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2023, 38(1)

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2023, 38(1): .

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Recent advances in porous carbons for electrochemical energy storage

LIU Yu-si, MA Chao, WANG Kai-xue, CHEN Jie-sheng

2023, 38(1): 1-17. doi: 10.1016/S1872-5805(23)60710-3

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Porous carbons are widely used in the field of electrochemical energy storage due to their light weight, large specific surface area, high electronic conductivity and structural stability. Over the past decades, the construction and functionalization of porous carbons have seen great progress. This review summarizes progress in the use of porous carbons in different energy storage devices, such as lithium-ion, lithium-oxygen, lithium-sulfur, and lithium-metal batteries for anode protection, sodium-ion and potassium-ion batteries, supercapacitors and metal ion capacitors. Methods for the synthesis and functionalization of porous carbons are discussed and the effects of their pore texture on the electrochemical performance of different energy storage systems are outlined. Strategies for their structural control are proposed, and the challenges and prospects for their use in energy storage devices are discussed.

A review of fibrous graphite materials: graphite whiskers, columnar carbons with a cone-shaped top, and needle- and rods-like polyhedral crystals

LIU Yu-hong, MA Zhao-kun, HE Yan, WANG Yue, ZHANG Xing-wei, SONG Huai-he, LI Cui-xia

2023, 38(1): 18-39. doi: 10.1016/S1872-5805(23)60719-X

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Fibrous graphite materials are highly attractive due to their unique morphologies, high degree of orientation of their graphite microcrystallites, extremely good mechanical and conductive properties, fascinating growth mechanisms, diverse preparation methods and potential applications. This review summarizes the preparation methods, Raman spectra and the growth mechanisms of graphite whiskers, columnar carbons with cone-shaped top cones, and needle- and rod-like polyhedral crystals, and their optical, electrical and magnetic properties and applications are outlined.

Biomass-derived carbon anodes for sodium-ion batteries

HUANG Si, QIU Xue-qing, WANG Cai-wei, ZHONG Lei, ZHANG Zhi-hong, YANG Shun-sheng, SUN Shi-rong, YANG Dong-jie, ZHANG Wen-li

2023, 38(1): 40-72. doi: 10.1016/S1872-5805(23)60718-8

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Sodium-ion batteries (SIBs) have attracted tremendous attention for large-scale stationary grid energy storage. With the upcoming commercialization of SIBs in the foreseeable future, developing high-performance carbon anodes from sustainable biomass is becoming increasingly important in the preparation of cost-effective SIBs. This review summarizes advanced carbon anodes for SIBs derived from various lignocellulose biomass waste. The history of our understanding of sodium storage mechanisms in carbon anodes is first discussed to clarify their structure-performance relationships. Conventional preparation strategies including pore structure design, heteroatom doping, control of the graphitic structure, and morphology control and their effects on the sodium storage capability of biomass-derived carbon anodes are then discussed. Finally, the practical applications, future research directions and challenges for the use of biomass-derived carbon anodes for SIBs are discussed from the aspects of synthesis methods, microstructure control and production costs.

Recent progress in the research and development of natural graphite for use in thermal management, battery electrodes and the nuclear industry

DUAN Sheng-zhi, WU Xiao-wen, WANG Yi-fan, FENG Jian, HOU Shi-yu, HUANG Zheng-hong, SHEN Ke, CHEN Yu-xi, LIU Hong-bo, KANG Fei-yu

2023, 38(1): 73-95. doi: 10.1016/S1872-5805(23)60717-6

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Natural graphite has many excellent properties such as high thermal and electrical conductivities, high temperature resistance, corrosion resistance, and radiation tolerance. It is widely used in many fields such as thermal management, battery electrodes, and the nuclear industry. The carbon content is an important factor that limits the applications of natural graphite minerals, but the impurities are difficult to remove from high-grade graphite minerals. This review discusses the types of natural graphite and mineral resources, followed by a discussion of traditional graphite purification processes and new methods to obtain high-purity graphite. Recent research on the development of natural graphite for use in thermal management, battery electrodes and the nuclear industry are summarized and the future applications of natural graphite are discussed.

