Status and Opportunities of Zinc Ion Hybrid Capacitors: Focus on Carbon Materials, Current Collectors, and Separators

Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.

Mechanochemical synthesis of oxygenated alkynyl carbon materials with excellent Hg(Ⅱ) adsorption performance from CaC2 and carbonates

Adsorptive removal of heavy metal ions from wastewater is very important,and the key is the development of efficient sorbents.In this work,oxygenated alkynyl carbon materials(OACMs)were synthesized via mechanochemical reaction of CaC_(2) and a carbonate(CaCO_(3),Na2CO_(3),or NaHCO_(3))at ambient temperature.The resultant OACMs are micro mesoporous carbon nanomaterials with high specific area(>648 m2 g^(-1)),highly crosslinked texture,and rich alkynyl and oxygenated groups.The OACMs exhibit excellent Hg(Ⅱ)adsorption due to the soft acid-soft base interaction between alkynyl and Hg(Ⅱ),and OACM-3 derived from CaC_(2) and NaHCO_(3) has the saturated Hg(Ⅱ)adsorbance of 483.9 mg g^(-1)along with good selectivity and recyclability.The adsorption is mainly chemisorption following the Langmuir mode.OACM-3 also shows high adsorbance for other heavy metal ions,e.g.256.6 mg g^(-1)for Pb(II),232.4 mg g^(-1)for Zn(II),and 198.7 mg g^(-1)for Cu(II).This work expands the mechnochemical reaction of CaC_(2)with carbonates and possibly other oxyanionic salts,provides a new synthesis approach for functional alkynyl carbon materials with excellent adsorption performance for heavy metal ions,as well as a feasible approach for CO2 resource utilization.

The influence of composition of asphaltenes of different genesis on the properties of carbon materials manufactured from them by plasma processing

The results of experimental studies of carbon materials, which are formed in the plasma of a direct current (DC) arc discharge initiated in open air from the asphaltenes of different origins, extracted from the natural asphaltite and from the oil of the Sredne-Ugutskoye Oilfield, are presented. The influence of the initial asphaltene composition on the composition and properties of the resulting carbon materials is analyzed. The initial asphaltenes and the samples of the carbon materials are characterized by the methods of X-ray diffraction, differential thermal analysis, X-ray fluorescence analysis, IR-Fourier spectroscopy, laser diffraction, transmission and scanning electron microscopy. The changes in the composition and structure of the asphaltenes are determined before and after their plasma treatment and the hypotheses are put forward concerning the chemical processes causing the changes in the molecular structure of the samples. As a result of plasma treatment of asphaltenes (100 A, 30 s), it was shown that graphitization occurs, as well as oxidation, and a decrease in sulfur content. Moreover, nanotubes and nano-onions have been detected using electron microscopy. Petroleum asphaltenes after plasma treatment give a less thermostable carbon material, but with a lower content of heteroatoms, and with a large amount of sulfur in the composition of sulfoxide structural fragments. This method is shown to be a promising technology for processing the petroleum feedstock enriched with heavy asphaltene components for the manufacture of carbon nanomaterials: nanotubes, nano-onions and polyhedral graphite.

Spectral and Morphological Analysis of Graphene-Based Two- Dimensional Carbon Materials

This paper describes the spectral and morphological analysis of graphene, N-doped graphene, and graphenemodified with functional groups. The similarities and differences in the surface and microstructure are characterizedby infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, andtransmission electron microscopy. Compared with high-purity graphene, the introduction of functional groups leads to moredefects in the two-dimensional structure. The quality of graphene, reflected by the intensity ratio of peak D and G modesin the Raman spectroscopy, is consistent with that observed by scanning electron microscopy and transmission electronmicroscopy. The infrared spectra of graphene-based two-dimensional carbon materials are different from that of high-puritygraphene, and the absorption peaks of the functional groups are obvious. The X-ray photoelectron spectroscopy resultsillustrate the diverse chemical states of carbon, and the atomic ratio of carbon to oxygen directly reflects the quality ofthe graphene-based materials. The results of electron microscopy and spectroscopic characterization of graphene samplesprovide an excellent basis for a wide range of applications in graphene production and quality control.

