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Research progress on low-rank coal-based carbon materials
SONG Wen-ge, ZENG Hong-jiu, WANG Bin, HUANG Xian-hong, LI Xiao-ming, SUN Guo-hua
 doi: 10.1016/S1872-5805(24)60872-3
Abstract(36) HTML(14) PDF(2)
Compared to the traditional carbon materials precursors, the low-rank coal has captured numerous attention because of a series of virtues, such as extensive reserves, high carbon content, and low cost. To better realize the optimal utilization and controllable conversion of low-rank coal to carbon materials, we firstly overview the physicochemical characteristics of low-rank coal, along with the precise design and controllable preparation of low-rank coal derived carbon materials by using various the methods and modification strategies and their application. Then, we analyze the potential effect of the ash and associated heteroatoms presence in low-rank coal on the application performance of coal-based carbon materials. Furthermore, we highlight present challenges and further opportunities in this field, such as the exploration of novel preparation technologies, in-depth exploration of material performance, and innovative applications in emerging fields such as energy storage, environmental purification, and catalytic reactions. The Review will guide future research works on the design of high-performance coal-derived carbon materials and the optimization of application performance.
In-situ thermal Raman mapping and stress analysis of CNT/CF/epoxy interfaces
HE Jing-zong, CHEN Shi, MA Zheng-kun, LU Yong-gen, WU Qi-lin
 doi: 10.1016/S1872-5805(24)60874-7
Abstract(42) HTML(12) PDF(2)
A study of the interfacial behavior and internal thermal stress distribution in fiber-reinforced composites is essential to assess their performance and reliability. CNT/carbon fiber (CF) hybrid fibers were constructed using electrophoretic deposition. The interfacial properties of CF/epoxy and CNT/CF/epoxy composites were statistically investigated and compared using in-situ thermal Raman mapping by dispersing CNTs as a Raman sensing medium (CNTR) in a resin. The associated local thermal stress changes can be simulated by capturing the G' band position distribution of CNTR in the epoxy at different temperatures. It was found that the G' band shifted to lower positions with increasing temperature, reaching a maximum difference of 2.43 cm−1 at 100 °C. The interfacial bonding between CNT/CF and the matrix and the stress distribution and changes during heat treatment (20–100 °C) were investigated in detail. The study is important for studying thermal stress in fiber-reinforced composites by in-situ thermal Raman mapping technology.
Revealing the correlation of high-frequency performance of supercapacitors with doped nitrogen species
FAN Ya-feng, YI Zong-lin, ZHOU Yi, XIE Li-jing, SUN Guo-hua, WANG Zhen-bing, Huang Xian-hong, SU Fang-yuan, CHEN Cheng-meng
 doi: 10.1016/S1872-5805(24)60849-8
Abstract(65) HTML(28) PDF(7)
Nitrogen doping strategy has been widely used to enhance the performance of carbon electrodes in supercapacitors, particularly in terms of high-frequency response. However, the charge storage and ion response mechanisms of different nitrogen dopants at high frequencies are still unclear. In this study, we employ carbonized melamine foam with an open surface structure as a simplified model electrode material, enabling a comprehensive analysis of their impact on the ionic response behavior of high-frequency supercapacitors. Through a combination of experiments and first-principles calculations, we uncover that pyrrolic nitrogen, characterized by a higher adsorption energy, enhances the charge storage capacity of the electrode at high frequencies. On the other hand, graphitic nitrogen, with a lower adsorption energy, promotes rapid ion response. Furthermore, we propose the use of adsorption energy as a practical descriptor for electrode/electrolyte design in high-frequency applications, offering a more universal approach for optimizing the performance of N-doped carbon materials. This research contributes to the advancement of high-frequency supercapacitor technology and provides guidance for the development of improved N-doped carbon materials.
Porous silicon/carbon composite for high-performance lithium-ion batteries
TIAN Zhen-yu, WANG Ya-fei, QIN Xin, Shaislamov Ulugbek, Hojamberdiev Mirabbos, ZHENG Tong-hui, DONG Shuo, ZHANG Xing-hao, KONG De-bin, ZHI Lin-jie
 doi: 10.1016/S1872-5805(24)60850-4
Abstract(125) HTML(113) PDF(36)
Silicon anodes are promising candidates for lithium-ion batteries. However, their practical application is severely limited due to their significant volume expansion leading to irreversible material fracture and electrical disconnection. This study proposes a new top-down strategy for preparing microsized porous silicon and introducing polyacrylonitrile (PAN) as nitrogen-doped carbon coating, which is designed to maintain the internal space and alleviate the outward expansion of the silicon anode during the lithiation and delithiation process. Subsequently, we explored the effect of temperature on the thermal transition behavior of PAN and the electrochemical behavior of the composite electrode. After the treatment at 400 °C, the PAN coating retained a high nitrogen doping content of 11.35%, which explicitly confirmed the existence of C―N and C―O bonds that improved the ionic-electronic transport properties. This treatment not only retained a more intact carbon layer structure, but also introduced carbon defects, exhibiting remarkably stable cycling even at high rates. When cycled at 4 A g−1, the optimized anode exhibited a specific capacity of 857.6 mAh g−1 even after 200 cycles, demonstrating great potential for high-capacity energy storage applications.
