Three-dimensional Carbon Research Articles

A rapid and scalable fabrication of flexible P/C-CNTs anodes for sodium-ion battery

Flexible sodium-ion batteries (SIBs) are a prior energy supply for the future wearable electronic devices. And red phosphorus (P) with high theoretical capacity (2596 mAh/g) is regarded as an optimal candidate for SIB anode. However, the huge volume expansion of red P during the sodiation/desodiation process deteriorates the structural integrity of electrodes, resulting in the rapid capacity fading, which hinders the successful deployment of red P in the flexible SIB anodes. Herein, we propose a rapid and scalable method to fabricate the flexible P-based electrodes, which is similar with the common blade-coating method. The three-dimensional carbon nanotubes (CNTs) matrix from monodispersed CNT solution with robust mechanical strength ensures the structural integrity of the flexible electrode during the long cyclic process. As a result, the flexible P/C-CNTs electrode using as SIB anode delivers a reversible capacity (calculated based on the whole mass of the electrodes, 35 wt% P in electrode) of 442 mA h g−1 at 0.5 A g−1 after 100 cycles, together with 83 % capacity retention. And this work could propel the practical application process of flexible SIB.

3D Porous VOx/N-Doped Carbon Nanosheet Hybrids Derived from Cross-Linked Dicyandiamide-Chitosan Hydrogels for Superior Supercapacitor Electrode Materials.

Three-dimensional porous carbon materials with moderate heteroatom-doping have been extensively investigated as promising electrode materials for energy storage. In this study, we fabricated a 3D cross-linked chitosan-dicyandiamide-VOSO4 hydrogel using a polymerization process. After pyrolysis at high temperature, 3D porous VOx/N-doped carbon nanosheet hybrids (3D VNCN) were obtained. The unique 3D porous skeleton, abundant doping elements, and presence of VOx 3D VNCN pyrolyzed at 800 °C (3D VNCN-800) ensured excellent electrochemical performance. The 3D VNCN-800 electrode exhibits a maximum specific capacitance of 408.1 F·g-1 at 1 A·g-1 current density and an admirable cycling stability with 96.8% capacitance retention after 5000 cycles. Moreover, an assembled symmetrical supercapacitor based on the 3D VNCN-800 electrode delivers a maximum energy density of 15.6 Wh·Kg-1 at a power density of 600 W·Kg-1. Our study demonstrates a potential guideline for the fabrication of porous carbon materials with 3D structure and abundant heteroatom-doping.

Self-Healing Polymer-Based Electrolyte Induced by Amorphous Three-Dimensional Carbon for High-Performance Solid-State Li Metal Batteries

Polyethylene oxide (PEO)-based solid-state electrolyte (SSE) is attractive due to its excellent adhesion with electrodes and good processability. However, PEO is easily penetrated by lithium dendrites because of its soft nature, which will result in inferior battery performance and safety issues. Here, a novel self-healing PEO-based SSE is prepared by incorporating 2 wt% amorphous three-dimensional carbon (3DC). This SSE with low electronic conductivity (in the order of 10-9 S cm-1) which is five orders of magnitude lower than its ionic conductivity (10-4 S cm-1) at 60 oC is suitable to be used in the battery. In addition, the strong adhesion between the 3DC and the PEO matrix as well as the excellent dispersion of 3DC both contribute to the self-healing ability of SSE, which will repair the cracks of SSE formed during battery cycling. Moreover, this SSE shows enhanced ionic and thermal conductivities and mechanical strength, suppressing the formation and growth of lithium dendrites. As a result, this SSE exhibits excellent electrochemical stability, achieving 5000 h of stable cycles in lithium symmetric cell (0.1 mA cm-2, 0.1 mAh cm-2) and 850 long-term stable cycles for the LFP//Li full cell at 1 C. Figure 1

F127/PDA dual-assisted fabricating high dispersed Ge nanoparticles /N-doped porous carbon composites with efficient lithium storage

