A Review on Engineering Transition Metal Compound Catalysts to Accelerate the Redox Kinetics of Sulfur Cathodes for Lithium–Sulfur Batteries

Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.

Regulating solid electrolyte interphases on phosphorus/carbon anodes via localized high-concentration electrolytes for potassium-ion batteries

The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.

Depolarization of Li-rich Mn-based oxide via electrochemically active Prussian blue interface providing superior rate capability

The high-rate cyclability of Li-rich Mn-based oxide(LMO)is highly limited by the electrochemical polarization resulting from the slow kinetic of the Li2MnO3 phase.Herein,the Prussian blue(PB)coating layer with specific redox potential is introduced as a functionalized interface to overcome the side effect and the escaping of O on the surface of LMO,especially its poor rate capability.In detail,the PB layer can restrict the large polarization of LMO by sharing overloaded current at a high rate due to the synchronous redox of PB and LMO.Consequently,an enhanced high rate performance with capacity retention of 87.8%over 300 cycles is obtained,which is superior to 50.5%of the pristine electrode.Such strategies on the high-rate cyclability of Li-rich Mn-based oxide compatible with good low-rate performances may attract great attention for pursuing durable performances.

液体丁腈橡胶增韧丁腈橡胶/硫酸铜复合材料的制备及再加工性能

在笔者课题组之前的工作中,成功地制备和分析了无水硫酸铜(CuSO_(4))填充丁腈橡胶(NBR)复合材料(NBR/CuSO_(4)),结果表明,CuSO_(4)的加入有效地提高了橡胶的强度,但同时也牺牲了断裂伸长率和可回收性,其实际应用受到了限制。文中使用低分子量的液体丁腈橡胶(LNBR)增韧NBR/CuSO_(4),并制备了具有高力学性能和优异可回收性的NBR/CuSO_(4)/LNBR复合材料。X射线衍射、硫化曲线、差示扫描量热分析结果表明,LNBR对CuSO_(4)与NBR的配位反应具有抑制作用;扫描电镜结果表明,LNBR降低了NBR/CuSO_(4)的交联密度。当LNBR的含量为4 phr时,断裂伸长率为583.0%、拉伸强度高达34.2 MPa、断裂能为71.58 MJ/m^(3)。此外,LNBR的加入促进了Cu-腈基(—CN)配位键的断裂和重建,从而提高了NBR/CuSO_(4)/LNBR复合材料的回收能力,其中的一种复合材料经二次加工后的回收率保持在93.6%。

Model reduction of fractional impedance spectra for time–frequency analysis of batteries, fuel cells, and supercapacitors

Joint time–frequency analysis is an emerging method for interpreting the underlying physics in fuel cells,batteries,and supercapacitors.To increase the reliability of time–frequency analysis,a theoretical correlation between frequency-domain stationary analysis and time-domain transient analysis is urgently required.The present work formularizes a thorough model reduction of fractional impedance spectra for electrochemical energy devices involving not only the model reduction from fractional-order models to integer-order models and from high-to low-order RC circuits but also insight into the evolution of the characteristic time constants during the whole reduction process.The following work has been carried out:(i)the model-reduction theory is addressed for typical Warburg elements and RC circuits based on the continued fraction expansion theory and the response error minimization technique,respectively;(ii)the order effect on the model reduction of typical Warburg elements is quantitatively evaluated by time–frequency analysis;(iii)the results of time–frequency analysis are confirmed to be useful to determine the reduction order in terms of the kinetic information needed to be captured;and(iv)the results of time–frequency analysis are validated for the model reduction of fractional impedance spectra for lithium-ion batteries,supercapacitors,and solid oxide fuel cells.In turn,the numerical validation has demonstrated the powerful function of the joint time–frequency analysis.The thorough model reduction of fractional impedance spectra addressed in the present work not only clarifies the relationship between time-domain transient analysis and frequency-domain stationary analysis but also enhances the reliability of the joint time–frequency analysis for electrochemical energy devices.

