process. However, the poor electrical conductivity resulting from the intrinsic short-range ordered structure in the carbon skeleton and limited active sites significantly hinders their electrochemical performance. Herein, hard and soft carbon composites with various configurations are developed using a layer-by-layer coating method with SiO2 nanospheres as templates. These composites, including the hard carbon coated soft carbon composite structure (SC@HC), soft carbon coated hard carbon composite structure (HC@SC), and uniformly mixed soft and hard carbon composites (HSC), are prepared through confined-carbonization under the outermost SiO2 layer. The resulting hollow nanospheres possess ultra-small diameters (approximately 50 nm), ultra-thin wall thicknesses (5-6 nm), and different hard/soft carbon layer arrangements. Evaluation of sodium storage properties showed that the combination of soft and hard carbon outperformed pure soft or hard carbon, with HC@SC configuration offering materials with larger interlayer spacing, higher defect concentration, and a more complete conductive network. This enhances sodium storage capacity (293 mAh g-1@1 A g-1) and rate performance (242 mAh g-1@5 A g-1). The findings of this study present a novel approach to designing soft and hard carbon composites for high-performance sodium-ion batteries.

Si anode with high initial Coulombic efficiency, long cycle life, and superior rate capability by integrated utilization of graphene and pitch-based carbon

A variety of strategies have been developed to enhance the cycling stability of Si-based anodes in lithium-ion batteries. Although significant progress has been made in enhancing the cycling stability of Si-based anodes, the low initial Coulombic efficiency (ICE) remains a significant challenge to their commercial application. Herein, pitch-based carbon (C) coated Si nanoparticles (NPs) were wrapped by graphene (G) to obtain Si@C/G composite with a small specific surface area of 11.3 m2 g−1, resulting in a high ICE of 91.2% at 500 mA g−1. Moreover, the integrated utilization of graphene and soft carbon derived from the low-cost petroleum pitch strongly promotes the electrical conductivity, structure stability, and reaction kinetics of Si NPs. Consequently, the synthesized Si@C/G with a Si loading of 54.7% delivers large reversible capacity (1191 mAh g−1 at 500 mA g−1), long cycle life over 200 cycles (a capacity retention of 87.1%), and superior rate capability (952 mAh g−1 at 1500 mA g−1). When coupled with a homemade LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode in a full cell, it exhibits a promising cycling stability for 200 cycles. This work presents an innovative approach for the manufacture of Si-based anode materials with commercial application.

Preparation of Hard–Soft Carbon via Co-Carbonization for the Enhanced Plateau Capacity of Sodium-Ion Batteries

Preparation of Hard–Soft Carbon via Co-Carbonization for the Enhanced Plateau Capacity of Sodium-Ion Batteries

Structural and magnetic properties of nitrogen-doped carbon materials derived from an ionic liquid precursor

In this report, effects of pyrolysis conditions on the structure and magnetic properties of nitrogen-doped graphitic carbon materials prepared from 1-Buthyl-3-methyl imidazolium tricyano methanide ( [BMIm] [TCM]) ionic liquids(ILs) were investigated. It was found that nitrogen-containing graphitic carbon was formed under pyrolysis temperature of 400 °C or higher. Under the experimental conditions, the maximum nitrogen content of the obtained sample was C4N1.10 at a pyrolysis temperature of 400 °C and it was found that the nitrogen content in the obtained samples decreased with increasing pyrolysis temperature. Ferromagnetism was not observed in all the obtained samples to 2 K. From the value of the orbital diamagnetic susceptibility and XRD, it was found that the obtained sample had the structural characteristics of soft carbon.

Dendrite-Free All-Solid-State Lithium Metal Batteries by In Situ Phase Transformation of the Soft Carbon-Li3N Interface Layer.

The accelerated formation of lithium dendrites has considerably impeded the advancement and practical deployment of all-solid-state lithium metal batteries (ASSLMBs). In this study, a soft carbon (SC)-Li3N interface layer was developed with both ionic and electronic conductivity, for which the in situ lithiation reaction not only lithiated SC into LiC6 with good electronic/ionic conductivity but also successfully transformed the mixed-phase Li3N into pure-phase β-Li3N with a high ionic conductivity/ion diffusion coefficient and stability to lithium metal. The mixed conductive interface layer facilitates fast Li+ transport at the interface and induces the homogeneous deposition of lithium metal inside it. This effectively inhibits the formation of lithium dendrites and greatly improves the performance of the ASSLMB. The ASSLMB assembled with the SC-Li3N interface layer exhibits high areal capacity (15 mA h cm-2), high current density (7.5 mA cm-2), and long cycle life (6000 cycles). These results indicate that this interface layer has great potential for practical applications in high-energy-density ASSLMBs.