Closed Pore Structure Research Articles

Construction of Microporous Structure in Hard Carbon via Adjustable Zn Salt Templates for High-Performance Sodium-Ion Batteries

Template method is an effective strategy for the construction of microporous structure in hard carbons. However, the introduction of templates will inevitably affect the original structure of hard carbon, making it necessary to develop an adjustable template for the high sodium storage property of Sodium-ion battery anodes. Herein, we propose an effective strategy of developing size-controlled ZnO microcrystal in precursor carbon by zinc salts templates and promoting the formation of numerous closed pores during subsequent pyrolysis. All of the obtained hard carbons exhibit high specific capacities of over 340 mAh/g, and initial Coulomb efficiencies of over 90%. Besides, the information of closed pore structure in hard carbon, accompanying with the diffusive behavior of Na+ and the in-situ Raman spectroscopy reveal a strong link between the increased plateau and the closed pore volume, providing a compelling insight for the mechanism of Na+ storage in hard carbon. The optimal sample exhibits the highest closed pore volume, which performs a remarkable specific capacity of 374 mAh/g and a high initial Coulombic efficiency of 92.4%. Furthermore, all zinc salt-derived hard carbon exhibit analogous microstructures and electrochemical behaviors, demonstrating the universality of utilizing both inorganic and organic zinc salts as templates for adjusting the microporous structure of hard carbon. These findings provide a systematic approach to enhance the reversible capacity and maintain high initial Coulombic efficiency for sodium-ion battery anodes.

Cell-Shearing Chemistry Directed Closed-Pore Regeneration in Biomass-Derived Hard Carbons for Ultrafast Sodium Storage.

The closed-pore structure of hard carbons holds the key to high plateau capacity and rapid diffusion kinetics when applied as sodium-ion battery (SIB) anodes. However, understanding and establishing the structure-electrochemistry relationship still remains a significant challenge. This work, for the first time, introduces an innovative deep eutectic solvent (DES) cell-shearing strategy to precisely tailor the cell structure of natural bamboo and consequently the closed-pore in its derived hard carbons. The DES shearing force effectively modifies the pore architecture by simultaneously shearing and dissolving amorphous components to form closed pore cores with adjustable sizes, as well as disintegrating crystalline cellulose through generation of competing hydrogen bonds to elaborately tune the pore wall thickness and ordering. The optimized closed-pore structure featuring appropriate pore size (∼2 nm) and ultra-thin (1-3 layers) disordered pore walls, exhibits abundant active sites and delivers rapid ion diffusion kinetics and high reaction reversibility. Consequently, a high reversible capacity of 422 mAh g-1 at 30 mA g-1 along with an exceptional rate capability (318.6 mAh g-1 at 6 A g-1) are achieved, outperforming almost all previous reported hard carbons. The new concept of cell-shearing chemistry for closed-pore regeneration significantly advances the applications of biomass materials for energy storage.

Understanding the Relationship of Closed Pore Structure in Biomass- derived Hard Carbon with Cellulose Regulating Strategy.

Recycling waste biomass to pyrolytic carbon has become a development direction of sodium-ion batteries (SIBs)anodes. However, it remains a challenge to precisely control the composition and structure of biomass to modify the properties of derived carbon. Herein, a strategy of hydrolyzing cellulose in phellem with sulfuric acid is proposed, which can promote cellulose fracture, reduce the graphitization and increase the content of closed pores in hard carbon. Accordingly, after the regulation of closed pore structure, the reversible capacity increased from 207 to 330 mAh g-1 at 20mA g-1, realizing an increase of ≈130 mAh g-1 in the plateau region and the initial Coulombic efficiency (ICE) is enhanced from 78% to 90%. When applied in full cell with O3-Na[Ni1/3Fe1/3Mn1/3]O2, it showed an energy density of 247Wh kg-1. This strategy has certain universality, and it provides the feasibility to use low-value cellulose-containing biomass to fabricate high-performance hard carbon materials.

