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.

First-Principles Study of the New Layered Ternary Metal Telluride,Eu_(2)InTe_(5)

In this study,we performed first-principles calculations using the VASP(Vienna Ab initio Simulation)software package to investigate the crystal structure,electronic structure,and optical properties of a new layered ternary metal chalcogenide,Eu_(2)InTe_(5).Our results show that Eu_(2)InTe_(5) is a non-zero-gap metal with a layered structure characterized by strong intra-layer atomic bonding and weak inter-layer interaction,which suggests its potential application as a nanomaterial.We also studied the optical properties,including the absorption coefficient,imaginary and real parts of the complex dielectric constant,and found that Eu_(2)InTe_(5) exhibits strong photoresponse characteristics at the junction of ultraviolet and visible light as well as blue-green light,with peaks at wavelengths of 389 nm and 477 nm.This suggests that it could be used in the development of UV(ultraviolet)detectors and other optoelectronic devices.Furthermore,due to its strong absorption,low loss,and low reflectivity,Eu_(2)InTe_(5) has the potential to be used as a promising photovoltaic absorption layer in solar cells.

Modification,application and expansion of electrode materials based on cobalt telluride

Metal(Li,Na,K,Al)-ion batteries and lithium-sulfur and lithium-tellurium batteries are gaining recognition for their eco-friendly characteristics,substantial energy density,and sustainable attributes.However,the overall performance of rechargeable batteries heavily depends on their electrode materials.Transition metal tellurides have recently gained significant attention due to their high electrical conductivity and density.Cobalt telluride has received the most extensive research due to its catalytic activity,unique magnetic properties,and diverse composition and crystal structure.Nevertheless,its limited conductivity and significant volume variation contribute to electrode structural deterioration and rapid capacity decline.This review comprehensively summarizes recent advances in rational design and synthesis of modified cobalt telluride-based electrodes,encompassing defect engineering(Te vacancies,cation vacancies,heterointerfaces,and homogeneous interfaces)and composite engineering(derived carbon from precursors,carbon fibers,Mxene,graphene nanosheets,etc.).Particularly,the intricate evolution mechanisms of the conversion reaction process during cycling are elucidated.Furthermore,these modified strategies applied to other transitional metal tellurides,such as iron telluride,nickel telluride,zinc telluride,copper telluride,molybdenum telluride,etc.,are also thoroughly summarized.Additionally,their application extends to emerging aqueous zinc-ion batteries.Finally,potential challenges and prospects are discussed to further propel the development of transition metal tellurides electrode materials for next-generation rechargeable batteries.

Novel ternary metals-based telluride electrocatalyst with synergistic effects of high valence non-3d metal and oxophilic Te for pH-universal hydrogen evolution reaction

Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline HER kinetics.Here,we design ternary transition metals-based nickel telluride(Mo WNi Te)catalysts consisting of high valence non-3d Mo and W metals and oxophilic Te as a first demonstration of non-precious heterogeneous electrocatalysts following the bifunctional mechanism.The Mo WNi Te showed excellent HER catalytic performance with overpotentials of 72,125,and 182 mV to reach the current densities of 10,100,and 1000 mA cm^(-2),respectively,and the corresponding Tafel slope of 47,52,and 58 mV dec-1in alkaline media,which is much superior to commercial Pt/C.Additionally,the HER performance of Mo WNi Te is well maintained up to 3000 h at the current density of 100 mA cm^(-2).It is further demonstrated that the Mo WNi Te exhibits remarkable HER activities with an overpotential of 45 mV(31 mV)and Tafel slope of 60 mV dec-1(34 mV dec-1)at 10 mA cm^(-2)in neutral(acid)media.The superior HER performance of Mo WNi Te is attributed to the electronic structure modulation,inducing highly active low valence states by the incorporation of high valence non-3d transition metals.It is also attributed to the oxophilic effect of Te,accelerating water dissociation kinetics through a bifunctional catalytic mechanism in alkaline media.Density functional theory calculations further reveal that such synergistic effects lead to reduced free energy for an efficient water dissociation process,resulting in remarkable HER catalytic performances within universal pH environments.