MXene Key Composites:A New Arena for Gas Sensors

With the development of science and technology,the scale of industrial production continues to grow,and the types and quantities of gas raw materials used in industrial production and produced during the production process are also constantly increasing.These gases include flammable and explosive gases,and even contain toxic gases.Therefore,it is very important and necessary for gas sensors to detect and monitor these gases quickly and accurately.In recent years,a new two-dimensional material called MXene has attracted widespread attention in various applications.Their abundant surface functional groups and sites,excellent current conductivity,tunable surface chemistry,and outstanding stability make them promising for gas sensor applications.Since the birth of MXene materials,researchers have utilized the efficient and convenient solution etching preparation,high flexibility,and easily functionalize MXene with other materials to pre-pare composites for gas sensing.This has opened a new chapter in high-performance gas sensing materials and provided a new approach for advanced sensor research.However,previous reviews on MXene-based composite materials in gas sensing only focused on the performance of gas sensing,without systematically explaining the gas sensing mechanisms generated by different gases,as well as summarizing and predicting the advantages and disadvantages of MXene-based composite materials.This article reviews the latest progress in the application of MXene-based composite materials in gas sensing.Firstly,a brief summary was given of the commonly used methods for preparing gas sens-ing device structures,followed by an introduction to the key attributes of MXene related to gas sensing performance.This article focuses on the performance of MXene-based composite materials used for gas sensing,such as MXene/graphene,MXene/Metal oxide,MXene/Transition metal sulfides(TMDs),MXene/Metal-organic framework(MOF),MXene/Polymer.It summarizes the advantages and disadvantages of MXene com-posite materials with different composites and discusses the possible gas sensing mechanisms of MXene-based composite materials for different gases.Finally,future directions and inroads of MXenes-based composites in gas sensing are presented and discussed.

A novel“Snowflake”--rGO-CuO for ultrasonic degradation of rhodamine and methyl orange

Graphene-doped CuO(rGO-CuO)nanocomposites with flower shapes were prepared by an improved solvothermal method.The samples were characterized by X-ray diffraction,X-ray photoelectron spectroscopy and UV–visible spectroscopy.The active species in the degradation reaction of rGO-CuO composites under ultrasonic irradiation were detected by electron paramagnetic resonance.On the basis of comparative experiments,the photodegradation mechanisms of two typical dyes,Rhodamine B(Rh B)and methyl orange(MO),were proposed.The results demonstrated that the doped CuO could improve the degradation efficiency.The catalytic degradation efficiency of rGO-CuO(2:1)to rhodamine B(RhB)and methyl orange(MO)reached 90%and 87%respectively,which were 2.1 times and 4.4 times of the reduced graphene oxide.Through the first-principles and other theories,we give the reasons for the enhanced catalytic performance of rGO-CuO:combined with internal and external factors,rGO-CuO under ultrasound could produce more hole and active sites that could interact with the OH·in pollutant molecules to achieve degradation.The rGO-CuO nanocomposite has a simple preparation process and low price,and has a high efficiency of degrading water pollution products and no secondary pollution products.It has a low-cost and high-efficiency application prospect in water pollution industrial production and life.

Ion association tailoring SEI composition for Li metal anode protection

Electrolyte additives play an important role in suppressing lithium dendrites through tailoring the composition/property of the SEI,however lacking of additives can achieve high performances both in ether and carbonate electrolytes hinders further enhancement of the high voltage lithium^-metal batteries.Here,lithium perchlorate(LiClO4)has been presented as an excellent additive to meet the above requirements.An optimized chemical composition of SEI can be achieved through the formation of ionic association.Our results indicate that the LiClO4 behaves like a catalyst,which promotes LiTFSI to form a better SEI to inhibit further reaction.Superior coulombic efficiencies and cycling performances were obtained both in ether and carbonate electrolytes.This study paves a new pathway for designing bi-soluble additives for safe lithium metal batteries.

Time-frequency analysis of Li solid-phase diffusion in spherical active particles under typical discharge modes