Nanocrystallization and carbon composite are effective methods to solve the mechanical instability and low conductivity of Ge-based anode materials. In this work, a meaningful phenomenon is discovered that F127 can effectively disperse GeO2 polycrystalline particles, which facilitates the formation of Ge nanoparticles embedded in N-doped carbon (Ge/N-C) composites. Polydopamine (PDA) has cross-linking effect, effectively alleviating the reaggregation of GeO2 nanoparticles, and its derived N-doped carbon ensures the uniform dispersion and independent structure of Ge nanoparticles. When assessed as anode material for lithium-ion batteries (LIBs), Ge/N-C composites exhibit a high discharge capacity of 1323 mA h g−1 in the second cycle at 0.2 A g−1 and 981 mA h g−1 after 100 cycles, with a capacity retention rate of 74%. Additionally, the composites show high-rate capability of 959 mA h g−1 at 2 A g−1. The excellent lithium storage performance is attributed to that the synergistic effect between three-dimensional carbon network structure and Ge nanoparticles, which provides stable mechanical structure and abundant redox sites, suppressing volume expansion and accelerating the electrochemical reaction kinetics.

(Invited) Recent Progress in the Synthesis of Functional and Three-Dimensional Carbon Nano-Composites By Gas-Liquid Interface Plasma

Carbon nanomaterials, such as fullerene, carbon nanotubes (CNT), graphene sheets, and so forth, play indispensable roles in nanotechnology research and applications. Due to their unique self-organized nanostructures and properties, various types of applications using them are expected and have been developed. Furthermore, in recent years, heteroatom-doped carbon nano-composite materials that exhibit catalytic activity are attracting much attention as non-platinum catalysts. Especially, nitrogen (N)-doped nanographene materials are well-known to have high catalytic activity. Pyridinic-N is known as a key component to express catalytic activity [1].There are two ways to obtain nitrogen-doped carbon nanomaterials. One is the addition of N into carbon nanomaterials during their synthesis, and the other is the post-nitridation after the synthesis, which often used nitrogen plasma. Especially in the latter case, the synthesis method of nanographene itself can be divided into two types of methods. One is the direct synthesis of the powder, and the other is the exfoliating from graphene oxide (GO) or bulk graphite in physical or chemical ways. Hydrothermal treatment using microwaves is one of the effective methods for simultaneous exfoliation, three-dimensional nanopore structuring, and nitrogen addition. While electronic device applications generally need high-quality graphene sheets synthesized by epitaxial growth, or chemical vapor deposition (CVD) methods at high temperatures up to 1,000°C, some kinds of applications, such as sensors, batteries, additives to polymers, and so forth, need a large amount of nanographene power. For that purpose, a reduction of GO is well known, but the quality of the synthesized graphene is not high enough.Recently, we have established a high-speed synthesis method of nanographene materials with high crystallinity by a plasma discharge at gas-liquid interfaces with alcohol sources. By this method, a synthesis rate of nanographene over 1 mg/min and higher crystallinity of nanographene than the reduced GO have been realized. On the other hand, there is a trade-off relationship between the synthesis rate and crystallinity, when different types of alcohols were used as a feedstock gas. When ethanol,1-propanol, and 1-butanol were used, it was found that the higher synthesis rates were obtained by the higher-molecular weight alcohols, while its crystallinity was lower. In the comparison between hexane (C6H14) and hexanol (C6H13OH), in the case of hexane, the synthesis rate is about twice as high as that in the case of hexanol, but the crystallinity is lowered. These results indicate that this trade-off relationship is attributed to a ratio of carbon (C) and oxygen (O) atoms. O-related radicals (O, OH, etc.) in plasma could have etching effects of amorphous or low-crystallinity carbon components. Actually, according to the results of plasma diagnostic measurements and residual liquid analyses, it was found that crystallinity of nanographene materials degraded with decrease in OH intensity in plasma. Furthermore, small radicals such as C2 and CHx contribute to the synthesis of nanographene rather than by-products with a six-membered ring structure. Furthermore, we have also found functionalization and structural control of nanographene materials by additive agents to alcohol sources at in-liquid plasma processes. Using an iron phthalocyanine with ethanol, size of carbon nanosheets increased up to micrometer. And they showed excellent catalytic characteristics thorough 4-electron reduction pathway. According to the verification results of dependence on synthesis conditions such as the type of additive, such the catalytic activity is induced by pyridinic C-N bonds. In the case of this way, to increase pyridinic C-N bonds and improve catalytic performance, iron phthalocyanine is much better than Hemin, even which also included Fe and N. These knowledges obtained in this study will open the way to the next-generation green energy solutions, such as high-performance catalytic electrode for the fuel cell.[1] D. Guo, R. Shibuya, C. Akiba, S. Saji, T. Kondo, and J. Nakamura. Science 351 (2016) 361–365.[2] J. Wang, W. Wu, H. Kondo, T. Fan, H. Zhou, Nanotechnology, NANO-132006.R1 (2022), online.[3] T. Hagino, H. Kondo, K. Ishikawa, H. Kano, M. Sekine, M. Hori, Appl. Phys. Express 5 (2012) 035101.[4] T. Amano, H. Kondo, K. Ishikawa, T. Tsutsumi, K. Takeda, M. Hiramatsu, M. Sekine, M. Hori, Appl. Phys. Express 11 (2017) 015102.[5] H. Kondo, R. Hamaji, T. Amano, K. Ishikawa, M. Sekine, M. Hiramatsu, M. Hori, Plasma Process. Polym. 19, (2022) 2100203.