Wet-composition-induced amorphous adhesion toward a high interfacial shear strength between carbon fiber and polyetherketoneketone
ZHANG Feng, LI Bo-lan, JIAO Meng-xiao, LI Yan-bo, WANG Xin, YANG Yu, YANG Yu-qiu, ZHANG Xiao-hua
 doi: 10.1016/S1872-5805(22)60646-2
Abstract(471) HTML(296) PDF(56)
Interfacial adhesion between carbon fiber (CF) and polyetherketoneketone (PEKK) is a key factor that affects the mechanical performances of their composites. Therefore, it is of great importance to impregnate PEKK into CF bundles as efficiently as possible. Here we report that owing to the high dissolubility, PEKK can be introduced onto CF surfaces via a wet strategy. The excellent wettability of PEKK guarantees a full covering and tight binding on CFs, making it possible to evaluate the interfacial shear strength (IFSS) with the microdroplet method. Furthermore, the interior of CF bundles can be completely and uniformly filled with PEKK by the solution impregnation, leading to a high interlaminar shear strength (ILSS). The maximum IFSS and ILSS can reach 107.8 and 99.3 MPa, respectively. Such superior shear properties are ascribed to the formation of amorphous PEKK confined in the limited spacing between CFs.
Cardo poly (ether sulfone) toughened E51/DETDA epoxy resin and its carbon fiber composites
WU Rong-peng, ZHANG Xing-hua, WEI Xing-hai, JING De-qi, SU Wei-guo, ZHANG Shou-chun
 doi: 10.1016/S1872-5805(23)60741-3
Abstract(242) HTML(146) PDF(54)
A toughener that can effectively improve the interlaminar toughness in carbon fiber composites is crucial for various applications. In this paper, the toughening effects of phenolphthalein-based cardo poly (ether sulfone) (PES-C) on E51/ DETDA epoxy and its carbon fiber composites (CFCs) were investigated. The SEM results showed that PES-C/epoxy blends formed a sea-island phase and bicontinuous phase structure, which was associated with reaction-induced phase separation. After adding 15 g m−2 PES-C, the glass transition temperature (Tg) of the blends was increased by 51.5 °C. Meanwhile, the flexural strength, impact strength and fracture toughness of the blends were improved by 41.1%, 186.2% and 42.7%, respectively. These improvements could be attributed to the phase separation structure of the PES-C/epoxy system. Moreover, PES-C film was used to improve the mode-II fracture toughness (GIIC) of CFCs. GIIC value of the 7 μm PES-C film toughened laminate was improved by 80.3% compared to that of the control laminate. The increase in GIIC could be attributed to the cohesive failure and plastic deformation in the interleaving region.
Preparation of high-performance synthetic pitch from N/Cl-bearing aromatic hydrocarbons
ZHANG Yu-kun, LIN Xiong-chao, GAO Hong-feng, XI Wen-shuai, WANG Cai-hong, WANG Yong-gang
 doi: 10.1016/S1872-5805(24)60864-4
Abstract(40) HTML(14) PDF(4)
Preparation of synthetic pitch using aromatic monomers could easily regulate the oriented structure at molecular level, which is conducive to the fabrication of high-performance carbon fiber. In this study, the isotopically synthetic pitch was successfully prepared using N- and Cl-bearing aromatic hydrocarbon precursors by halogen-induced method. The halogenation- enhanced synthetic process was systematically verified by investigating the structural variation under different synthetic conditions; and the reaction mechanism was thoroughly probed for preparation of high-performance carbon fibers. The result shows that the pyridine N in quinoline has strong electrophilic function, which is found be the effective active site to induce the polymerization reaction by coupling with Cl-bearing aromatic hydrocarbons. The mutual reaction among such free radicals would cause strong homopolymerization and oligomerization. Higher synthesis temperature and longer retention time are beneficial to increase the polymerization degree and thus elevate the softening point of synthetic pitch. Moreover, linear molecular structure was formed by the designated Cl and methyl substitution process, which was available for the preparation of highly spinnable pitch. Consequently, a high-quality spinnable pitch with a softening point of 258.6 °C and as-prepared carbon fiber with a tensile strength of 1163.82 MPa was obtained. This study is expected to provide a relatively simple and safe method for the preparation of high-quality spinnable pitch.