Preparation and oxidation resistance of mullite/SiC coating for carbon materials at 1150 ℃

To protect carbon materials from oxidation, mullite/SiC coatings were prepared on graphite by chemical vapor reaction (CVR) and slurry sintering. The XRD analyses show that the phase of the outer-layer coating is composed of SiO2 and mullite, and the inner-layer coating is mainly composed of β-SiC. The anti-oxidation behavior of the coating and the Rockwell hardness (HRB) of the coating after oxidation were investigated. The oxidation test shows that the as-prepared multi-layer coating exhibits excellent antioxidation and thermal shock resistance at high temperature. After oxidation at 1150 ℃ for 109 h and thermal shock cycling between 1150 ℃ and room temperature for 12 times, the mass gain of the coated sample is 0.085%. Meanwhile, the indentation tests also demonstrate that the as-prepared coating has good bonding ability between the layers.

A perspective on carbon materials for future energy application

Nanocarbon materials play a critical role in the development of new or improved technologies and devices for sustainable production and use of renewable energy. This perspective paper defines some of the trends and outlooks in this exciting area, with the effort of evidencing some of the possibilities offered from the growing level of knowledge, as testified from the exponentially rising number of publications, and putting bases for a more rational design of these nanomaterials. The basic members of the new carbon family are fullerene, graphene, and carbon nanotube. Derived from them are carbon quantum dots, nanohorn, nanofiber, nano ribbon, nanocapsulate, nanocage and other nanomorphologies. Second generation nanocarbons are those which have been modified by surface functionalization or doping with heteroatoms to create specific tailored properties. The third generation of nanocarbons is the nanoarchitectured supramolecular hybrids or composites of the first and second genera- tion nanocarbons, or with organic or inorganic species. The advantages of the new carbon materials, relating to the field of sustainable energy, are discussed, evidencing the unique properties that they offer for developing next generation solar devices and energy storage solutions.

Carbon materials for stable Li metal anodes: Challenges, solutions, and outlook

Lithium(Li)metal is regarded as the ultimate anode for next-generation Li-ion batteries due to its highest specific capacity and lowest electrochemical potential.However,the Li metal anode has limitations,including virtually infinite volume change,nonuniform Li deposition,and an unstable electrode-electrolyte interface,which lead to rapid capacity degradation and poor cycling stability,significantly hindering its practical application.To address these issues,intensive efforts have been devoted toward accommodating and guiding Li deposition as well as stabilizing the interface using various carbon materials,which have demonstrated excellent effectiveness,benefiting from their vast variety and excellent tunability of the structure-property relationship.This review is intended as a guide through the fundamental challenges of Li metal anodes to the corresponding solutions utilizing carbon materials.The specific functionalities and mechanisms of carbon materials for stabilizing Li metal anodes in these solutions are discussed in detail.Apart from the stabilization of the Li metal anode in liquid electrolytes,attention has also been paid to the review of anode-free Li metal batteries and solid-state batteries enabled by strategies based on carbon materials.Furthermore,we have reviewed the unresolved challenges and presented our outlook on the implementation of carbon materials for stabilizing Li metal anodes in practical applications.

Research progress on carbon materials as negative electrodes in sodium-and potassium-ion batteries

Carbon materials,including graphite,hard carbon,soft carbon,graphene,and carbon nanotubes,are widely used as high-performance negative electrodes for sodium-ion and potassium-ion batteries(SIBs and PIBs).Compared with other materials,carbon materials are abundant,low-cost,and environmentally friendly,and have excellent electrochemical properties,which make them especially suitable for negative electrode materials of SIBs and PIBs.Compared with traditional carbon materials,modifications of the morphology and size of nanomaterials represent effective strategies to improve the quality of electrode materials.Different nanostructures make different contributions toward improving the electrochemical performance of electrode materials,so the synthesis of nanomaterials is promising for controlling the morphology and size of electrode materials.This paper reviews the progress made and challenges in the use of carbon materials as negative electrode materials for SIBs and PIBs in recent years.The differences in Na+and K+storage mechanisms among different types of carbon materials are emphasized.