Li transient concentration distribution in spherical active material particles can affect the maximum power density and the safe operating regime of the electric vehicles(EVs). On one hand, the quasiexact/exact solution obtained in the time/frequency domain is time-consuming and just as a reference value for approximate solutions;on the other hand, calculation errors and application range of approximate solutions not only rely on approximate algorithms but also on discharge modes. For the purpose to track the transient dynamics for Li solid-phase diffusion in spherical active particles with a tolerable error range and for a wide applicable range, it is necessary to choose optimal approximate algorithms in terms of discharge modes and the nature of active material particles. In this study, approximation methods,such as diffusion length method, polynomial profile approximation method, Padé approximation method,pseudo steady state method, eigenfunction-based Galerkin collocation method, and separation of variables method for solving Li solid-phase diffusion in spherical active particles are compared from calculation fundamentals to algorithm implementation. Furthermore, these approximate solutions are quantitatively compared to the quasi-exact/exact solution in the time/frequency domain under typical discharge modes, i.e., start-up, slow-down, and speed-up. The results obtained from the viewpoint of time-frequency analysis offer a theoretical foundation on how to track Li transient concentration profile in spherical active particles with a high precision and for a wide application range. In turn, optimal solutions of Li solid diffusion equations for spherical active particles can improve the reliability in predicting safe operating regime and estimating maximum power for automotive batteries.

Fabrication of C@MoxTi1-xO2-δ nanocrystalline with functionalized interface as efficient and robust PtRu catalyst support for methanol electrooxidation

A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of anatase TiO2 was inhibited by the simultaneous presence of the hydrothermal etching/regrowth process,infiltration of Mo dopants and carbon coating,which endows the C@MTNC-FI with an ultrafine crystalline architecture that has a Mo-functionalized interface and carbon-coated shell.Pt Ru nanoparticles(NPs)were supported on C@MTNC-FI by employing a microwave-assisted polyol process(MAPP).The obtained Pt Ru/C@MTNC-FI catalyst has 2.68 times higher mass activity towards methanol electrooxidation than that of the un-functionalized catalyst(Pt Ru/C@TNC)and 1.65 times higher mass activity than that of Pt Ru/C catalyst with over 25%increase in durability.The improved catalytic performance is due to several aspects including ultrafine crystals of TiO2 with abundant grain boundaries,Mofunctionalized interface with enhanced electron interactions,and core shell architecture with excellent electrical transport properties.This work suggests the potential application of an interface-functionalized crystalline material as a sustainable and clean energy solution.

ZnO Interface Modified LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)Toward Boosting Lithium Storage

In this work,an amorphous ZnO was coated on LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM)using a sol-gel strategy method.The NCM coated with 1 wt.%Zn O and a thickness of about 3 nm exhibits an improved cycling performance,accompanied by a lower capacity fading(from 194.8 to 133.8 m Ah g^(-1),i.e.,68%)than that of the pristine one(i.e.,only 34%)after 300 cycles at 0.2 C.The cyclic voltammetry(CV)and electrochemical impedance spectroscopy(EIS)indicate that the Zn O coating can improve extraction/insertion of Li+and inhibit the increase in impedance of the NCM cathode material.This approach may benefit the performance improvement of the Ni-rich cathode materials in Lithium-ion batteries(LIBs).

The synthesis of carbon microspheres film composed of nano-onions and its application as flexible supercapacitors

Flexible electrodes with superior mechanical and electrochemical properties are essential for flexible supercapacitors.A convenient and scalable colloidal film-assisted chemical vapor deposition(CF-CVD)method is developed for the one-step fabrication of the carbon microspheres films composed of carbon nano-onions(CMS-CNO films).The influence of growth conditions(such as growth temperature,time,and gas ratio)during CF-CVD process on the carbon structures and the growth mechanism of the CMS-CNO films have been investigated.By controlling the growth conditions,the controllable preparation of CMS-CNO films is realized.Such binder-free films can be used for the assembly of flexible supercapacitors,and unique architecture can achieve excellent performance.Benefitting from the composite of nano-micro zero dimensional structures,the performance of the film in supercapacitors is remarkably improved.At the current density of 5 mA cm^(-2),the area-specific capacity can be 903 mF cm^(-2).When the current density is increased to 500 mA cm^(-2),the area-specific capacity can be increased to 729 mF cm^(-2).This simple and low-cost preparation process and the superb electrochemical performance suggest great potential applications of CMS-CNO films in flexible supercapacitors.

