Structural Engineering of Anode Materials for Low-Temperature Lithium-Ion Batteries:Mechanisms,Strategies,and Prospects

The severe degradation of electrochemical performance for lithium-ion batteries(LIBs)at low temperatures poses a significant challenge to their practical applications.Consequently,extensive efforts have been contributed to explore novel anode materials with high electronic conductivity and rapid Li^(+)diffusion kinetics for achieving favorable low-temperature performance of LIBs.Herein,we try to review the recent reports on the synthesis and characterizations of low-temperature anode materials.First,we summarize the underlying mechanisms responsible for the performance degradation of anode materials at subzero temperatures.Second,detailed discussions concerning the key pathways(boosting electronic conductivity,enhancing Li^(+)diffusion kinetics,and inhibiting lithium dendrite)for improving the low-temperature performance of anode materials are presented.Third,several commonly used low-temperature anode materials are briefly introduced.Fourth,recent progress in the engineering of these low-temperature anode materials is summarized in terms of structural design,morphology control,surface&interface modifications,and multiphase materials.Finally,the challenges that remain to be solved in the field of low-temperature anode materials are discussed.This review was organized to offer valuable insights and guidance for next-generation LIBs with excellent low-temperature electrochemical performance.

Integrated Practice of Cultivating Innovative Ability and Ideological Education for Graduate Students of Materials Science Major

Aiming at the problem of weak integration of innovation ability and ideological education of postgraduates in materials major,this paper explores postgraduates’cultivation work under the support of Liaocheng University.It is found that the cultivation of the innovation ability of postgraduates in materials can be the realization path and sublimation carrier of ideological education,ideological education can provide spiritual support and methodological guidance for the former,and the organic integration of the two is feasible.Constructing the fit relationship between innovation ability and ideological education,institutionalizing tutor guidance,establishing tutor+counselor+professional teacher communication mechanism,and taking disciplinary competitions as a handhold can achieve the integration of innovation ability cultivation and ideological education of graduate students in materials major.

Engineering g-C_(3)N_(4)based materials for advanced photocatalysis:Recent advances

Photocatalysis driven by abundant yet intermittent solar energy has considerable potential in renewable energy generation and environmental remediation.The outstanding electronic structure and physicochemical properties of graphitic carbon nitride(g-C_(3)N_(4)),together with unique metal-free characteristic,make them ideal candidates for advanced photocatalysts construction.This review summarizes the up-to-date advances on g-C_(3)N_(4)based photocatalysts from ingenious-design strategies and diversified photocatalytic applications.Notably,the advantages,fabrication methods and limitations of each design strategy are systemically analyzed.In order to deeply comprehend the inner connection of theory–structure–performance upon g-C_(3)N_(4)based photocatalysts,structure/composition designs,corresponding photocatalytic activities and reaction mechanisms are jointly discussed,associated with introducing their photocatalytic applications toward water splitting,carbon dioxide/nitrogen reduction and pollutants degradation,etc.Finally,the current challenges and future perspectives for g-C_(3)N_(4)based materials for photocatalysis are briefly proposed.These design strategies and limitations are also instructive for constructing g-C_(3)N_(4) based materials in other energy and environment-related applications.

Vanadium oxide nanospheres encapsulated in N-doped carbon nanofibers with morphology and defect dual-engineering toward advanced aqueous zinc-ion batteries

Vanadium-based electrodes are regarded as attractive cathode materials in aqueous zinc ion batteries(ZIBs)caused by their high capacity and unique layered structure.However,it is extremely challenging to acquire high electrochemical performance owing to the limited electronic conductivity,sluggish ion kinetics,and severe volume expansion during the insertion/extraction process of Zn^(2+).Herein,a series of V_(2)O_(3)nanospheres embedded N-doped carbon nanofiber structures with various V_(2)O_(3)spherical morphologies(solid,core-shell,hollow)have been designed for the first time by an electrospinning technique followed thermal treatments.The N-doped carbon nanofibers not only improve the electrical conductivity and the structural stability,but also provides encapsulating shells to prevent the vanadium dissolution and aggregation of V_(2)O_(3)particles.Furthermore,the varied morphological structures of V_(2)O_(3)with abundant oxygen vacancies can alleviate the volume change and increase the Zn^(2+)pathway.Besides,the phase transition between V_(2)O_(3)and Zn_XV_(2)O_(5-m)·n H_(2)O in the cycling was also certified.As a result,the as-obtained composite delivers excellent long-term cycle stability and enhanced rate performance for coin cells,which is also confirmed through density functional theory(DFT)calculations.Even assembled into flexible ZIBs,the sample still exhibits superior electrochemical performance,which may afford new design concept for flexible cathode materials of ZIBs.