Comparative study on chalcopyrite bioleaching with assistance of different carbon materials by mixed moderate thermophiles

The catalysis of four carbon materials including artificial graphite(AG), carbon black(CB), activated carbon(AC) and carbon nanotube(CN) on chalcopyrite bioleaching by mixed moderate thermophiles was comparatively investigated. In AC and AG added bioleaching groups, low solution pH and suitable redox potential values, high total iron and ferric iron concentrations, and large number of adsorbed bacteria were obtained, resulting in high copper extractions. CB and CN inhibited the growth of bioleaching bacteria and led to the low bioleaching efficiency.X-ray diffraction analysis showed that jarosite and sulfur film were the main components of passivation layer with the addition of AG and AC,but did not hinder the dissolution of chalcopyrite. Microbial community structures of free and attached cells in AC and AG added groups changed dramatically compared with mixed moderate thermophiles. The sulfur-oxidizing bacteria of A. caldus S1 strain dominated the microbial community(93%-98%) at the end of bioleaching.The iron-oxidizing bacteria of L.ferriphilum YSK only accounted for low percentage(1%-2%).

Adsorption of phenol from aqueous solution by a hierarchical micro-nano porous carbon material

A hierarchical micro-nano porous carbon material (MNC) was prepared using expanded graphite (EG), sucrose, and phosphoric acid as raw materials, followed by sucrose-phosphoric acid solution impregnation, solidification, carbonization and activation. Nitrogen adsorption and mercury porosimetry show that mixed nanopores and micropores coexist in MNC with a high specific surface area of 1978 m2·g-1 and a total pore volume of 0.99 cm3·g-1. In addition, the MNC is found to consist of EG and activated carbon with the latter deposited on the interior and the exterior surfaces of the EG pores. The thickness of the activated carbon layer is calculated to be about one hundred nanometers and is further confirmed by scanning electron microscope (SEM) and transmission election microscope (TEM). A maximum static phenol adsorption of 241.2 mg·g-1 was obtained by using MNC, slightly higher than that of 220.4 mg·g-1 by using commercial activated carbon (CAC). The phenol adsorption kinetics were investigated and the data fitted well to a pseudo-second-order model. Also, an intra-particle diffusion mechanism was proposed. Furthermore, it is found that the dynamic adsorption capacity of MNC is nearly three times that of CAC. The results suggest that the MNC is a more efficient adsorbent than CAC for the removal of phenol from aqueous solution.

Functional carbon materials for high-performance Zn metal anodes

The realization of“carbon peak”and“carbon neutralization”highly depends on the efficient utilization of renewable energy sources.Exploring reliable and low-cost electrochemical energy storage systems is an ever-growing demand for renewable energy integration.Among available candidates,aqueous zinc-ion batteries(AZIBs)receive extensive researchers'attention because of their material abundance,high capacity,high safety,and environmental friendliness.However,the irreversible issues of Zn anode in terms of notorious dendric Zn growth,Zn corrosion/hydrogen evolution,and passivation significantly impede the commercialization of high-performance AZIBs.Carbon materials have advantages of large specific surface area,low cost,high electrical conductivity,controllable structure,and good stability.Their application provides remedies for improving the comprehensive performance of Zn anodes.In this review,the fundamentals and issues of Zn anodes,and the research progress with functional carbon materials for Zn anodes in recent years are presented.Three major strategies are described in detail,including the use of carbon materials(carbon nanotubes,graphene,carbon fiber,metal-organic framework(MOF)derived host,etc.)as Zn plating/stripping substrates,as protective coating layers on Zn,and as electrolyte additives.Finally,the remaining challenges and perspectives of carbon materials in high-performance AZIBs are outlined.

Carbon materials from melamine sponges for supercapacitors and lithium battery electrode materials: A review

With the increasing energy demand together with the deteriorating environment and decreasing fossil fuel resources,the development of highly efficient energy conversion and storage devices is one of the key challenges of both fundamental and applied research in energy technology.Melamine sponges(MS)with low density,high nitrogen content,and high porosity have been used to design and obtain three‐dimensional porous carbon electrode materials.More importantly,they are inexpensive,environment‐friendly,and easy to synthesize.There have been many reports on the modification of carbonized MS and MS‐based composites for supercapacitor and lithium battery electrode materials.In this paper,recent studies on the fabrication of electrode materials using MS as raw materials have been mainly reviewed,including carbonation,doping activation,and composite modification of MS,and expectations for the development of porous carbon materials for energy storage as a reference with excellent performance,environment‐friendliness,and long life.