Electrogenerative Process as an Alternate Technique for Nickel Recovery from Its Sulphate Solution at Low Concentration

In this study, a static batch reactor equipped with three-dimensional (3-D) carbon felt (CF) as cathode material was fully optimized to recover a low nickel concentration from its sulphate solution. Nickel recovery was performed using several nickel concentrations ranging from 50, 100, 250, 400 and 500 mg/L. Moreover, within 30 min of electrogenerative operation, it was discovered that the recovery of nickel achieved > 90 % in acidic conditions. At last, the deposition of nickel into CF was further investigated by scanning electron microscopy (SEM) to visualize the surface morphology of nickel on CF.

Cobalt-loaded three-dimensional mesoporous carbon as sulfur host for lithium‑sulfur batteries

The practical application of lithium‑sulfur batteries has been limited due to the poor electrical conductivity of sulfur, the shuttling effect of polysulfide, and the slow redox kinetics of sulfur species. Designing a multifunctional sulfur host with good conductivity, strong adsorption, and high catalytic activity could effectively address these issues. In this work, the cobalt nanoparticles-loaded three-dimensional mesoporous carbon (Co-TDMC) composite was developed as the multifunctional host for lithium‑sulfur batteries. Due to its large specific surface area (2404.7 m2 g−1), abundant mesopores, and good-catalytic performance, the composite could effectively contain sulfur, adsorb polysulfide, and accelerates the conversion reaction of sulfur species. Therefore, when Co-TDMC was used as the sulfur carrier, the sulfur cathode had an excellent initial discharge capacity (1403 mAh g−1 at 0.1C) and a good rate performance (780.2 mAh g−1 at 1C)·In addition, it has excellent long-term cycling stability (a low decay rate of 0.06 % per cycle during 500 cycles at 1C). This work provides a feasible strategy for improving the cycle stability of lithium‑sulfur batteries.

Graphitized Carbon-Coated Iron Fluoride Nanocavities for Enhanced Kinetics of Multielectron Cathode Conversion Reactions.

As for the conversion-type iron fluoride (FeF3) cathode material with multielectron reactions for lithium-ion batteries (LIBs), sluggish reaction kinetics and low electrical conductivity pose certain limitations for the long-lasting reversible conversion processes. Herein, the three-dimensional porous nitrogen-doped carbon matrix in situ anchoring FeF3 nanocavities coated by graphitized carbon (FeF3/GC) are rationally prepared. Through the Kirkendall effect, the low-temperature fluorination of NF3 enables the resultant hollow FeF3 nanoparticles to possess a large number of lithium storage cavities and outer graphitized carbon structure, further effectively buffering the expansion of volume. The FeF3/GC cathode delivers a superior discharge capacity of 504.2 mAh g-1 after 1200 cycles at 1000 mA g-1, with a capacity decay rate of only 0.01% per cycle. Even at a rate of 5000 mA g-1, the composite cathode still delivers a discharge capacity of 309.6 mAh g-1. Impressively, the existence of graphitized carbon and the short Li+ diffusion length ensure fast electron/ion transfer, which significantly enhances the conversion reaction kinetics. This study aims to provide a promising strategy for the efficiency enhancement of multielectron cathode conversion reactions for LIBs.