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.

High-efficiency sodium storage of Co_(0.85)Se/WSe_(2) encapsulated in N-doped carbon polyhedron via vacancy and heterojunction engineering

With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.

Heterointerface engineering of rhombic Rh nanosheets confined on MXene for efficient methanol oxidation

Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely limits the overall electrocatalytic performance due to their insufficient cooperative effects.Herein,we report a controllable and robust heterointerface engineering strategy for the bottom-up fabrication of rhombic Rh nanosheets in situ confined on Ti_3C_(2)T_x MXene nanolamellas(Rh NS/MXene)via a convenient stereoassembly process.This unique design concept gives the resulting 2D/2D Rh NS/MXene heterostructure intriguing textural features,including large accessible surface areas,strong"face-toface"interfacial interactions,homogeneous Rh nanosheet distribution,ameliorative electronic structure,and high electronic conductivity.As a consequence,the as-prepared Rh NS/MXene nanoarchitectures exhibit exceptional electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area of 126.2 m~2 g_(Rh)~(-1),a high mass activity of 1056.9 mA mg_(Rh)-~1,and a long service life,which significantly outperform those of conventional particle-shaped Rh catalysts supported by carbon black,carbon nanotubes,reduced graphene oxide,and MXene matrixes as well as the commercial Pt nanoparticle/carbon black and Pd nanoparticle/carbon black catalysts with the same noble metal loading amount.Density functional theory calculations further demonstrate that the direct electronic interaction at the well-contacted 2D/2D heterointerfaces effectively enhances the adsorption energy of Rh nanosheets and induces a left shift of the d-band center,thereby making the Rh NS/MXene configuration suffer less from CO poisoning.This work highlights the importance of rational heterointerface design in the construction of advanced noble metal/MXene electrocatalysts,which may provide new avenues for developing the next-generation DMFC devices.

Suppress oxygen evolution of lithium-rich manganese-based cathode materials via an integrated strategy

Improving the reversibility of anionic redox and inhibiting irreversible oxygen evolution are the main challenges in the application of high reversible capacity Li-rich Mn-based cathode materials.A facile synchronous lithiation strategy combining the advantages of yttrium doping and LiYO_(2) surface coating is proposed.Yttrium doping effectively suppresses the oxygen evolution during the delithiation process by increasing the energy barrier of oxygen evolution reaction through strong Y–O bond energy.LiYO_(2) nanocoating has the function of structural constraint and protection,that protecting the lattice oxygen exposed to the surface,thus avoiding irreversible oxidation.As an Li^(+) conductor,LiYO_(2) nano-coating can provide a fast Li^(+) transfer channel,which enables the sample to have excellent rate performance.The synergistic effect of Y doping and nano-LiYO_(2) coating integration suppresses the oxygen release from the surface,accelerates the diffusion of Li^(+)from electrolyte to electrode and decreases the interfacial side reactions,enabling the lithium ion batteries to obtain good electrochemical performance.The lithium-ion full cell employing the Y-1 sample(cathode)and commercial graphite(anode)exhibit an excellent specific energy density of 442.9 Wh kg^(-1) at a current density of 0.1C,with very stable safety performance,which can be used in a wide temperature range(60 to-15℃)stable operation.This result illustrates a new integration strategy for advanced cathode materials to achieve high specific energy density.

Recent Progress in Improving Rate Performance of Cellulose-Derived Carbon Materials for Sodium-Ion Batteries

Cellulose-derived carbon is regarded as one of the most promising candidates for high-performance anode materials in sodium-ion batteries;however,its poor rate performance at higher current density remains a challenge to achieve high power density sodium-ion batteries.The present review comprehensively elucidates the structural characteristics of cellulose-based materials and cellulose-derived carbon materials,explores the limitations in enhancing rate performance arising from ion diffusion and electronic transfer at the level of cellulose-derived carbon materials,and proposes corresponding strategies to improve rate performance targeted at various precursors of cellulose-based materials.This review also presents an update on recent progress in cellulose-based materials and cellulose-derived carbon materials,with particular focuses on their molecular,crystalline,and aggregation structures.Furthermore,the relationship between storage sodium and rate performance the carbon materials is elucidated through theoretical calculations and characterization analyses.Finally,future perspectives regarding challenges and opportunities in the research field of cellulose-derived carbon anodes are briefly highlighted.