Promise of commercialization: Carbon materials for low-cost perovskite solar cells

Perovskite solar cells （PVSCs） have attracted extensive studies due to their high power conversion efficiency （PCE） with low-cost in both raw material and processes. However, there remain obstacles that hinder the way to their commer- cialization. Among many drawbacks in PVSCs, we note the problems brought by the use of noble metal counter electrodes （CEs） such as gold and silver. The costly Au and Ag need high energy-consumption thermal evaporation process which can be made only with expensive evaporation equipment under vacuum. All the factors elevate the threshold of PVSCs＇ commercialization. Carbon material, on the other hand, is a readily available electrode candidate for the application as CE in the PVSCs. In this review, endeavors on PVSCs with low-cost carbon materials will be comprehensively discussed based on different device structures and carbon compositions. We believe that the PVSCs with carbon-based CE hold the promise of commercialization of this new technology.

Recent progress on MOF-derived carbon materials for energy storage

Metal-organic frameworks(MOFs)are of quite a significance in the field of inorganic-organic hybrid crystals.Especially,MOFs have attracted increasing attention in recent years due to their large specific surface area,desirable electrical conductivity,controllable porosity,tunable geometric structure,and excellent thermal/chemical stability.Some recent studies have shown that carbon materials prepared by MOFs as precursors can retain the privileged structure of MOFs,such as large specific surface area and porous structure and,in contrast,realize in situ doping with heteroatoms(eg,N,S,P,and B).Moreover,by selecting appropriate MOF precursors,the composition and morphology of the carbon products can be easily adjusted.These remarkable structural advantages enable the great potential of MOF-derived carbon as high-performance energy materials,which to date have been applied in the fields of energy storage and conversion systems.In this review,we summarize the latest advances in MOF-derived carbon materials for energy storage applications.We first introduce the compositions,structures,and synthesis methods of MOF-derived carbon materials,and then discuss their applications and potentials in energy storage systems,including rechargeable lithium/sodium-ion batteries,lithium-sulfur batteries,supercapacitors,and so forth,in detail.Finally,we put forward our own perspectives on the future development of MOF-derived carbon materials.

The application of carbon materials in nonaqueous Na‐O2 batteries

Na‐O2 batteries are advantageous as the candidates of next‐generation electric vehicles due to their ultrahigh theoretical energy density and have attracted enormous attention recently.Tremendous efforts have been devoted to improve the Na‐O2 battery performance by designing advanced electrodes with various carbonbased materials.Carbon materials used in Na‐O2 batteries not only function as the air electrode to provide active sites and accommodate discharge products but also as Na anode protectors against dendrite growth and chemical/electrochemical corrosion.In this review,we mainly focus on the application of various carbonbased materials in Na‐O2 batteries and highlight their advances.The scientific understanding on the fundamental design of the material microstructure and chemistry in relation to the battery performance are summarized.Finally,perspectives on enhancing the overall battery performance based on the optimization and rational design of carbon‐based cell components are also briefly anticipated.

Honeycomb-like carbon materials derived from coffee extract via a “salty” thermal treatment for high-performance Li-I2 batteries

Sustainable,conductive,and porous carbon materials are ideal for energy storage materials.In this study,honeycomb-like carbon materials(HCM)are synthesized via a“salty”thermal treatment of abundant and sustainable coffee extract.Systematic materials characterization indicates that the as-prepared HCM consists of heteroatoms(N and O,etc.)doped ultra-thin carbon framework,possesses remarkable specific surface area,and excellent electrical conductivity.Such properties bestow HCM outstanding materials to be the blocking layer for Li-I2 battery,significantly eliminating the dissolution of I2 in the cathode region and stopping the I2 from shutting to anode compartment.Furthermore,our electrochemical investigation suggests that HCM could incur surface pseudo-capacitive iodine-ions charge storage and contribute additional energy storage capacity.As a result,the resultant Li-I2 battery achieves a robust and highly reversible capacity of 224.5 mAh·g−1 at the rate of 10 C.Even under a high rate of 50 C,the remarkable capacity of the as-prepared Li-I2 battery can still be maintained at 120.2 mAh·g−1 after 4000 cycles.