Preparation, pore structure and properties of uniformly porous glass-ceramics sintered from granite powder using SiC@SiO2 foaming agent

Granite sludge produced during the processing of granite blocks should be efficiently recycled for environmental protection and as a sustainable resource. In this work, porous glass-ceramics were prepared by stepwise sintering of granite powder using core-shell SiC@SiO2 foaming agent. The SiC and SiC@SiO2 foaming agents were compared in terms of the sintering and foaming behaviors of the powder compacts by thermal expansion, thermogravimetry and mass spectroscopy. The foaming agent and foaming temperature were investigated to study their effects on the pore structure and properties of the porous glass-ceramics. The SiO2 shells of the SiC@SiO2 particles inhibited the oxidation of the SiC cores and the release of CO2 at the early stage of the sintering process, thus preventing pore coalescence and increasing the densification and specific strength of the sintered glass-ceramics. As the foaming temperature increased, the porous glass-ceramics exhibited a linear relationship between pore size and foaming temperature, and the specific strength first increased and then decreased due to pore coalescence and reduced crystallinity. Furthermore, the linear relationship between thermal conductivity and porosity indicates a closed pore structure, as demonstrated by computed tomography. At a foaming temperature of 1220 °C, the porous glass-ceramic has a porosity of 50.1 %, a specific strength of 16.6 kN⋅m/kg and a thermal conductivity of 0.747 W/(m⋅K). Numerical simulation confirms that lightweight glazed glass-ceramics have potential applications in energy-efficient building tiles.

Deconstruction Engineering of Lignocellulose Toward High-Plateau-Capacity Hard Carbon Anodes for Sodium-Ion Batteries.

Biomass-derived hard carbon is a promising anode material for commercial sodium-ion batteries due to its low cost, high capacity, and stable cycling performance. However, the intrinsic tight lignocellulosic structure in biomass hinders the formation of sufficient closed pores, limiting the specific capacity of obtained hard carbons. In this contribution, a mild, industrially mature pretreatment method is utilized to selectively regulate biomass components. The hard carbon with a rich closed pore structure is prepared by optimizing the appropriate ratio of biomass composition. Optimized etching conditions enhanced the closed pore volume of hard carbon from 0.15 to 0.26 cm3 g-1. Consequently, the engineered hard carbon exhibited excellent electrochemical performance, including a high reversible capacity of 346 mAh g-1 with a high plateau capacity of 254 mAh g⁻¹ at 50 mA g⁻¹, robust rate capability, and cycling stability. The optimized hard carbon shows an 88 mAh g⁻¹ increase in plateau capacity compared to hard carbon from directly carbonizing bamboo fibers. This mature approach provides an easy-to-operate industrial pathway for designing high-capacity biomass-based hard carbons for sodium-ion batteries.

The induced formation and regulation of closed-pore structure for biomass hard carbon as anode in sodium-ion batteries

Biomass hard carbon is regarded as an advanced anode materials for sodium ion batteries (SIBs) since it possesses balanced performance including satisfactory specific capacity, suitable operating voltage window and low cost. Although numerous instances of utilizing biomass-derived hard carbon in SIBs have been observed, the unregulated pore structure of these hard carbon materials significantly constrains the electrochemical performance of SIBs, leading to diminished initial Columbic efficiency (ICE) and plateau capacity. Herein, taking a biomass hard carbon derived from waste camellia seed shells (CSSHCs) as a template, we display a correlation between synthesis conditions and pore structure of CSSHCs. CSSHCs are synthesized via a facile route including pre‑carbonization, purifying, mechanical ball-milling and high-temperature carbonization, and it is found that adjusting the secondary calcination temperature can induce the formation of closed pore structure, which is of great benefit to increase the ICE and the plateau-capacity. Besides, it is also proved that the obtained CSSHCs anodes obey a sodium storage mechanism that can be classified as “adsorption-intercalation-pore filling”, which endows SIBs with a competitive electrochemical performance. Specifically, the obtained biomass hard carbons at 1300 °C exhibits the best electrochemical performance among these anodes with the reversible capacity of as high as 270.0 mAh g−1 and a high ICE of 80.1 %, together with an excellent cycle stability (91.0 % capacity retention after 200 cycles at 0.1C, 1C = 300 mA g−1). Therefore, this study provides a significant exploration and raw material support for the further utilization of the waste biomass and sustainable development of the anode materials for the large-scale application of SIBs.