Effect of crystal morphology of ultrahigh-nickel cathode materials on high temperature electrochemical stability of lithium ion batteries

Higher nickel content endows Ni-rich cathode materials LiNi_(x)Co_yMn_(1-x-y)O_(2)(x>0.6)with higher specific capacity and high energy density,which is regarded as the most promising cathode materials for Li-ion batteries.However,the deterioration of structural stability hinders its practical application,especially under harsh working conditions such as high-temperature cycling.Given these circumstances,it becomes particularly critical to clarify the impact of the crystal morphology on the structure and high-temperature performance as for the ultrahigh-nickel cathodes.Herein,we conducted a comprehensive comparison in terms of microstructure,high-temperature long-cycle phase evolution,and high-temperature electrochemical stability,revealing the differences and the working mechanisms among polycrystalline(PC),single-crystalline(SC)and Al doped SC ultrahigh-nickel materials.The results show that the PC sample suffers a severe irreversible phase transition along with the appearance of microcracks,resulting a serious decay of both average voltage and the energy density.While the Al doped SC sample exhibits superior cycling stability with intact layered structure.In-situ XRD and intraparticle structural evolution characterization reveal that Al doping can significantly alleviate the irreversible phase transition,thus inhibiting microcracks generation and enabling enhanced structure.Specifically,it exhibits excellent cycling performance in pouch-type full-cell with a high capacity retention of 91.8%after 500 cycles at 55℃.This work promotes the fundamental understanding on the correlation between the crystalline morphology and high-temperature electrochemical stability and provides a guide for optimization the Ni-rich cathode materials.

Self-derivation and reconstruction of silver nanoparticle reinforced cobalt-nickel bimetallic hydroxides through interface engineering for overall water splitting

Designing efficient and long-lasting non-metal electrocatalysts is an urgent task for addressing the issue of kinetic hysteresis in electrochemical oxidation reactions.The bimetallic hydroxides,catalyzing the oxygen evolution reaction(OER),have significant research potential because hydroxide reconstruction to generate an active phase is a remarkable advantage.Herein,the complete reconstruction of ultrathin CoNi(OH)_(2) nanosheets was achieved by embedding Ag nanoparticles into the hydroxide to induce a spontaneous redox reaction(SRR),forming heterojunction Ag@CoNi(OH)_(2) for bifunctional hydrolysis.Theoretical calculations and in situ Raman and ex situ characterizations revealed that the inductive effect of the Ag cation redistributed the charge to promote phase transformation to highly activate Ag-modified hydroxides.The Co-Ni dual sites in Co/NiOOH serve as novel active sites for optimizing the intermediates,thereby weakening the barrier formed by OOH^*.Ag@CoNi(OH)_(2) required a potential of 1.55 V to drive water splitting at a current density of 10 mA cm^(-2),with nearly 98.6% Faraday efficiency.Through ion induction and triggering of electron regulation in the OER via the synergistic action of the heterogeneous interface and surface reconstruction,this strategic design can overcome the limited capacity of bimetallic hydroxides and bridge the gap between the basic theory and industrialization of water decomposition.

A review of classical hydrogen isotopes storage materials

Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactive tritium.Commonly used HSAs in the hydrogen isotopes field are Zr2M(M=Co,Ni,Fe)alloys,metallic Pd,depleted U,and ZrCo alloy.Specifically,Zr2M(M=Co,Ni,Fe)alloys are considered promising tritium-getter materials,and metallic Pd is utilized to separate and purify hydrogen isotopes.Furthermore,depleted U and ZrCo alloy are well suited for storing and delivering hydrogen isotopes.Notably,all the aforementioned HSAs need to modulate their hydrogen storage properties for complex operating conditions.In this review,we present a comprehensive overview of the reported modification methods applied to the above alloys.Alloying is an effective amelioration method that mainly modulates the properties of HSAs by altering their local geometrical/electronic structures.Besides,microstructural modifications such as nano-sizing and nanopores have been used to increase the specific surface area and active sites of metallic Pd and ZrCo alloys for enhancing de-/hydrogenation kinetics.The combination of metallic Pd with support materials can significantly reduce the cost and enhance the pulverization resistance.Moreover,the poisoning resistance of ZrCo alloy is improved by constructing active surfaces with selective permeability.Overall,the review is constructive for better understanding the properties and mechanisms of hydrogen isotope storage alloys and provides effective guidance for future modification research.