Carbon material-based anodes in the microbial fuel cells

For the performance improvement of microbial fuel cells(MFCs),the anode becomes a breakthrough point due to its influence on bacterial attachment and extracellular electron transfer(EET).On other level,carbon materials possess the following features:low cost,rich natural abundance,good thermal and chemical stability,as well as tunable surface properties and spatial structure.Therefore,the development of carbon materials and carbon-based composites has flourished in the anode of MFCs during the past years.In this review,the major carbon materials used to decorate MFC anodes have been systematically summarized,based on the differences in composition and structure.Moreover,we have also outlined the carbon material-based hybrid biofilms and carbon material-modified exoelectrogens in MFCs,along with the discussion of known strategies and mechanisms to enhance the bacteria-hosting capabilities of carbon material-based anodes,EET efficiencies,and MFC performances.Finally,the main challenges coupled with some exploratory proposals are also expounded for providing some guidance on the future development of carbon material-based anodes in MFCs.

An Approach for Preparation of Excellent Antiwear PTFE Nanocomposites by Filling As-prepared Carbon Nanotubes/Nanorods(CNT/CNR)Mixed Nano-Carbon Material

The one-dimensional carbon nanotubes/nanorods(CNT/CNR)mixed nano-carbon material was successfully prepared by halloysite nanotubes(HNTs)as the template for the first time,in which CNT was formed through PVA modification in internal surface of HNTs and CNR was obtained by nanocasting PVA in hollow nanostructure of HNTs.The CNT of the mixture with flexible structure has ca.20 nm in pore diameter and ca.500 nm in length,whereas the CNR with hard and solid structure shows ca.30 nm in diameter and ca.2μm in length.For application as fillers,the CNT/CNR mixed nano-material is used to reinforce the properties of polytetrafluoroethylene(PTFE).The mechanical and tribological properties of PTFE nanocomposites were intensively examined by a series of testing.The ring-on-ring counterface was used to evaluate the tribological behavior of the nanocomposites.The results showed that the volume wear rate of the CNT/CNR-reinforced PTFE nanocomposite after being filled with 0.3%of CNT/CNR was only 1/700 of that of the pure PTFE under a load of 200 N and a rotary speed of 200 r/min,while other mechanical and tribological performance was comparable to the performance of pure PTFE,which exhibited a desirable application prospect.

Carbon materials:The burgeoning promise in electronics

Current electronic technology based on silicon is approaching its physical and scientific limits. Carbon-based devices have numer- ous advantages for next generation electronics (e.g., fast speed, low power consumption and simple process), that when combined with the unique nature of the versatile allotropes of carbon elements, are creating an electronics revolution. Carbon electronics are greatly advancing with new preparations and sophisticated designs. In this perspective, representatives with various dimensions, e.g., carbon nanotubes, graphene, bulk diamond, and their extraordinary performance, are reviewed. The associated state-of-the-art devices and composite hybrid all-carbon structures are also emphasized to reveal their potential in the electronics field. Advances in commercial production have improved the cost effi-ciency, material quality, and device design, accelerating the promise of carbon materials.

Converting furfural residue wastes to carbon materials for high performance supercapacitor

Sustainable development based on the value-added utilization of furfural residues(FRs)is an effective way to achieve a profitable circular economy.This comprehensive work highlights the potential of FRs as precursor to prepare porous carbons for high performance supercapacitors(SCs).To improve the electrochemical performance of FR-based carbon materials,a facile route based on methanol pretreatment coupled with pre-carbonization and followed KOH activation is proposed.More defects could be obtained after methanol treatment,which is incline to optimize textural structure.The activated methanol treated FR-based carbon materials(AFRMs)possess high specific surface area(1753.5 m^(2) g^(-1)),large pore volume(0.85 cm^(3) g^(-1)),interconnected micro/mesoporous structure,which endow the AFRMs with good electrochemical performance in half-cell(326.1 F g^(-1) at 0.1 Ag^(-1),189.4 Fg^(-1) at 50 A g^(-1) in 6 mol L^(-1) KOH).The constructed symmetric SCs based on KOH,KOH–K_(3)Fe(CN)_(6) and KOH-KI electrolyte deliver energy density up to 8.9,9.9 and 10.6 Wh kg^(-1) with a capacitance retention of over 86%after 10,000 cycles.Furthermore,the self-discharge can be restrained by the addition of K_(3)Fe(CN)_(6) and KI in KOH electrolyte.This study provides an effective approach for high-valued utilization of FR waste.