Recent Advances on Challenges and Strategies of Manganese Dioxide Cathodes for Aqueous Zinc-Ion Batteries

Aqueous zinc-ion batteries(AZIBs)are regarded as promising electrochemical energy storage devices owing to its low cost,intrinsic safety,abundant zinc reserves,and ideal specific capacity.Compared with other cathode materials,manganese dioxide with high voltage,environmental protection,and high theoretical specific capacity receives considerable attention.However,the problems of structural instability,manganese dissolution,and poor electrical conductivity make the exploration of high-performance manganese dioxide still a great challenge and impede its practical applications.Besides,zinc storage mechanisms involved are complex and somewhat controversial.To address these issues,tremendous efforts,such as surface engineering,heteroatoms doping,defect engineering,electrolyte modification,and some advanced characterization technologies,have been devoted to improving its electrochemical performance and illustrating zinc storage mechanism.In this review,we particularly focus on the classification of manganese dioxide based on crystal structures,zinc ions storage mechanisms,the existing challenges,and corresponding optimization strategies as well as structure-performance relationship.In the final section,the application perspectives of manganese oxide cathode materials in AZIBs are prospected.

A Rising 2D Star:Novel MBenes with Excellent Performance in Energy Conversion and Storage

As a flourishing member of the two-dimen-sional(2D)nanomaterial family,MXenes have shown great potential in various research areas.In recent years,the continued growth of interest in MXene derivatives,2D transition metal borides(MBenes),has contributed to the emergence of this 2D material as a latecomer.Due to the excellent electrical conductivity,mechanical properties and electrical properties,thus MBenes attract more researchers’interest.Extensive experimental and theoretical studies have shown that they have exciting energy conversion and elec-trochemical storage potential.However,a comprehensive and systematic review of MBenes applications has not been available so far.For this reason,we present a comprehen-sive summary of recent advances in MBenes research.We started by summarizing the latest fabrication routes and excellent properties of MBenes.The focus will then turn to their exciting potential for energy storage and conversion.Finally,a brief summary of the challenges and opportunities for MBenes in future practical applications is presented.

MXene Ti_(3)C_(2) decorated g-C_(3)N_(4)/ZnO photocatalysts with improved photocatalytic performance for CO_(2) reduction

Photocatalytic reduction of CO_(2) is considered as a kind of promising technologies for solving the greenhouse effect.Herein,a novel hybrid structure of g-C_(3)N_(4)/ZnO/Ti_(3)C_(2) photocatalysts was designed and fabricated to investigate their abilities for CO_(2) reduction.As demonstration,heterojunction of g-C_(3)N_(4)/ZnO can improve photogenerated carriers’separation,the addition of Ti_(3)C_(2) fragments can further facilitate the photocatalytic performance from CO_(2) to CO.Hence,g-C_(3)N_(4)/ZnO/Ti_(3)C_(2) has efficiently increased CO production by 8 and 12 times than pristine g-C_(3)N_(4) and ZnO,respectively.Which is ascribed to the photogenerated charge migration promoted by metallic Ti_(3)C_(2).This work provides a guideline for designing efficient hybrid catalysts on other applications in the renewable energy fields.

Capacitive energy storage from single pore to porous electrode identified by frequency response analysis

Rate capability,peak power,and energy density are of vital importance for the capacitive energy storage(CES)of electrochemical energy devices.The frequency response analysis(FRA)is regarded as an efficient tool in studying the CES.In the present work,a bi-scale impedance transmission line model(TLM)is firstly developed for a single pore to a porous electrode.Not only the TLM of the single pore is reparameterized but also the particle packing compactness is defined in the bi-scale.Subsequently,the CES properties are identified by FRA,focused on rate capability vs.characteristic frequency,peak power vs.equivalent series resistance,and energy density vs.low frequency limiting capacitance for a single pore to a porous electrode.Based on these relationships,the CES properties are numerically simulated and theoretically predicted for a single pore to a porous electrode in terms of intra-particle pore length,intra-particle pore diameter,inter-particle pore diameter,electrolyte conductivity,interfacial capacitance&exponent factor,electrode thickness,electrode apparent surface area,and particle packing compactness.Finally,the experimental diagnosis of four supercapacitors(SCs)with different electrode thicknesses is conducted for validating the bi-scale TLM and gaining an insight into the CES properties for a porous electrode to a single pore.The calculating results suggest,to some extent,the inter-particle pore plays a more critical role than the intra-particle pore in the CES properties such as the rate capability and the peak power density for a single pore to a porous electrode.Hence,in order to design a better porous electrode,more attention should be given to the inter-particle pore.