On-Surface Carbon Nitride Growth from Polymerization of 2,5,8-Triazido-s-heptazine.

Carbon nitrides have recently come into focus for photo- and thermal catalysis, both as support materials for metal nanoparticles as well as photocatalysts themselves. While many approaches for the synthesis of three-dimensional carbon nitride materials are available, only top-down approaches by exfoliation of powders lead to thin-film flakes of this inherently two-dimensional material. Here, we describe an in situ on-surface synthesis of monolayer 2D carbon nitride films as a first step toward precise combination with other 2D materials. Starting with a single monomer precursor, we show that 2,5,8-triazido-s-heptazine can be evaporated intact, deposited on a single crystalline Au(111) or graphite support, and activated via azide decomposition and subsequent coupling to form a covalent polyheptazine network. We demonstrate that the activation can occur in three pathways, via electrons (X-ray illumination), via photons (UV illumination), and thermally. Our work paves the way to coat materials with extended carbon nitride networks that are, as we show, stable under ambient conditions.

Ultrafine red phosphorus confined in reasonably designed pitch-based carbon matrix built of well-interconnected carbon nanosheets for high-performance lithium and potassium storage

Red phosphorus has been well-recognized as promising anode materials for lithium-ion batteries (LIBs) and potassium-ion batteries (PIBs) due to its extremely high theoretical capacity and low cost. However, the huge volume change and poor electric conductivity severely limit its further practical application. Herein, the nanoscale ultrafine red phosphorus has been successfully confined in a three-dimensional pitch-based porous carbon skeleton composed of well-interconnected carbon nanosheets through the vaporization-condensation method. Except for the traditional requirement of high electric conductivity and stable mechanical stability, the micropores and small mesopores in the porous carbon matrix centered at 1 to 3 nm and the abundant amount of oxygen-containing functional groups are also beneficial for the high loading and dispersion of red phosphorus. As anode for LIBs, the composite exhibits high reversible discharge capacities of 968 mAh g−1, excellent rate capabilities of 593 mAh g−1 at 2 A g−1, and long cycle performance of 557 mAh g−1 at 2 A g−1. More impressively, as the anode for PIBs, the composite presents a high reversible capacity of 661 mAh g−1 and a stable capacity of 312 mAh g−1 at 0.5 A g−1 for 500 cycles with a capacity retention up to 84.3%. This work not only sheds light on the structure design of carbon hosts with specific pore structure but also open an avenue for high value-added utilization of coal tar pitch.

Directional manipulation of electron transfer in copper/nitrogen doped carbon by Schottky barrier for efficient anodic hydrazine oxidation and cathodic oxygen reduction

Development of bifunctional hydrazine oxidation and oxygen reduction electrocatalysts with high activity and stability is of great significance for the implementation of direct hydrazine fuel cells. Combining zero-dimensional metal nanoparticles with three-dimensional nitrogen-doped carbon nanosheets is an attractive strategy for balancing performance and cost. However, the precise construction of these composites remains a significant challenge, and thorough study of their interaction mechanisms is lacking. Herein, the CuNPs/CuSA-NPCF catalyst was constructed by anchoring copper nanoparticles on a three-dimensional nitrogen-doped porous carbon nanosheet framework through coordination of polyvinyl pyrrolidone and copper ions. The Schottky barrier of metal–semiconductor matched the Fermi level of the rectifying contact, thus enabling directional electron transfer. The resulting electron-deficient Cu nanoparticles surface exhibited Lewis acidity, which was beneficial to adsorption of hydrazine molecule. While the electron-enriched Cu–N4/carbon surface improved the adsorption of oxygen molecule, and accelerated electron supply from Cu-N4 active sites to various oxygen intermediates. The CuNPs/CuSA-NPCF Mott-Schottky catalyst exhibited excellent catalytic activity for hydrazine oxidation reaction and oxygen reduction reaction in an alkaline media. The directional manipulation of electron transfer in heterogeneous materials was an attractive universal synthesis method, providing new approach for the preparation of efficient and stable hydrazine fuel cell catalysts.