Formation of mesophase microbeads from bulk mesophase pitch induced by fullerene
CHEN Wen-sheng, LIU Lan-tao, WANG Zheng, DUAN Chun-feng, ZHANG Xing-wei, MA Zhao-kun, CHEN Xiao-hong, SONG Huai-he
 doi: 10.1016/S1872-5805(24)60866-8
Abstract(58) HTML(26) PDF(1)
The controllable transformation of mesophase pitch (MP) exhibits great practical significance for studying the formation mechanism and application of MP. This work accomplished the reversible transformation of the mesophase morphology from bulk to spherical type by heat-treating naphthalene-based mesophase pitch (NMP) uniformly dispersed with fullerenes (C60). The effects of C60 loading and reaction temperature on the morphological transformation of mesophase are investigated by polarizing microscope and scanning electron microscopy. The physical induction of NMP by C60 was characterized by thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray diffractometry and Raman spectroscopy. The results show that the bulk type of NMP can be converted to spherical type at 300–320 °C heat treatment temperature with the addition of 5% C60, and the size of mesophase microbeads increases with increasing temperature. Furthermore, a model is established to explain the unique induction effect of C60 in the reversible transformation process. This work makes the morphological transformation of MP controllable, which provides a new idea for the subsequent research on MP morphology.
A review on catalytic preparation of mesophase pitch
MA Zi-hui, YANG Tao, SONG Yan, CHEN Wen-sheng, DUAN Chun-feng, SONG Huai-he, TIAN Xiao-dong, GONG Xiang-jie, LIU Zheng-yang, LIU Zhan-jun
 doi: 10.1016/S1872-5805(24)60862-0
Abstract(133) HTML(57) PDF(15)
Mesophase pitch, due to its high purity and excellent orientation, is a superior precursor for high-performance carbon materials. However, the preparation of top-notch mesophase pitch faces challenges. Catalytic polycondensation at low temperature is more favorable for synthesizing mesophase pitch, which circumvents the high-temperature free radical reaction of other thermal polycondensation approaches. Besides, the reaction is gentle and could be easily controlled. It has the potential to significantly improve the yield of mesophase pitch and easily introduce the naphthenic characteristics into the molecules, hence, catalytic polycondensation is a preferentially recommended methodology to synthesize highly spinnable mesophase pitch. This paper furnishes a synopsis of the selection pretreatment of raw materials to prepare diverse mesophase pitches, and explains the reaction mechanism and associated research advancements of different catalytic systems in recent years. Ultimately, how to manufacture high-quality mesophase pitch by employing a catalyst-promoter system is summarized and proposed, it is expected to present original concepts and dependable theoretical direction for the design of high-quality pitch molecules in the future.
Study on the preparation of highly graphitized porous carbon and its ethane/ethylene separation performance
LIU Ru-shuai, TANG Fan, SHI Xiao-dong, HAO Guang-ping, LU An-hui
 doi: 10.1016/S1872-5805(24)60859-0
Abstract(168) HTML(52) PDF(19)
Efficient separation of ethane (C2H6) and ethylene (C2H4) is crucial for the preparation of polymer-grade C2H4, necessitating the development of highly selective and stable C2H6/C2H4 adsorbent. In this study, highly graphitized porous carbon, denoted as GC-800, was synthesized via room temperature polymerization followed by carbonization at 800 ºC using phenolic resin as the precursor and FeCl3 as the iron source. VASP calculations confirmed higher binding energy between C2H6 molecules and graphitized porous carbon surfaces. The increase in graphitization degree effectively enhanced the adsorption capacity of porous carbon for C2H6, but the catalytic graphitization process of Fe at high temperatures could disrupt the microporous structure of porous carbon, thereby reducing the separation ability of C2H6/C2H4. By controlling the carbonization temperature, the graphitization degree and pore structure of the porous carbon were synergistically optimized. Raman spectra and XPS spectra revealed that GC-800 exhibited high graphitization degree, with a sp2 C content as high as 73%. Low-temperature N2 physical adsorption measurements estimated the specific surface area of GC-800 to be as high as 574 m2·g−1. At 298 K and 1 bar, GC-800 exhibited an equilibrium adsorption capacity of 2.16 mmol·g−1 for C2H6, with C2H6/C2H4 (1∶1 and 1∶9, v/v) IAST selectivity respectively reaching 2.4 and 3.8, significantly higher than those of most reported high-performance C2H6 selective adsorbents. Dynamic breakthrough experiments demonstrated that GC-800 could obtain high-purity C2H4 in a single step from a mixture of C2H6 and C2H4. Dynamic cycle tests confirmed the good cyclic stability of GC-800 exhibited good cyclic stability, which could efficiently separate C2H6/C2H4 even under humid conditions.