Progress in the graphitization and applications of modified resin carbons

YANG Ping-jun, LI Tie-hu, LI Hao, DANG A-lei, YUAN Lei

2023, 38(1): 96-110. doi: 10.1016/S1872-5805(23)60715-2

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Resin carbons have favorable mechanical, electrical and thermal properties, and are widely used as structural and functional materials in aviation, aerospace and energy storage, etc. The inherent molecular structures of resins make their graphitization difficult, which greatly limits wide applications. Research progress on the graphitization and applications of resin carbons in recent years are reviewed. Their graphitized carbon content can be increased and their graphitization temperature reduced by adding catalysts, carbon nanomaterials and easily graphitized co-carbonization agents. Most studies have been devoted to increasing their graphitized carbon content using catalysts and carbon nanomaterials. The degree of graphitization of resin carbons at temperatures below 1400 °C can reach 74% by adding a catalyst, and above 2000 °C by adding carbon nanomaterials. Co-carbonization agents may increase their degree of graphitization and also their carbon yield. The thermal and electrical conductivities of carbon/carbon composites could be improved by increasing the degree of graphitization of resin carbons, and this would improve the conductivity, rate performance and power density of supercapacitors and secondary batteries. Challenges and research prospects for the graphitization of resin carbons and their applications are discussed.

Recent progress in increasing the electromagnetic wave absorption of carbon-based materials

LI Wen-yi, GAO Ming-yang, MIAO Yang, WANG Xiao-min

2023, 38(1): 111-129. doi: 10.1016/S1872-5805(23)60703-6

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High-performance electromagnetic wave absorbing materials (EWAMs) are expected to solve electromagnetic wave radiation problems in both the military and civil fields. The desired features of EWAMs include strong absorption over a broad bandwidth, low density, thinness, oxidation resistance, wear resistance, ability to withstand high-temperatures and high strength. Carbon-based materials, including nanostructures and composites, are attractive alternatives to EWAMs because of their unique structures and properties. We summarize recent achievements in carbon-based EWAMs, including different dimensional (0D, 1D, 2D and 3D) carbon nanostructures and various types of carbon composites (dielectric/carbon, magnetic/carbon) and hybrids. The factors affecting the absorption of electromagnetic microwaves include electrical conductivity (σ), permittivity (ε) and permeability (μ) are discussed based on the electromagnetic microwave absorption mechanisms. Representative carbon-based EWAMs and the corresponding mechanisms of improving their electromagnetic microwave absorption are highlighted and analyzed. Strategies for the modification of carbon-based EWAMs are summarized and research trends are proposed.

Status and development trends for fluorinated carbon in China

FENG wei

2023, 38(1): 130-142. doi: 10.1016/S1872-5805(23)60716-4

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Fluorinated carbon (CF_x) are a class of carbon derivatives with C―F bonds formed by the fluorination of carbon materials, including graphite, graphene, and carbon nanotubes. Because of their different carbon skeletons with polar C―F bonds, they have many excellent properties such as chemical stability, band gap adjustability and superhydrophobicity. Based on their structure and properties, we review the status and development trends of CF_x for use in chemical energy, lubrication and semiconductors in recent years in China. We discuss the industrialization of CF_x in China and the main reasons for their limited use in civil fields, as well as the problems and future development opportunities of CF_x, which suggests some practical applications.

Nitrogen doped hollow porous carbon fibers derived from polyacrylonitrile for Li-S batteries

NIU Jing-yi, JING De-qi, ZHANG Xing-hua, SU Wei-guo, ZHANG Shou-chun

2023, 38(1): 143-153. doi: 10.1016/S1872-5805(22)60615-2

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Hollow porous carbon fibers for Li-S battery electrodes were prepared by the KOH activation of carbon prepared from hollow polyacrylonitrile fibers. The fibers had a high specific surface area of 2 491 m²·g⁻¹, a large pore volume of 1.22 cm³·g⁻¹ and an initial specific capacity of 330 mAh·g⁻¹ at a current density of 1 C. To improve their electrochemical performance, the fibers were modified by treatment with hydrazine hydrate to prepare nitrogen-doped hollow porous carbon fibers with a specific surface area of 1 690 m²·g⁻¹, a pore volume of 0.84 cm³·g⁻¹ and a high nitrogen content of 8.81 at%. Because of the increased polarity and adsorption capacity produced by the nitrogen doping, the initial specific capacity of the fibers was increased to 420 mAh·g⁻¹ at a current density of 1 C.