T-C20 Carbon: A Three-Dimensional Topological Carbon Allotrope Constructed from Zigzag Carbon Chains

Carbon materials have attracted much attention due to their excellent electronic structure and topological properties. By linking the zigzag carbon chains with carbon dimers, we propose a new stable three-dimensional (3D) carbon allotrope: T-C20 carbon. This carbon structure has four nodal lines in the Brillouin zone (BZ) protected by mirror symmetry. Moreover, T-C20 carbon exhibits strong anisotropic optical properties and strong absorption in the whole infrared, visible and ultraviolet regions, which is suitable for the broadband photodetector. Our research provides a new idea for the construction of novel 3D topological carbon allotropes.

Three-dimensional hierarchical carbon architecture of porous carbon derived from cross-linked polycyclophosphazenes as supercapacitor electrode material

Three-dimensional hierarchical carbon architecture of porous carbon derived from cross-linked polycyclophosphazenes as supercapacitor electrode material

Fe-Fe3N composite nitrogen-doped carbon framework: Multi-dimensional cross-linked structure boosting performance for the oxygen reduction reaction electrocatalysis and zinc-air batteries

Taking into consideration the sluggish kinetics of the oxygen reduction reaction (ORR) and the distinct three-phase environment of the electrode, it is crucial to optimize the surface structure of the electrocatalyst. This study employs a sol–gel approach to synthesize a Fe-Fe3N composite three-dimensional nitrogen-doped carbon framework (Fe-Fe3N/3DNC) and utilize it as the electrocatalyst for a zinc-air battery. The material possesses a multi-dimensional cross-linking frame structure comprised of one-dimensional and two-dimensional crosslinks, which effectively reduce the diffusion mean-free path of oxygen. Moreover, the iron–nitrogen site and nitrogen-rich carbon substrate both exhibit exceptional electrocatalytic activity for ORR. Consequently, a conventional liquid zinc-air battery utilizing this material as the air cathode catalyst exhibits a maximum power density of 242.8 mW cm−2, surpassing that of commercial Pt/C. Additionally, DFT calculations further confirm the crucial enhancing influence of Fe3N in the Fe-Fe3N/3DNC composite on ORR. This research provides valuable insights for the development of ORR electrocatalysts with outstanding efficiency.

Three-dimensional carbon network-supported black phosphorus-cobalt heterojunctions: An efficient electrocatalyst for high-rate oxygen evolution

Black phosphorus (BP), as a burgeoning two-dimensional material, has shown good electrocatalytic activity due to its unique electronic structure and abundant active sites.However, the presence of lone pair electrons in black phosphorus leads to its poor stability and rapid degradation in an oxygen/water environment, which greatly limits its practical application. Herein, BP-Co heterojunctions were synthesized on carbon nanotube@nitrogen-doped carbon (BP-Co/CNT@NC) by the pyrolysis of ZnCo-zeolitic imidazolate frameworks and subsequent solvothermal treatment. The BP-Co Schottky junction improved the electrocatalytic stability of BP, modulated its electronic structure, improved its conductivity and electron transfer during the electrocatalytic reaction. Density functional theory calculation was used to confirm the electron transfer and redistribution at the interface between BP and Co, which constructed an oppositely charged region and formed a strong built-in field. Energy band configuration analysis revealed a narrowed band gap because of the formation of BP-Co Schottky junction. Consequently, the optimized BP-Co/CNT@NC exhibited a superior oxygen evolution reaction (OER) performance, a low overpotential of 370 mV@100 mA/cm2, with a small Tafel slope of 40 mV/dec and good long-term stability. Particularly, the catalyst has an excellent OER performance at the high current density of 100–400 mA/cm2. This strategy improves the stability of BP electrocatalysts and strengthens their utilization in electrocatalytic applications.