Semi-quantitative analysis on the structural evolution of mesophase pitch-based carbon foams by Raman and FTIR spectroscopy
LIU Yue, CHANG Sheng-kai, SU Zhan-peng, HUANG Zu-jian, QIN Ji, YANG Jian-xiao
 doi: 10.1016/S1872-5805(24)60867-X
Abstract(64) HTML(23) PDF(3)
In this work, graphitized carbon foams (GFm) were prepared using mesophase pitch (MP) as a raw material through the foaming (450 °C), pre-oxidation (320 °C), carbonization (1000 °C), and graphitization (2800 °C) processes. Further, the differences in structure and properties of GFm prepared from different MP precursors which were pretreated by ball milling or liquid phase extraction were investigated and compared, and semi-quantitative calculations were conducted on the Raman and FTIR spectra of samples at each preparation stage. Semi-quantitative spectroscopic analysis provided the detailed information on the structure and chemical composition evolutions of MP and its derived GFm. Combined with microscopic observation for confirmation, the evolution mechanism from precursors to GFm during the preparation process was systematically analyzed. The results showed that ball milling could concentrate the mass distribution of aromatics in pitch, which contributed to uniform foaming, obtaining GFm with uniform pore distribution, and fine comprehensive properties. Liquid phase extraction helped to remove light components while retaining large aromatics to form carbonaceous planes with the largest average size during post-treatments, obtaining GFm with the highest graphitization degree and the fewest open holes, thus presenting the best compression resistance (2.47 MPa), the highest thermal conductivity (64.47 W/(m·K)) and the lowest electrical resistance (13.02 μΩ·m). The characterization strategy by combining semi-quantitative spectroscopic analysis with microscopic observation proposed in this work could provide the receivable theory of knowledge for controlling the preparation of MP-derived GFm.
Synergistic enhancement of toughness and viscosity of carbon nanotubes/polyether imide/polyether ether ketone nanocomposites
SONG Jiu-peng, ZHAO Yan, LI Xue-kuan, XIONG Shu, LI Shuang, WANG Kai
 doi: 10.1016/S1872-5805(22)60643-7
Abstract(542) HTML(278) PDF(38)
Polyether ether ketone (PEEK) has favorable mechanical properties. However, its high melt viscosity limits its applications because it is hard to process. In this study, PEEK nanocomposites modified with carbon nanotubes (CNTs) and polyether imide (PEI) were prepared using a direct wet powder blending method. The melt viscosity of the nanocomposites decreased by approximately 50%. Under optimal conditions, the addition of CNTs and PEI resulted in a synergistic increase in the toughness of the nanocomposites. The elongation at break increased by 129%, and the fracture energy increased by 97%. The uniformly dispersed CNTs/PEI powder reduces the processing difficulty of PEEK nanocomposites without affecting the heat resistance. The nanocomposites prepared by this method have lower melt viscosity. This improvement of the properties of PEEK would facilitate its use in the preparation of thermoplastic composites by powder impregnation or laser sintering technology.
Ablation behaviour and mechanical performance of ZrB2-ZrC-SiC modified carbon/carbon composites prepared by vacuum filtration combined with reactive melt infiltration
ZHANG Jia-ping, SU Xiao-xuan, LI Xin-gang, WANG Run-ning, FU Qian-gang
 doi: 10.1016/S1872-5805(24)60841-3
Abstract(231) HTML(135) PDF(54)
The development of advanced aircrafts relies on high performance thermal-structural materials and composites of carbon/carbon (C/C) with ultrahigh-temperature ceramics are ideal candidates. However, traditional routes of compositing are either inefficient and expensive or lead to non-uniform distribution of ceramics in the matrix. Here, vacuum filtration of ZrB2 was successfully applied to introduce ZrB2-ZrC-SiC into C/C as a supplement for reactive melt infiltration ZrSi2, which contributed to the content increase and uniform distribution of the introduced ceramic phases. The mass and linear ablation rates of the composites were reduced by 68.9% and 29.7%, respectively, compared to those of C/C-ZrC-SiC composites prepared through reactive melt infiltration. The ablation performance was improved because of the volatilization of B2O3, taking a part of the heat away, and more uniformly distributed ZrO2 that could promote the formation of ZrO2-SiO2 continuous protective layer. This efficiently resisted the mechanical denudation and hindered the oxygen infiltration.
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2024, 39(3): 1-1.  
Abstract(104) HTML(40) PDF(45)
2024, 39(3): 1-7.  
Abstract(97) HTML(42) PDF(21)
A review of the synthesis, characterization, and mechanism of bimetallic catalysts for electrocatalytic CO2 reduction
LIAO Yin-li, HUANG Heng-bo, ZOU Ru-yu, SHEN Shu-ling, LIU Xin-juan, TANG Zhi-hong
2024, 39(3): 367-387.   doi: 10.1016/S1872-5805(24)60860-7
Abstract(219) HTML(75) PDF(62)
The electrocatalytic CO2 reduction reaction (CO2RR) is an environmentally friendly way to convert CO2 into valuable chemicals. However, CO2 conversion is a complex process, which contains 2, 4, 6, 8, and 12 electron transfer processes. It is very important to develop efficient catalysts to precisely control the number of electron transfers for the chemicals required. Single-metal catalysts have some deficiencies, including slow reaction kinetics, low product selectivity and inadequate stability. In response to these challenges, bimetallic catalysts have received significant attention owing to their unique structure and improved performance. The introduction of secondary metals alters the catalyst’s electronic structure, and creates novel active sites, as well as optimizing their interaction with the intermediates. This review provides a comprehensive account of atomically distributed bimetals based on carbon materials and non-atomic distributed bimetals such as alloys and heterostructures, including their synthesis methods, characterization, and the outcomes of different catalysts. Catalytic mechanisms of different bimetallic catalysts are proposed and challenges encountered in the CO2RR are considered.