Tailoring closed pore structure in phenolic resin derived hard carbon enables excellent sodium ion storage

The existed plenty of oxygen-containing species in phenolic resin easily inhibit the migration and rearrangement of carbon atoms during pyrolysis, which disfavors the formation of pseudo-graphite structure with larger lateral length (La) and hence leads to poor closed pores, accounting for a low capacity and initial Coulombic efficiency (ICE). Herein, hard carbon with rich closed pores and the most suitable pore size and volume is constructed via a two-step carbonization strategy. It is found that the pre-annealing step can effectively decrease oxygen content by changing the interconnection form of molecule chains, which promotes the growth of La during post-carbonization process, accelerating the formation of closed pores. Besides, with decreasing oxygen content, closed pore size gradually increases, while closed pore number and volume both first increase and then decrease, unveiling that an excessive high and too low oxygen content are unfavorable for the formation of ideal closed pores, resulting from an unsuitable La size. Therefore, the resulting sample, featured by the optimal balance between closed pore number, size (2.52 nm), and volume (0.215 cm3 g−1), delivers a high capacity of 351 mAh g−1 along with an excellent ICE of 83 %.

Migration and retention of human osteosarcoma cells in bioceramic graft with open channel architecture designed for bone tissue engineering

The microstructure of a porous bioceramic bone graft, especially the pore architecture, plays a crucial role in the performance of the graft. Conventional bioceramic grafts typically feature a random, closed-pore structure, limiting biological activity to the periphery of the graft. This can lead to delay in full integration with the host site. Bioceramic forms with open through pores can perform better because their inner regions are accessible for natural bone remodeling. This study explores the influence of open through pores in a bioceramic graft on the migration and retention of the local cellsin vitro, which will correlate to the rate of healingin vivo.Hydroxyapatite ceramic forms with aligned channels were fabricated using slip casting technique, employing sacrificial fibers. The sorption characteristics across the graft were evaluated using human osteosarcoma cell line. Seven-day cultures showed viable cells within the channels, confirmed by live/dead assay, scanning electron microscope analysis, and cytoskeletal staining, indicating successful cell colonization. The channel architecture effectively enhances cell migration and retention throughout its entire structure, suggesting potential applications in bone tissue engineering based on the results obtained.

Regulating the closed pore structure of biomass-derived hard carbons towards enhanced sodium storage

Hard carbon (HC) stands out as a promising anode material for sodium storage due to its unique structure. However, the pore structure regulation of HC still poses a significant challenge. Herein, we propose a combined method of hydrothermal pretreatment, freeze-drying, and high-temperature carbonization to regulate the pore structure of HC. During the hydrothermal processes, the assembly of graphene oxide (GO) with starch facilitates the formation of open pores, which are subsequently transformed into closed pores during high-temperature carbonization. Impressively, a hard carbon with a reversible capacity of 434 mA h g −1 at 30 mA g −1 has been prepared through the structure regulation. Compared to the sample without structural regulation, it demonstrates a remarkable increase of 184.21 mA h g−1, with an enhancement rate of 73.80 %. Simultaneously, the skeletal structure of GO serves as a conductive network and framework support, enabling favorable rate performance and excellent cycling stability. Furthermore, the sodium storage mechanism is deduced as “adsorption -- intercalation -- pore filling”. Overall, this study can offer valuable insights into pore structure regulation for anode materials and shed light on sodium storage mechanisms.

Enhancing the sodium storage performance of hard carbon by constructing thin carbon coatings via esterification reactions

Hard carbons derived from pitch are considered a competitive low-cost anode for sodium-ion batteries. However, the preparation of pitch-based hard carbon (PHC) requires the aid of a pre-oxidation strategy, which introduces unnecessary defects and oxygen elements, which leads to low initial Coulombic efficiency (ICE) and poor cycling stability. Herein, we demonstrate a new surface engineering strategy by grafting chemically active glucose molecules on the PHC surface via esterification reactions, which can achieve low-cost nano-scaled carbon coating. Thin glucose coating can be carbonized at a lower temperature, which results in a more closed pore structure and fewer functional groups. The as prepared PHC exhibits a high reversible capacity of 328.5 mAh/g with a high ICE of 92.08 % at 0.02 A/g. It is noteworthy that the PHC can be adapted to a variety of cathode materials for full-cell assembling without pre-sodiation, which maintains the characteristics of high capacity and excellent cycling stability. The performance of resin-based hard carbon coated with a similar method was also improved, demonstrating the universality of the technique.