The synthesis of iron-nitrogen sites embedded in electrospun carbon nanofibers with an excellent oxygen reduction reaction activity in alkaline/acidic media

XU Xiang-xiang, ZHANG Nian-chao, WANG Jun-ying, WANG Jun-zhong

2023, 38(1): 154-161. doi: 10.1016/S1872-5805(22)60649-8

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Metal-nitrogen carbon catalysts have received great attention in the field of gas-evolving electrocatalysis due to their high activity, large specific surface area and efficient gas diffusion paths. A solution of porphyrin iron, g-C₃N₄ and polyacrylonitrile in N,N-dimethylformamide was sonicated and electrospun into doped polyacrylonitrile nanofibers (NFs), and the NFs were then stabilized and carbonized at 900 °C to prepare Fe-N/CNF catalyst for oxygen reduction reaction (ORR). It was found that the addition of g-C₃N₄ to the electrospinning precursor led to the formation of abundant Fe-N species in Fe³⁺ and Fe²⁺ valence states, while Fe₃C nanoparticles were formed without adding g-C₃N₄. Compared to Fe₃C/CNF prepared without g-C₃N₄, the Fe-N/CNF catalyst presents an 4e⁻ improved oxygen reduction reaction activity in both alkaline and acidic media. Furthermore, as a cathode in Zn-air batteries, the Fe-N/CNF catalyst exhibits high performance with an open-circuit voltage of 1.49 V, a power density of 146 mW cm⁻² and a specific capacity of 703 mAh g⁻¹. This work suggests a way to prepare metal-nitrogen-carbon catalysts for energy-related electrocatalytic applications.

Preparation of carbon nanotube/cellulose hydrogel composites and their uses in interfacial solar-powered water evaporation

WANG Xue, SUN Yang, ZHAO Guan-yu, WANG Xu-zhen, QIU Jie-shan

2023, 38(1): 162-172. doi: 10.1016/S1872-5805(22)60621-8

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Cellulose extracted from corncobs, a bulk agricultural waste product, by a solvent at −12 °C, was composited with carbon nanotubes (CNTs) with excellent light absorption properties to construct CNT/cellulose hydrogel composites. Taking advantage of the superior water retention ability and degradability of cellulose hydrogels, and the high-efficiency solar-thermal conversion performance, excellent mechanical properties and biocompatibility of CNTs, CNT/cellulose hydrogel composites are used in water purification by interfacial solar-powered evaporation. The effects of the addition of CNTs on the solar energy absorption, mechanical properties and interfacial solar-thermal water evaporation efficiency of the composites were investigated. With an optimum CNT content of 0.2 wt.%, the composite had an average evaporation rate of ~1.52 kg m⁻² h⁻¹ and a solar-steam conversion efficiency of about 92%. After continuous evaporation in seawater for 8 h, the evaporation rate of the composite remained at about 1.37 kg m⁻² h⁻¹ without salt precipitation, indicating its strong resistance to salt. The quality of the purified water was superior to the WHO and EPA standards for drinking water. When the composite was used in concentrated acid/alkaline aqueous systems, dye wastewater and heavy metal ion polluted water, the evaporation rates remained in the range 1.30-1.40 kg m⁻² h⁻¹, and the solar-steam conversion efficiencies reached 80-86%. The retention rates for both organic pollutants and salt were as high as 99.9%, confirming the evaporation stability of the composite. This work indicates that an evaporator based on the composite has broad application prospects in the fields of seawater desalination and industrial wastewater purification.