A review of graphdiyne in aqueous ion batteries
XU Xian-min, FENG Wen-cong, REN Jing-ke, LUO Wen
2024, 39(3): 388-406.   doi: 10.1016/S1872-5805(24)60852-8
Abstract(262) HTML(63) PDF(69)

Graphdiyne is a novel carbon material with a special carbon hybrid arrangement, unique chemical and electronic structure and numerous pores that has promising applications in electrochemical energy storage. Emerging aqueous ion batteries have advantages of low cost and high safety, but the development of high-performance electrode materials, the design of new membrane systems and ways of stabilizing the interface remain the main challenges in their manufacture. With its unique porous structure and excellent electrochemical properties, graphdiyne can improve ion transport, interface deposition behavior and electrolyte instability in the aspects of anode protection, cathode cladding, membrane design and stabilizing the pH value of the interface. A bottom-up molecular structural design strategy makes graphdiyne easy to modify and dope, improving the properties of its analogues and thus expanding their applications in aqueous ion batteries. We systematically summarize the structure, properties, and synthesis methods of graphdiyne, and summarize the research of graphdiyne in aqueous ion batteries. A comprehensive evaluation of the existing problems and challenges of the use of graphdiyne in aqueous ion batteries is given, and future trends and developments are suggested.

A review of carbon-supported single-atom catalysts for electrochemical reactions
WANG Yi-cheng, MA Xiao-bo, Ayeza, WANG Chen-xu, LI Yang, YANG Cheng-long, WANG Zhe-fan, WANG Chao, HU Chao, ZHANG Ya-ting
2024, 39(3): 407-438.   doi: 10.1016/S1872-5805(24)60863-2
Abstract(263) HTML(78) PDF(88)
Recent advances in the use of carbon-supported single-atom catalysts (SACs) for electrochemical reactions are comprehensively reviewed. The development and advantages of carbon-supported SACs are briefly introduced, followed by a detailed summary of the synthesis strategies used, including vapor phase transport, high temperature pyrolysis and wet chemical methods. Advanced characterization techniques for carbon-supported SACs are also reviewed. The use of carbon-supported SACs in different fields, such as the oxygen reduction reaction, carbon dioxide reduction reaction, nitrogen reduction reaction, hydrogen evolution reaction, and oxygen evolution reaction are summarized. Special emphasis is given to the modification strategies used to enable carbon-supported SACs to have an excellent electrocatalytic performance. Finally, the prospects and challenges associated with using carbon-supported SACs for electrochemical reactions are discussed.
Advances in graphene/molybdenum dichalcogenide-based van der Waals heterostructure photodetectors
ZHANG Xin-hua, LIU Wei-di, GONG You-pin, LIU Qing-feng, CHEN Zhi-gang
2024, 39(3): 439-457.   doi: 10.1016/S1872-5805(24)60853-X
Abstract(233) HTML(76) PDF(67)
Graphene is widely used in photodetection because of its high carrier mobility and wide spectral absorption range. However, its high dark current caused by its low light absorption severely limits its performance. Molybdenum dihalide (MoX2, X= S, Se and Te) has a high absorption coefficient, which can compensate for the high dark current in graphene-based photodetectors and result in outstanding photoelectronic properties of those based on a graphene/MoX2 van der Waals heterostructure (vdWH). In this review, we firstly review working principles, performance indicators, and structures of photodetectors. After that, the significance of graphene/MoX2 vdWH photodetectors is highlighted from the fundamental perspective. Preparation methodologies and performance enhancement strategies of graphene/MoX2 vdWH photodetectors are correspondingly summarized. In the end, we highlight the current challenges and future directions of the graphene/MoX2 vdWH photodetectors. This review will guide the design of high-performance vdWH photodetectors.