Efficient hydrogen peroxide production enabled by exploring layered metal telluride as two electron oxygen reduction reaction electrocatalyst

It is of great interest to develop the novel transition metal-based electrocatalysts with high selectivity and activity for two electron oxygen reduction reaction(2e^(-) ORR).Herein,the nickel ditelluride(NiTe_(2)) with layered structure was explored as the 2e^(-) ORR electrocatalyst,which not only showed the highest 2e^(-) selectivity more than 97%,but also delivered a slight activity decay after 5000 cycles in alkaline media.Moreover,when NiTe_(2) was assembled as the electrocatalyst in H-type electrolyzer,the on-site yield of H_(2)O_(2) could reach up to 672 mmol h^(-1)g^(-1) under 0.45 V vs.RHE.Further in situ Raman spectra,theoretical calculation and post microstructural analysis synergistically unveiled that such a good 2e^(-) ORR performance could be credited to the intrinsic layered crystal structure,the high compositional stability,as well as the electron modulation on the active site Ni atoms by neighboring Te atoms,leading to the exposure of active sites as well as the optimized adsorption free energy of Ni to –OOH.More inspiringly,such telluride electrocatalyst has also been demonstrated to exhibit high activity and selectivity towards 2e^(-) ORR in neutral media.

Novel Synthesis of Benzotriazol-1-yl Methyl Selenides and Tellurides

Benzotriazol-1-yl methyl selenides and tellurides 4a-h can be simply synthesized by the reaction of 2a-b with 3 in good yields.

Built‑In Electric Field‑Driven Ultrahigh‑Rate K‑Ion Storage via Heterostructure Engineering of Dual Tellurides Integrated with Ti_(3)C_(2)T_(x)MXene

Exploiting high-rate anode materials with fast K+diffusion is intriguing for the development of advanced potassium-ion batteries(KIBs)but remains unrealized.Here,heterostructure engineering is proposed to construct the dual transition metal tellurides(CoTe_(2)/ZnTe),which are anchored onto two-dimensional(2D)Ti_(3)C_(2)T_(x)MXene nanosheets.Various theoretical modeling and experimental findings reveal that heterostructure engineering can regulate the electronic structures of CoTe_(2)/ZnTe interfaces,improving K+diffusion and adsorption.In addition,the different work functions between CoTe_(2)/ZnTe induce a robust built-in electric field at the CoTe_(2)/ZnTe interface,providing a strong driving force to facilitate charge transport.Moreover,the conductive and elastic Ti_(3)C_(2)T_(x)can effectively promote electrode conductivity and alleviate the volume change of CoTe_(2)/ZnTe heterostructures upon cycling.Owing to these merits,the resulting CoTe_(2)/ZnTe/Ti_(3)C_(2)T_(x)(CZT)exhibit excellent rate capability(137.0 mAh g^(-1)at 10 A g^(-1))and cycling stability(175.3 mAh g^(-1)after 4000 cycles at 3.0 A g^(-1),with a high capacity retention of 89.4%).More impressively,the CZT-based full cells demonstrate high energy density(220.2 Wh kg^(-1))and power density(837.2 W kg^(-1)).This work provides a general and effective strategy by integrating heterostructure engineering and 2D material nanocompositing for designing advanced high-rate anode materials for next-generation KIBs.

Rational design of metal selenides nanomaterials for alkali metal ion(Li^(+)/Na^(+)/K^(+))batteries:current status and perspectives

Recently,metal selenides have obtained widespread attention as electrode materials for alkali(Li^(+)/Na^(+)/K^(+))batteries due to their promising theoretical capacity and mechanism.Nevertheless,metal selenides,similar to metal oxides and sulfides,also suffer from severe volume explosion during repeated charge/discharge processes,which results in the structure collapse and the following pulverization of electrode materials.Hence,it leads to poor cycle stability and influencing their further application.In order to solve these issues,some special strategies,including elemental doping,coupling with carbon materials,synthesis of the bimetal selenides with heterostructure,etc.,have been gradually applied to design novel electrode materials with outstanding electrochemical performance.Herein,the recent research progress on metal selenides as anodes for alkali ion batteries is summarized,including the regulation of crystal structure,synthesis strategies,modification methods,and electrochemical mechanisms and kinetics.Besides,the challenges of metal selenides and the perspective for future electrode material design are proposed.It is hoped to pave a way for the development of metal selenide electrode materials for the potential applications for alkali metal ion(Li^(+)/Na^(+)/K^(+))batteries.