An innovative and efficient method for the preparation of mesocarbon microbeads and their use in the electrodes of lithium ion batteries and electric double layer capacitors

DONG Si-lin, YANG Jian-xiao, CHANG Sheng-kai, SHI Kui, LIU Yue, ZOU Jia-ling, LI Jun

2023, 38(1): 173-189. doi: 10.1016/S1872-5805(22)60606-1

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An innovative and efficient method for preparation of mesocarbon microbeads (MCMBs) was developed based on the dripping behavior and rheological properties of molten pitch during melt-spinning, where a string of beads was formed after the pitch was extruded from spinnerets and dropped into a receiving solvent (tetrohydrofuran or water). The pitch droplets were first carbonized, then activated by KOH or graphitized at 2800 °C to prepare A-MCMBs or G-MCMBs, respectively, and these were respectively used as the electrode materials for electric double layer capacitors (EDLCs) and lithium-ion batteries (LIBs). Results showed that both MCMB-W prepared using water as the receiving solvent and MCMB-T prepared using tetrohydrofuran as the receiving solvent had a spherical shape with sizes of 1-2 μm. A-MCMB-T had a high specific surface area (1 391 m² g⁻¹), micropore volume (0.55 cm³ g⁻¹) and mesopore volume (0.24 cm³ g⁻¹), with a 30% higher specific capacitance than an activated mesophase carbon prepared under the same conditions, and its capacitance retention was significantly improved when it was used as an electrode material for EDLCs. G-MCMB-T had a high degree of graphitization (0.895) and when it was used as an electrode material for LIBs it had a high specific capacity of 353.5 mAh g⁻¹ after 100 cycles at 100 mA g⁻¹. This work reports a new preparation method for MCMBs, which could be used to prepare energy storage materials.

Se with Se-C bonds encapsulated in a honeycomb 3D porous carbon as an excellent performance cathode for Li-Se batteries

XIA Zhi-gang, ZHANG Jing-jing, FAN Mei-qiang, LV Chun-ju, CHEN Zhi, LI Chao

2023, 38(1): 190-199. doi: 10.1016/S1872-5805(22)60596-1

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Li-Se batteries have risen to prominence as promising lithium-ion batteries thanks to their ultrahigh volumetric energy density and the high electrical conductivity of Se. However, the use of Li-Se batteries is limited not only by the large volume expansion and dissolution of polyselenides in the cathodes during cycling, but also the low selenium loading. A highly effective and currently feasible approach to simultaneously tackle these problems is to position the selenium in a carbon matrix with a sufficient pore volume to accommodate the expansion while increasing the interfacial interaction between the selenium and carbon. We have synthesized a novel cathode material (Se@HPC) for Li-Se batteries of a honeycomb 3D porous carbon derived from a tartrate salt, that was impregnated with Se to produce Se-C bonds. The pore volume of the honeycomb 3D porous carbon was as high as 1.794 cm³ g⁻¹, which allowed 65 wt% selenium to be uniformly encapsulated. Moreover, the strong chemical bonds between selenium and carbon stabilize the selenium, thus inhibiting its huge volume expansion and the dissolution of polyselenides, and promoting charge transfer during cycling. As expected, a Se@HCP cathode has excellent cyclability and a good rate performance. After 200 cycles at 0.2 C, its specific capacity remains at 561 mA h g⁻¹, 83% of the theoretical value, and decays by only 0.058% per cycle. It also has a large capacity of 472.8 mA h g⁻¹ under a high current density of 5 C.

A carbon catalyst doped with Co and N derived from the metal-organic framework hybrid (ZIF-8@ZIF-67) for efficient oxygen reduction reaction

ZHANG Ya-ting, LI Si-yi, ZHANG Na-na, LIN Gang, WANG Rui-qi, YANG Meng-nan, LI Ke-ke

2023, 38(1): 200-210. doi: 10.1016/S1872-5805(22)60609-7

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Carbon-based catalysts for the oxygen reduction reaction (ORR) are considered potential substitutes for the expensive platinum-based catalysts. Recently, transition metal and nitrogen co-doped carbon materials (M-N-C) have attracted much attention from researchers due to their low cost and excellent activity. A cobalt- and nitrogen-co-doped porous carbon material (Co-N@CNT-C800) was prepared by the simple one-step pyrolysis of a star fruit-like MOF hybrid (ZIF-8@ZIF-67) at 800 °C. It consisted of CNTs with substantial Co and N co-doping and had a large surface area (428 m²·g⁻¹). It had an excellent half-wave potential and good current density in alkaline media in the ORR with values of 0.841 V and 5.07 mA·cm⁻², respectively. Compared with commercial Pt/C materials it also had excellent electrochemical stability and methanol tolerance. This research provides an effective way to fabricate low cost, high activity electrocatalysts for use in energy conversion.

2023 Vol. 38, No. 1

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