Oxygen-driven closing pore formation in coal-based hard carbon for low-voltage rapid sodium storage

The coal-derived hard carbon is considered a promising anode material for sodium-ion batteries (SIBs) due to its ample resources, low cost, and unique pore structure. However, the ordered carbon microstructure of this material leads to inferior sodium storage capacity and low initial Coulombic efficiency (ICE). Herein, we propose a strategy to inhibit over-graphitization and promote the formation of closed pores during subsequent carbonation processes through oxygen-driven carbon sheets development. The formation mechanism of closed pores in coal-based hard carbon has been systematically established, and its contribution to the capacity of the low-voltage plateau in hard carbon anode for SIBs has been explained. In-situ characterizations demonstrate that the presence of abundant closed pores and moderate graphitization provides sufficient active sites for Na+ ion pore-filling. The closed pore structure ensured the realization of a high plateau capacity, resulting in a high reversible capacity of 303.1 mA h g−1, which was significantly higher than that of the open-pore dominant carbon (161.1 mA h g−1). This study offers innovative perspectives on designing high-performance carbon anodes with closed porosity, utilizing cost-effective and highly aromatic precursors.

Regulating the “core-shell” microstructure of hard carbon through sodium hydroxide activation for achieving high-capacity SIBs anode

Pore structure engineering has been acknowledged as suitable approach to creating active sites and enhancing ion transport capabilities of hard carbon anodes. However, conventional porous carbon materials exhibit high BET and surface defects. Additionally, the sodium storage mechanism predominantly occurs in the slope region. This contradicts practical application requirements because the capacity of the plateau region is crucial for determining the actual capacity of batteries. In our work, we prepared a novel “core-shell” carbon framework (CNA1200). Introducing closed pores and carboxyl groups into coal-based carbon materials to enhance its sodium storage performance. The closed pore structure dominates in the “core” structure, which is attributed to the timely removal of sodium hydroxide (NaOH) to prevent further formation of active carbon structure. The presence of closed pores is beneficial for increasing sodium ion storage in the low-voltage plateau region. And the “shell” structure originates from coal tar pitch, it not only uniformly connects hard carbon particles together to improve cycling stability, but is also rich in carboxyl groups to enhance the reversible sodium storage performance in slope region. CNA1200 has excellent electrochemical performance, it exhibits a specific capacity of 335.2 mAh g−1 at a current density of 20 mA g−1 with ICE = 51.53 %. In addition, CNA1200 has outstanding cycling stability with a capacity retention of 91.8 % even when cycling over 200 times. When CNA1200 is used as anode paired with Na3V2(PO4)3 cathode, it demonstrates a capacity of 109.54 mAh g−1 at 0.1 C and capacity retention of 94.64 % at 0.5 C. This work provides valuable methods for regulating the structure of sodium-ion battery (SIBs) anode and enhances the potential for commercialization.

Synergetic enhancement of ultimate strength and damping properties by pore structure in novel porous Cu-Al-Mn shape memory alloy

To meet the higher device vibration reduction requirements, novel porous Cu71Al18Mn11 shape memory alloys (SMAs) with controllable porosity were prepared using Cu, Al, and Mn elemental powders as raw materials. To further enhance the strength and damping performance of SMAs, a low-temperature reactive synthesis combined with spark plasma sintering (LTRS+SPS) process was used. In this paper, the effects of LTRS+SPS process on pore structure and texture, compressive strength, and damping properties of porous Cu71Al18Mn11 alloy were studied. The outcomes indicated that LTRS+SPS process can effectively improve both compressive strength and damping properties. The associated closed pore structure caused by this process and the second phase γ2 phase formed by element diffusion result in a variety in compressive strength from 324.6 MPa to 617.9 MPa, which were 3.9 times that of the comparable porosity alloy with alloy powder as raw material by vacuum sintering. Meanwhile, the damping value changed from 0.27 to 0.10, which was 4.5 times that of the homogeneous dense alloy. The increase in damping property is caused by the increase of motionable interfaces in the matrix for the introduction of pores, which leads to the increase of energy dissipation. Besides. the interaction between the second phase γ2 and dislocation contributes to the improvement of damping, as well as the compressive strength. These findings in this paper provide new insights and references for the structural design and microstructure design of high-performance Cu-based alloys.