A review of carbon material-based Z-scheme and S-scheme heterojunctions for photocatalytic clean energy generation
Sahil Rana, Amit Kumar, WANG Tong-tong, Gaurav Sharma, Pooja Dhiman, Alberto García-Penas
2024, 39(3): 458-482.   doi: 10.1016/S1872-5805(24)60857-7
Abstract(147) HTML(34) PDF(41)
Carbon materials, including carbon nanotubes/nanofibers, graphene, graphene oxide, reduced graphene oxide, graphyne, graphdiyne, carbon quantum dots and fullerenes, have received considerable attention in recent years because of their unique properties such as high conductivity, excellent stability and biocompatibility. The integration of these materials into Z-scheme and S-scheme heterojunctions has emerged as a transformative strategy to increase their photocatalytic efficiency for energy conversion applications. We first consider the fundamental principles of clean energy generation such as photocatalytic H2 generation and CO2 reduction, elucidating their respective mechanisms and advantages. Various types of carbon materials, their synthesis and construction of Z-scheme and S-scheme heterojunctions are then discussed, emphasizing their role in promoting charge separation, reducing recombination losses and extending the spectral response range. With a focus on solar energy production, recent advances in carbon-based Z-scheme and S-scheme heterojunctions are discussed and summarized for photocatalytic H2 generation and CO2 reduction. Lastly, the current problems in the field of carbon-based photocatalysts are discussed with insights for the future development of this field.
A review of the high-concentration processing, densification, and applications of graphene oxide and graphene
WANG Yue, LUO Jia-liang, LU Zhe-hong, DI Jun, WANG Su-wei, JIANG Wei
2024, 39(3): 483-505.   doi: 10.1016/S1872-5805(24)60856-5
Abstract(107) HTML(47) PDF(39)
Dense graphene assemblies, composed of tightly stacked graphene sheets, have outstanding chemical stability and excellent mechanical, thermal, and electrical properties. They also do not have the problems of low density, low mechanical strength, poor electrical conductivity, or poor thermal conductivity found in porous graphene aerogels, making them ideal materials for future portable electronic and smart devices. We summarize work on high-concentration graphene oxide (GO) and graphene dispersions prepared by mechanical dispersion, evaporation concentration, centrifugal concentration, and liquid phase exfoliation, as well as two-dimensional (2D) dense graphene-based films and three-dimensional (3D) dense graphene-based structures prepared by vacuum-assisted filtration, interfacial self-assembly, and press-forming, and evaluate the advantages and disadvantages of each method. The applications of dense graphene-based assemblies in energy storage, thermal management, and electromagnetic interference (EMI) shielding are summarized. Finally, their challenges and prospects in future research are outlined. This review provides a reference for exploring and developing their large-scale, cost-effective manufacture and use.
Research articles
Boron and nitrogen co-doped sodium alginate-based porous carbons for durable and fast Zn-ion hybrid capacitors
LU Ya-ping, WANG Hong-xing, LIU Lan-tao, PANG Wei-wei, CHEN Xiao-hong
2024, 39(3): 506-514.   doi: 10.1016/S1872-5805(24)60847-4
Abstract(213) HTML(75) PDF(72)
In recent years, zinc-ion hybrid capacitors (ZIHCs) have attracted increasing attention due to their environmental friendliness and excellent electrochemical properties. However, their performance is mainly limited by the electrochemical performance of the cathode, so it is necessary to develop an advanced cathode material. N, B co-doped sodium alginate-based porous carbon (NBSPC) was prepared by one-step co-carbonization using sodium alginate as the matrix and NH4B5O8 as the N and B source. This N, B co-doping strategy improves the pore structure of the carbon materials and increases the number of surface functional groups, greatly improving the capacitive behavior of the raw materials and thus improving their electrochemical performance. When used as the cathode in ZIHCs, the NBSPC had an excellent rate performance (85.4 mA h g1 even at ultra-high current density of 40 A g1) and good cycling stability (15 000 cycles at 20 A g1 with a capacity retention rate of 94.5%).
Controlled growth of a graphdiyne/cobalt hydroxide heterointerface for efficient chlorine production
LIU Hui-min, LUAN Xiao-yu, YAN Jia-yu, BU Fan-le, XUE Yu-rui, LI Yu-liang
2024, 39(3): 515-525.   doi: 10.1016/S1872-5805(24)60861-9
Abstract(125) HTML(56) PDF(38)
The chlor-alkali process plays a key and irreplaceable role in the chemical industry because of its use in various industrial processes. However, the low selectivity and efficiency of the reported chlorine evolution reaction (CER) electrocatalysts obviously hinder its practical use. We report a simple method for the controlled growth of high-performance CER electrocatalysts by first growing cobalt hydroxide on the surface of carbon cloth, followed by the in-situ growth of graphdiyne (GDY/Co(OH)2). As expected, the as-synthesized catalyst has a small overpotential of only 83 mV at 10 mA cm2, a maximum Faradaic Efficiency (FE) of 91.54%, and a high chlorine yield of 157.11 mg h1 cm2 in acidic simulated seawater. Experimental results demonstrate that the in-situ growth of GDY on the Co(OH)2 surface leads to the formation of heterointerfaces with strong electron transfer between GDY and Co atoms, resulting in a higher conductivity, larger active specific surface area and more active sites, thereby improving the overall electrocatalytic selectivity and efficiency.