The design and engineering strategies of metal tellurides for advanced metal-ion batteries

Owning various crystal structures and high theoretical capacity,metal tellurides are emerging as promising electrode materials for high-performance metal-ion batteries(MBs).Since metal telluride-based MBs are quite new,fundamental issues raise regarding the energy storage mechanism and other aspects affecting electrochemical performance.Severe volume expansion,low intrinsic conductivity and slow ion diffusion kinetics jeopardize the performance of metal tellurides,so that rational design and engineering are crucial to circumvent these disadvantages.Herein,this review provides an in-depth discussion of recent investigations and progresses of metal tellurides,beginning with a critical discussion on the energy storage mechanisms of metal tellurides in various MBs.In the following,recent design and engineering strategies of metal tellurides,including morphology engineering,compositing,defect engineering and heterostructure construction,for high-performance MBs are summarized.The primary focus is to present a comprehensive understanding of the structural evolution based on the mechanism and corresponding effects of dimension control,composition,electron configuration and structural complexity on the electrochemical performance.In closing,outlooks and prospects for future development of metal tellurides are proposed.This work also highlights the promising directions of design and engineering strategies of metal tellurides with high performance and low cost.

Effect of Zircon Addition on Properties of Corundum Porous Materials

This paper aims to improve the corrosion resistance of dispersive purging plugs.White fused corundum particles and fine powder,α-Al_(2)O_(3) micropowder,Cr_(2)O_(3) micropowder,Guangxi clay and zircon powder were used as the main raw materials.The mass ratio of white fused corundum particles and fine powder was fixed at 85:15,and 0,1%,2%,or 3%(by mass)of zircon fine powder was added to replace the same amount of white fused corundum fine powder.The corundum porous material was prepared by the particle stacking pore-forming method at 1650℃for 3 h.The effect of the zircon addition on the properties and microstructure of porous materials was investigated.The results show that:after adding zircon,the permeability of the porous material increases,the cold and hot strengths increase obviously,and the expansion rate after firing decreases.When the addition of zircon is 2%,the comprehensive performance of the specimen is optimal with the smallest linear change rate and the highest permeability.

Anode surface engineering of zinc-ion batteries using tellurium nanobelt as a protective layer for enhancing energy storage performance

Over the years,zinc-ion batteries(ZIBs)have attracted attention as a promising next-generation energy storage technology because of their excellent safety,long cycling performance,eco-friendliness,and high-power density.However,issues,such as the corrosion and dissolution of the Zn anode,limited wet-tability,and lack of sufficient nucleation sites for Zn plating,have limited their practical application.The introduction of a protective layer comprising of tellurium(Te)nanobelts onto the surface of Zn anode has emerged as a promising approach to overcome these limitations and improve the electrochemical behav-ior by enhancing the safety and wettability of ZIBs,as well as providing numerous nucleation sites for Zn plating.In the presence of a Te-based protective layer,the energy power density of the surface-engineered Zn anode improved significantly(ranging from 310 to 144 W h kg^(-1),over a power density range of 270 to 1,800 W kg^(-1)),and the lifespan capability was extended.These results demonstrate that the proposed strategy of employing Te nanobelts as a protective layer holds great promise for enhancing the energy storage performance of zIBs,making them even more attractive as a viable energy storage solution forthefuture.