Three-Dimensional Carbon Networks Decorated with Co Nanocatalysts as Multifunctional Interlayers for a High-Performance Lithium–Sulfur Battery

Three-Dimensional Carbon Networks Decorated with Co Nanocatalysts as Multifunctional Interlayers for a High-Performance Lithium–Sulfur Battery

Porous CoO/carbon foam composites synthesized by solvothermal method for supercapacitor and enhanced microwave absorption applications

Composite materials comprising porous carbon foam and transition metal oxides exhibit significant potential for applications as supercapacitor electrodes and electromagnetic microwave absorbers. In this work, N-doped three-dimensional carbon foam was obtained by carbonizing melamine foam, and subsequently, a solvothermal method was used to construct a 0D/3D structure by integrating CoO nanoparticles with the three-dimensional carbon foam. The carbon foam serves dual purpose as a growth substrate and a conductive framework, effectively enhancing the electronic conductivity between the components and mitigating issues related to CoO nanoparticle aggregation. Due to the synergistic effect of pseudocapacitance and double-layer capacitance, CoO/CF exhibits enhanced supercapacitor performance, demonstrating an outstanding specific capacitance of 221 F g−1 at 1 A g−1, and surpassing that of individual component. The assembled asymmetric supercapacitor achieves a satisfactory energy density of 28.8 Wh kg−1 at a power density of 804.3 W kg−1, and retains 80.3 % of its initial capacitance after 5000 cycles at 10 A g−1. Furthermore, the microstructure was designed by the combination of carbon foam's excellent dielectric loss and CoO's magnetic loss compensating for the magnetic loss deficiency of carbon foam, thereby significantly enhancing the composite's capacity for electromagnetic wave absorption. At a thickness of 3 mm, the composite attains a minimum RL value of −14.1 dB at 14 GHz, with an effective absorption frequency width of 2.1 GHz. This well-designed and adjustable composite strategy holds great promise for applications in the fields of supercapacitors and microwave absorption.

Disulfide bond cross-linked three-dimensional graphitic carbon nitride nanocomposites with glutathione responsive fluorescence for cancer-cell specific bioimaging

The polymeric graphitic carbon nitride (g-C3N4) nanomaterials with non-toxicity, high stability, and photoluminescence property have promising application in bioimaging and biosensing. In this work, smart three-dimensional (3D) disulfide bond cross-linked g-C3N4 (CL-g-C3N4) nanocomposites with glutathione (GSH)-responsive fluorescence property were designed and developed for cancer cell-specific imaging. The g-C3N4 layered nanosheets with an average lateral size of 80–120 nm and mean thickness of ca. 0.5–1.0 nm were fabricated and used as building blocks. By combining several g-C3N4 nanosheets with non-fluorescent redox-sensitive disulfide bond-contained cross-linker, CL-g-C3N4 nanocomposites with a hydrodynamic particle size of ca. 270.5 nm were synthesized. The fluorescence of the CL-g-C3N4 nanocomposites was initially quenched due to the assembly of 2D g-C3N4 nanosheets into 3D structured nanocomposite caused by the crosslinking process. However, upon stirring them in a GSH solution with a concentration of 2 mM, which simulates the content in the cytoplasm of cells, the fluorescence was recovered to 89.3 % of its original intensity. This recovery was achieved through a thiol-disulfide exchange reaction, highlighting the GSH-responsive fluorescence recovery property of the nanocomposites. The cellular uptake traced images of CL-g-C3N4 in human cervix carcinoma (HeLa) cancer cells exhibited almost 3.5 times higher fluorescence intensity than that in human embryonic kidney (HEK 293 T) healthy cells owing to higher GSH concentration in cancer cells than that in healthy cells. The constructed CL-g-C3N4 nanocomposites should hold great promise as a fluorescence detector of cancer cells for early cancer diagnose.

A bimetallic sulfide Co9S8/MoS2/C heterojunction in a three-dimensional carbon structure for increasing sodium ion storage

A bimetallic sulfide Co9S8/MoS2/C heterojunction in a three-dimensional carbon structure for increasing sodium ion storage

Prediction of a three-dimensional carbon allotrope moC12 with one-dimensional metallicity, superconductivity and mechanical anisotropy

Prediction of a three-dimensional carbon allotrope moC12 with one-dimensional metallicity, superconductivity and mechanical anisotropy