Controllable construction of CoP nanoparticles anchored on a nitrogen-doped porous carbon as an electrocatalyst for highly efficient oxygen reduction in Zn-air batteries
YAN Xiao-li, WANG Kui, HAO Shu-wei, ZHOU Guang-da, YANG Hao-wei, ZHANG Hua, GUO Jun-jie
2024, 39(3): 526-537.   doi: 10.1016/S1872-5805(24)60848-6
Abstract(197) HTML(91) PDF(63)
Exploring cost-efficient and highly-efficient noble metal-free catalysts for the oxygen reduction reactions (ORRs) involved in sustainable energy devices remains a great challenge. Transition-metal phosphides supported on heteroatom-doped carbons have shown potential as alternative candidates for precious metals because of their tunable electronic structures and higher catalytic performance. Phosphating was used to construct CoP nanoparticles (NPs) anchored on a nitrogen-doped porous carbon framework (CoP@NC) from Co NPs loaded on NC, using PH3 gas released from NaH2PO2 during heat treatment. The dodecahedral structure of Co NPs was retained in their transformation to CoP NPs. The CoP@NC electrocatalyst shows a remarkable ORR activity with a half-wave potential up to 0.92 V under alkaline conditions, which is attributed to the combined coupling between the well dispersed CoP nanoparticles on the nitrogen-doped carbon and the efficient mass transport in the porous structure. Zinc-air batteries assembled with the CoP@NC electrocatalyst as a cathode have a high open-circuit voltage of 1.51 V and power density of 210.1 mW cm2. This work provides a novel strategy to develop low-cost catalysts with an excellent ORR performance to promote their practical use in metal-air batteries.
Sulfonyl chloride-intensified metal chloride intercalation of graphite for efficient sodium storage
LAN Shu-qin, REN Wei-cheng, WANG Zhao, YU Chang, YU Jin-he, LIU Ying-bin, XIE Yuan-yang, ZHANG Xiu-bo, WANG Jian-jian, QIU Jie-shan
2024, 39(3): 538-548.   doi: 10.1016/S1872-5805(24)60851-6
Abstract(124) HTML(46) PDF(49)
Metal chloride-intercalated graphite with excellent conductivity and a large interlayer spacing is highly desired for use in sodium ion batteries. However, halogen vapor is usually indispensable in initiating the intercalation process, which makes equipment design and experiments challenging. In this work, SO2Cl2 was used as a chlorine generator to intensify the intercalation of BiCl3 into graphite (BiCl3-GICs), which avoided the potential risks, such as Cl2 leakage, in traditional methods. The operational efficiency in the experiment was also improved. After the reaction of SO2Cl2, BiCl3, and graphite at 200 °C for 20 h, the synthesized BiCl3-GICs had a large interlayer spacing (1.26 nm) and a high amount of BiCl3 intercalation (42%), which gave SIBs a high specific capacity of 213 mAh g1 at 1 A g1 and an excellent rate performance (170 mAh g1 at 5 A g1). In-situ Raman spectra revealed that the electronic interaction between graphite and intercalated BiCl3 is weakened during the first discharge, which is favorable for sodium storage. This work broadly enables the increased intercalation of other metal chloride-intercalated graphites, offering possibilities for developing advanced energy storage devices.
Increasing the interlayer spacing and generating closed pores to produce petroleum coke-based carbon materials for sodium ion storage
ZHUANG Hong-kun, LI Wen-cui, HE Bin, LV Jia-he, WANG Jing-song, SHEN Ming-yuan, LU An-hui
2024, 39(3): 549-560.   doi: 10.1016/S1872-5805(24)60858-9
Abstract(137) HTML(61) PDF(65)
Petroleum coke (PC) is a valuable precursor for sodium-ion battery (SIB) anodes due to its high carbon content and low cost. The regulation of the microcrystalline state and pore structure of the easily-graphitized PC-based carbon is crucial for creating abundant Na+ storage sites. Here we used a precursor transformation strategy to increase the carbon interlayer spacing and generate abundant closed pores in PC-based carbon, significantly increasing its Na+ storage capacity in the plateau region. This was achieved by introducing a large number of oxygen functional groups through mixed acid treatment and then using high-temperature carbonization to decompose the oxygen functional groups and rearrange the carbon microcrystallites, resulting in a transition from open to closed pores. The optimized samples provide a large reversible capacity of 356.0 mAh g1 at 0.02 A g1, of which approximately 93% is below 1.0 V. Galvanostatic intermittent titration (GITT) and in-situ X-ray diffraction (XRD) analysis indicate that the sodium storage capacity in the low voltage plateau region involves a joint contribution of interlayer insertion and closed pore filling processes. This study presents a comprehensive method for the development of high-performance carbon anodes using low-cost and highly aromatic precursors.