Phase engineering of Ni-Mn binary layered oxide cathodes for sodiumion batteries

Nickel-manganese binary layered oxides with high working potential and low cost are potential candidates for sodium-ion batteries,but their electrochemical properties are highly related to compositional diversity.Diverse composite materials with various phase structures of P3,P2/P3,P2,P2/O3,and P2/P3/O3 were synthesized by manipulating the sodium content and calcination conditions,leading to the construction of a synthetic phase diagram for Na_(x)Ni_(0.25)Mn_(0.75)O_(2)(0.45≤x≤1.1).Then,we compared the electrochemical characteristics and structural evolution during the desodiation/sodiation process of P2,P2/P3,P2/03,and P2/P3/O3-Na_(x)Ni_(0.25)Mn_(0.75)O_(2).Among them,P2/P3-Na0.75Ni0.25Mn0.75O2exhibits the best rate capability of 90.9 mA h g^(-1)at 5 C,with an initial discharge capacity of 142.62 mA h g^(-1)at 0.1 C and a capacity retention rate of 78.25%after 100 cycles at 1 C in the voltage range of 2-4.3 V.The observed superior sodium storage performance of P2/P3 hybrids compared to other composite phases can be attributed to the enhanced Na^(+)transfer dynamic,reduction of the Jahn-teller effect,and improved reaction reversibility induced by the synergistic effect of P2 and P3 phases.The systematic research and exploration of phases in Na_(x)Ni_(0.25)Mn_(0.75)O_(2)provide new sights into high-performance nickel-manganese binary layered oxide for sodium-ion batteries.

Research Progress of High Entropy Ceramic Materials

High-entropy materials(HEMs)have better mechanical,thermal,and electrical properties than traditional materials due to their special"high entropy effect".They can also adjust the performance of high entropy ceramics by adjusting the proportion of raw materials,and have broad application prospects in many fields.This article provides a review of the high entropy effect,preparation methods,and main applications of high entropy ceramic materials,especially exploring relevant research on high entropy perovskite ceramics.It is expected to provide reference for the promotion of scientific research and the development of further large-scale applications of high-entropy ceramic materials.

Preparation and Performance Study of Cementitious Capillary Crystalline Waterproof Materials

Cementitious capillary crystalline waterproof materials(CCCW for short)offer durability and excellent waterproofing properties,making them a popular option for building waterproofing.Some scholars have studied the proportioning of such materials.However,these studies lack the relationship between the impermeability pressure of mortar and the components,and the mechanism of action is somewhat debatable.Therefore,we adopted a two-step method in our experiments.Firstly,we screened out the components that significantly impact impermeability from a variety of active components by orthogonal test.We then optimized the design of the active group ratio using the simplex lattice method.Lastly,we conducted a performance test of the optimal ratio and explored the waterproofing mechanism of homemade CCCW.

Integrated Computational Materials Engineering for the Development and Design of High Modulus Al Alloys

Integrated computational materials engineering(ICME)is to integrate multi-scale computational simulations and key experimental methods such as macroscopic,mesoscopic,and microscopic into the whole process of Al alloys design and development,which enables the design and development of Al alloys to upgrade from traditional empirical to the integration of compositionprocess-structure-mechanical property,thus greatly accelerating its development speed and reducing its development cost.This study combines calculation of phase diagram(CALPHAD),Finite element calculations,first principle calculations,and microstructure characterization methods to predict and regulate the formation and structure of composite precipitates from the design of highmodulus Al alloy compositions and optimize the casting process parameters to inhibit the formation of micropore defects in the casting process,and the final tensile strength of Al alloys reaches420 MPa and Young's modulus reaches more than 88 GPa,which achieves the design goal of the high strength and modulus Al alloys,and establishes a new mode of the design and development of the strength/modulus Al alloys.

Development of Integrated Computational Materials Engineering(ICME)Model for Mg Alloy Design and Process Optimization

Integrated computational materials engineering(ICME)has emerged to be one of the most powerful materials genome engineering(MGE)approaches in designing new materials and manufacturing processes in recent years.It has successfully deployed many new products for the electronic,automotive,and aerospace industries.This paper reviews the current status of research on first principles in the design of high-strength Mg alloys,discusses the application of crystal plasticity finite element models to the microscale slip,twinning,microstructure morphology,texture evolution,and macroscopic forming of Mg alloys,and introduces the research progress of crystal plasticity finite element models and phase field models,meta cellular automata models and first principles coupled models respectively,around the need for multi-scale coupled simulations of Mg alloys.The key technology obstacles of integrating the first principles,crystal plasticity finite element,and microstructure models for Mg alloys have been solved.This paper can provide a reference for the design of new Mg alloy compositions and the development of high-performance Mg alloys.