Identifying the plateau sodium storage behavior of hard carbon through the spin state

Hard carbon has emerged as a promising anode material for rechargeable sodium-ion batteries, owing to its abundant precursor sources and remarkable reversible charge storage capacity. The key to achieving an extended sodium storage capacity lies in the plateau capacity largely associated with the closed-pore structure, yet a comprehensive understanding in this area remains incomplete. In our study, we utilized electron paramagnetic resonance (EPR) spectra to discern the spin state of unpaired electrons within hard carbon materials, enabling the identification of sodium storage plateau regions. Hard carbon anodes with plateau capacity predominantly exhibit delocalized spins, evident in the EPR spectrum by limited spin density and a linewidth exceeding 100 G. These spins originate from the extended aromatic structure within small-sized but curved nano-graphite and the closed-pore walls, which are crucial for plateau capacity. Conversely, hard carbon anodes exclusively possessing slope capacity are characterized by localized spins, presenting a typical narrow and intense Lorentzian EPR signal. These localized spins arise from the edge defects of the nano-graphite structure, serving as favourable sites for sodium adsorption. Our development of a methodology to discern hard carbon plateau capacity behavior based on EPR spectra presents a facile and rapid approach for advancing high-performance hard carbon materials.

Vinasse-based hard carbon: Preparation and study on its compatibility with ester/ether-based electrolyte for sodium ion storage

In this work, a simple method was used to prepare vinasse based hard carbon (HC) for sodium ion storage. The interlayer spacing and closed pore structure of the materials were regulated by different pyrolysis temperature, and the electrochemical evaluations were conducted in ether-based and ester-based electrolytes, respectively. The initial coulombic efficiency (ICE) of 91.1 %, capacity retention rate of 63.1 % at high rate of 10 A g-1 (platform capacity of 121.7mAh g-1), and ultra-long cycle stability of 93.7 % after 8000 cycles at 5 A g-1 fully shows better compatibility in the ether-based electrolyte. The coordination number, de-solvation energy, and diffusion rate of Na+ in the two electrolytes were simulated and calculated by molecular dynamics (MD) combined with density functional theory (DFT). It was elucidated that Na+ partially co-embeds in ether-based electrolytes, avoiding slow de-solvation processes, in addition, when Na+ is embedded alone, it has a lower de-solvation free energy than that in ester-based electrolytes, therefore, the ion diffusion coefficient obtained in ether-based electrolytes is above three times than that in ester-based electrolytes. The ultrafast dynamics achievements excellent rate performance and cycling stability for the sample of optimal structure. This research has a promoting effect on the commercial application of biomass-based hard carbon for sodium ions storage.

Simultaneously improving strength and abradability for abradable seal coatings by localized bonding hollow spheres

To solve the long-standing contradiction between the bonding strength and abradability of an abradable seal coating (ASC), a novel spherical closed-pore structure was proposed. The new structure consisted of three discontinuous phases, including locally enriched metals, hollow thin-shell spheres, and pores. The results show that the bonding strength of the abradable seal coating reaches 25.4 MPa, and the abrasion ratio between the coating and blade tip, as a characteristic of the abradability of ASCs, is > 5900. The dewetting kinetics of the metal film on the ceramic sphere were calculated. The size of the shrink metal hemisphere is 3.6 times the metal film thickness. The locally enriched metal enables a high bonding strength, while the fragmentation of the hollow thin-shell spheres enhances the abradability, thus simultaneously improving the strength and abradability. The coating is expected to be used in next-generation turbines to improve efficiency and stability.