Plasma-assisted preparation of NiCoAl-layered double hydroxides with a large interlayer spacing on carbon cloth for electrochemical deionization
JIANG Qiu-tong, WANG Guo-qing, LI Yi, HUANG Hong-wei, LI Qian, YANG Jian
2024, 39(3): 561-572.   doi: 10.1016/S1872-5805(24)60854-1
Abstract(234) HTML(100) PDF(61)

Capacitive deionization has been considered an emerging desalination technique in recent years, especially for its economic and energy-saving characteristics for brackish water. However, there are currently few studies on chloride ion removal electrodes, and the slow desalination kinetics limits their development. Ar-NiCoAl-layered double hydroxide (LDHs)@ACC materials with an increased interlayer spacing were prepared by the in-situ growth of NiCoAl-LDHs nanosheet arrays on acid-treated carbon cloth (ACC) and subsequent argon plasma treatment. The carbon cloth suppresses the agglomeration of the NiCoAl-LDHs nanosheets and improves the electrical conductivity, while the plasma treatment increases the interlayer spacing of NiCoAl-LDHs and improves its hydrophilicity. This provides rapid diffusion channels and more interlayer active sites for chloride ions, achieving high desalination kinetics. A hybrid capacitive deionization (HCDI) cell was assembled using Ar-NiCoAl-LDHs@ACC as the chloride ion removal electrode and activated carbon as the sodium ion removal electrode. This HCDI cell achieved a high desalination capacity of 93.26 mg g1 at 1.2 V in a 1 000 mg L1 NaCl solution, a remarkable desalination rate of 0.27 mg g1 s1, and a good charge efficiency of 0.97. The capacity retention remained above 85% after 100 cycles in a 300 mg L1 NaCl solution at 0.8 V. The work provides new ideas for the controlled preparation of two-dimensional metal hydroxide materials with a large interlayer spacing and the design of high-performance electrochemical chlorine ion removal electrodes.

Electrochemical methods for the removal of impurities from the graphite anode in spent ternary lithium-ion batteries
ZHANG Rui, TIAN Yong, ZHANG Wei-li, SONG Jia-yin, MIN Jie, PANG Bo, CHEN Jian-jun
2024, 39(3): 573-582.   doi: 10.1016/S1872-5805(24)60843-7
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The use of lithium-ion batteries (LIBs) is becoming increasingly widespread, and a large number are reaching their end of life. The recycling and re-use of spent LIBs has attracted great attention. Because of the unchanged layer structure of the graphite anode in these batteries, their recycling does not require high-temperature graphitization, and only focuses on the removal of internal impurities. We used electrochemical treatment for the deep removal of internal metal impurities after the heat treatment, ultrasonic separation, and acid leaching of spent graphite. By comparing and analyzing the graphite in different recovery stages, it was found that the presence of organic impurities seriously affects the electrochemical performance. The presence of trace inorganic impurities such as Cu and Fe has little effect on the initial discharge specific capacity, but reduces the cycling stability of graphite. The content of the main metal impurities in the final recycled graphite was less than 20 mg/kg. The discharge specific capacity reached 358.7 mAh/g at 0.1 C, and the capacity remained at 95.85% after 150 cycles. Compared with the reported methods for recycling spent graphite, this method can efficiently remove impurities in the graphite, solve the current problems of high acid and alkali consumption, incomplete impurity removal and high energy consumption. The recycled graphite anode has a good electrochemical performance. Our work provides a new recycling and regeneration path for spent LIB graphite anodes.

Recent progress in the preparation of ordered mesoporous carbons using a self-assembled soft template
HUANG Zheng-hong
2012, 27(05): 321-336.  
Abstract(2058) PDF(85)
The preparation of self-assembled ordered mesoporous carbons (SA-OMCs) using a soft template method has many advantages, such as low cost, ease of preparation and control. This paper review the development periods, the basic principles and preparation procedures with an emphasis on the control of morphology and multi-level pore structure of OMCs based on SA-OMCs. And suggest that further research in this area can be focused on expanding the scope of the precursor, improving the flexibility and conductivity of the shaped products, such as fibers and membranes.
Preparation of graphene by chemical vapor deposition
REN Wen-cai, GAO Li-bo, MA Lai-peng, CHENG Hui-ming
2011, 26(01): 71-80.  
Abstract(3570) PDF(438)
Chemical vapor deposition (CVD) is an effective way for the preparation of graphene with large area and high quality. In this review, the mechanism and characteristics of the four main preparation methods of graphene are briefly introduced, including micromechanical cleavage, chemical exfoliation, SiC epitaxial growth and CVD. The recent advances in the CVD growth of graphene and the related transfer techniques in terms of structure control, quality improvement and large area graphene synthesis were discussed. Other possible methods for the CVD growth of graphene were analyzed including the synthesis and nondestructive transfer of large area single crystalline graphene, graphene nanoribbons and graphene macrostructures.