Review and prospect of NiCo_(2)O_(4)-based composite materials for supercapacitor electrodes

Supercapacitors known as typical electrochemical capacitors have been considered as one of the most promising candidates of energy storage systems owing to their advantages such as high-power density,long life span and lower production cost.The electrode materials play a crucial role on properties of supercapacitors.Hence,many researches have been focused on the development of novel electrode materials for high-performance supercapacitors.NiCo_2O_4as supercapacitor electrode material has drawn more and more attentions in recent years due to its outstanding advantages,such as high theoretical capacity,low cost,natural abundance and easy of synthesis.However,the NiCo_2O_4always suffer from severe capacity deterioration because of the low electrical conductivity and small surface area.Hence,it is necessary to systematically and comprehensively summarize the progress in understanding and modifying NiCo_2O_4-based materials from various aspects.In this review,the structure and synthesis method of NiCo_2O_4-based materials are discussed in detail.And then,the major goal of this review is to highlight new progress in using proposed strategies to improve the cycling stability and rate capacity of NiCo_2O_4-based materials,including synthesis,control of special morphologies and design of composite materials.Finally,an insight into the future research and development of Ni Co_2O_4-based materials for supercapacitors is prospected.

Carbon nanomaterials and their composites for supercapacitors

As a type of energy storage device between traditional capacitors and batteries,the supercapacitor has the advantages of energy saving and environmental protection,high power density,fast charging and discharging speed,long cycle life,and so forth.One of the key factors affecting the performance of supercapacitor is the electrode material.Carbon materials,such as carbon nanotube,graphene,activated carbon,and carbon nanocage,are most widely concerned in the application of supercapacitors.The synergistic effect of composites can often obtain excellent results,which is one of the common strategies to increase the electrochemical performance of supercapacitors.To further improve the performance of binary composites,it is a relatively simple method to increase the components as the“bridge”between the two materials to form the ternary composites.The review mainly introduces the current research progress of supercapacitors with pure carbon nanomaterials and multistage carbon nanostructures(composites)as electrodes.The characteristics and application directions of different pure carbon nanomaterials are introduced in detail.Different ways of multilevel structure(material)composite have their own effects on the development of high-performance supercapacitors.We also highlight the recent advances related to these fields and provide our insight into high-energy supercapacitors.

High-performance self-assembly MnCo2O4 nanosheets for asymmetric supercapacitors

In this study,MnCo2O4 nanosheets were proposed to be utilized as an electrode material for supercapacitors.A two-step hydrothermal method with post-annealing treatment was employed in preparation of the nanostructures.MnCo2O4 electrode delivered a high specific capacitance of 2000 F g^-1 at 0.5 A g^-1,remarkable high-rate capability of 1150 F g^-1 at 20 A g^-1,and an excellent cycling stability of 92.3%at 5 A g^-1 after 5000 cycles.It is found that a three-electrode supercapacitor based on MnCo2O4 exhibits a promising electrochemical performance,better than the other similar materials,benefited from the synergistic effects of MnCo2O4 nanosheets.In fact,the self-assembly of nanosheets structure with high specific surface area and mesoporous structure can potentially enhance the electrochemical performance of supercapacitors.

Nitrogen/sulphur dual-doped hierarchical carbonaceous fibers boosting potassium-ion storage

The carbon materials as anode electrodes have been widely studied for potassium ion batteries(PIBs).However,the large size of potassium ions prevents their intercalation/deintercalation,resulting in poor storage behaviors.Herein,a novel design of N/S codoped hierarchical carbonaceous fibers(NSHCF)formed from nanosheets self-assembled by catalyzing Aspergillus niger with Sn is reported.The asprepared NSHCF at 600℃(NSHCF-600)exhibits a high reversible capacity of 345.4 m Ah g^(-1) at 0.1 A g^(-1) after 100 cycles and an excellent rate performance of 124.5 m Ah g^(-1) at 2 A g^(-1).The excellent potassium storage performance can be ascribed to the N/S dual-doping,which enlarges interlayer spacing(0.404 nm)and introduces more defects.The larger interlayer spacing and higher pyridinic N active sites can promote K ions diffusion and storage.In addition,the ex situ transmission electron microscopy reveals the high reversibility of potassiation/depotassiation process and structural stability.