A superior sodium-ion anode material from PAN/lignin-derived carbon nanofibers with inter-connected structure prepared through phosphoric acid induced cross-linking

A feasible route to fabricate phosphorus-doped carbon nanofibers (P-CNFs) with an inter-connected structure has been demonstrated through electrospinning, stabilization, and subsequent phosphoric acid impregnation and carbonization processes using polyacrylonitrile and lignin as carbon sources. The results illustrate that the phosphoric acid induced cross-linking could be beneficial to acquire the closed-pore structure and the heteroatom-doped surface chemistry of nanofibers. As a result, the P-CNFs exhibit higher interlayer spacing of graphite and lower BET specific surface area compared to the pristine CNFs. The P-CNFs as an anode material for sodium-ion batteries (SIBs) present a high reversible capacity 278 mA h g−1 at 0.2 A g−1 and a superior initial Coulomb efficiency (ICE) of 78.86 %. Moreover, the reversible capacity of P-CNFs can be stably maintained near the initial capacity after 5000 cycles at 1 A g−1, showing exceptional structural stability and cycling durability. Meanwhile, the sodium storage mechanism of P-CNFs was investigated using in-situ Raman and ex-situ XRD analysis to understand the exceptional structural stability and Na+ adsorption capacity of P-CNFs. This work provides valuable insights for the design of carbon nanofibers with an inter-connected structure as anode materials for SIBs, exhibiting outstanding electrochemical properties.

Closed pore engineering of activated carbon enabled by waste mask for superior sodium storage

Carbonaceous materials with closed pore structure have emerged as intriguing anode materials for sodium-ion batteries (SIBs). However, it remains a significant challenge to precisely regulate the structure of closed pores to achieve superior electrochemical Na-storage performance. Herein, a simple but practical strategy is proposed to convert the open pores in activated carbon (AC) into closed pores with the assistance of polypropylene (PP) waste masks. This transition occurs via the carbonization of light aromatic compounds from PP, which deposit on the entrance of the AC's open pore and generate PP-based carbon layer thus regulating the pore configuration of AC. When configured as an anode for SIBs, the hard carbon with optimal closed pores (CMAC-2) delivered a high reversible capacity of 335.5 mAh g−1 with satisfactory initial coulombic efficiency of 88.7 % as well as remarkable cycle and rate capability. Additionally, the assembled O3-NaNi1/3Fe1/3Mn1/3O2//CMAC-2 full cell achieves a high energy density of 277.5 Wh kg−1 (based on the total mass of anode and cathode) with an outstanding rate capability. This work not only offers an ingenious method to fabricate closed pore structure with boosted Na+ storage performance, but also provides a sustainable practice by repurposing polyolefin waste into value-added energy storage products.

The multi-scale pore structure of superfine pulverized coal. Part 2. Mesopore and closed pore morphology

Superfine pulverized coal exhibits extraordinary properties in thermal conversion processes like pyrolysis and combustion. The exploration of closed pores is of great significance for studying of the macromolecular structure, and developing advanced clean combustion technologies. In this work, the influences of coal rank and particle size on the mesopore characteristics (i.e., pore size, volume, and specific surface area), especially closed pores, were obtained by combining nitrogen adsorption and synchrotron-based small-angle X-ray radiation (SAXS). In addition, combined with the closed pore volume measured by He density and SAXS, research focuses on the formation and opening mechanisms of closed pores in different rank coals at a molecular level. The results indicate that both the bituminous (NMG) and anthracite coal (HN) have a few large open pores (>100 nm), with large amount of small mesopores and micropores (<2 nm). The HN coal has more open mesopores which have a smaller pore size than NMG coal. The closed pore proportion of HN coal in the studied pore size range is between 2 and 52 %, while that of NMG coal is between 47 and 67 %. In addition, both coals have a certain amount of closed pores formed by shear force and ash blockage, while the matrix compression also contribute to certain types of closed pores in NMG. These findings contribute to illustrating the closed pore structure in coal at the molecular level, which sheds light on constructing comprehensive macromolecular pore models of coal and thus promoting the development of clean coal utilization technologies.

Closed pore structure engineering from ultra-micropores with the assistance of polypropylene for boosted sodium ion storage

Closed pore architectures with exceptional Na-storage performance have been successfully fabricated from ultra-micropores with the assistance of polypropylene.