Inhibiting shuttle effect of lithium polysulfides by double metal selenides for high-performance lithium-sulfur batteries

Lithium-sulfur batteries(LSBs)have attracted the attention of more and more researchers due to the advantages of high energy density,environmental friendliness,and low production cost.However,the low electronic conductivity of active material and shuttling effect of lithium polysulfides(LiPSs)limit the commercial development of LSBs.To solve these problems,we design a core-shell composite with nitrogen-doped carbon(NC)and two types of selenides(FeSe_(2)-NC@ZnSe-NC).The FeSe_(2)-NC@ZnSe-NC has a strong adsorption capacity,and can effectively adsorb LiPSs.At the same time,it also effectively alleviates the shuttling effect of LiPSs,and improves the utilization of the active substance during the charge/discharge reaction processes.The mechanism involved in FeSe_(2)-NC@ZnSe-NC is demonstrated by both experiments and density-functional theory(DFT)calculations.The electrochemical test results indicate that LSB with S/FeSe_(2)-NC@ZnSe-NC delivers an initial discharge capacity of 1260 mAh·g^(-1)at 0.2C.And after 500 cycles at 1C,the capacity decay rate per cycle is 0.031%,and the capacity retention rate is 85%.The FeSe_(2)-NC@ZnSe-NC core-shell structure verifies a rational strategy to construct an electrode material for high-performance LSBs.

Abnormal physics of group-Ⅱ telluride system:valence contribution of d electrons

The physical trend of group-I/tellurides is unexpected and contrary to the conventional wisdom. The present firstprinciples calculations give fundamental insights into the extent to which group-Ⅱ telluride compounds present special properties upon mixing the d valence character. Our results provide explanations for the unexpected experimental observations based on the abnormal binding ordering of metal d electrons and their strong perturbation to the band edge states. The insights into the binary tellurides are useful for the study and control of the structural and chemical perturbation in their ternary alloys and heterostructures.

Synthesis of Novel Quaternary Selenide K_2CdSnSe_4

A novel quaternary metal selenide, K2CdSnSe4, was synthesized via a molten-salt reaction at 550 ℃. The compound has a one-dimensional structure containing a chain of ∞^1[CdSnSe4]^2- anions separated by K^＋ cations. The crystal belongs to the space group I-4^-2m, with the unit cell parameters a=0.80298（11） nm, b=0.80298（11） nm, c=0.69217（14） nm, α=β=γ=90°. A reflectance spectroscopy study reveals the nature of the semiconductor with an energy gap of 1.7 eV for the compound and it has a strong optical absorotion in a range of 2--5 eV.

Advances in green colloidal synthesis of metal selenide and telluride quantum dots

During the past three decades, metal selenide and telluride quantum dots (QDs) have been deemed one of the most vital nanomaterials in virtue of their extensive applications, including lighting, solar harvesting,photocatalysis, biolabelling, quantum computing and so forth. With the growing demands for the QDrelated products, environmental friendly, energy-efficient and timesaving approaches to synthesize functional metal selenide and telluride QDs are greatly welcome. On the basis of the development in synthesis of chalcogen precursors, this mini review summarizes the recent progress in the green methods for synthesizing metal selenide and telluride QDs. At first, the panorama of basic synthetic methodology of metal chalcogenide QDs is briefly introduced. Then, numerous evolving colloidal synthetic methods are discussed, highlighting the phosphine-free precursors and the aqueous ionic precursors. Finally, this review ends with remaining challenges and future prospects in synthetic schemes. We hope this review will provide some stimulating information to promote further advancement in this area.

MoSe_(2)/Co-MOF/NF复合材料的制备及电催化产氧性能

设计高效的催化剂对于电解水制氢至关重要。基于过渡金属硒化物(TMSe)的高催化活性和金属有机骨架(MOFs)的灵活结构,我们提出了一种将MOFs与TMSe复合的策略,在导电基底泡沫镍(NF)上生长的复合材料不仅继承了2种单体的优点,还有效地改善了MOFs导电性差、TMSe易团聚的缺点。MoSe_(2)/Co-MOF/NF在碱性溶液中展示出优异的电催化产氧活性,在电流密度为10 mA·cm^(-2)时其过电位仅为242 mV,塔菲尔斜率仅为50.64 mV·dec^(-1)。此外,该材料在碱性溶液中经1 000圈循环伏安(CV)循环测试和30 h的恒电压电解测试均表现出良好的稳定性。

金属硒化物储能机理及其在锂离子电容器中的应用

锂离子电容器(lithium-ion capacitors,LICs)是一种兼具锂离子电池和双电层电容器优点的新型功率型储能器件。然而,电池型负极的缓慢电化学动力学性能限制LICs的应用。金属硒化物因其良好的导电性、快速的反应动力学和高理论比容量等优点备受关注。本文对金属硒化物的分类、结构和性质进行系统介绍,并重点讨论插层机制、转化机制和合金化机制的三种储能机制。最后,分析结构调控、碳材料协同和双金属硒化物构筑等改性方案对电化学性能的影响,并介绍由以上三种改性方法制备的结构稳定和高离子/电子传输能力的金属硒化物材料在锂离子电容器中的应用。

过渡金属碲化物XTe_(2)(X=Ti,Zr,Hf,V)高压下力学性质的密度泛函研究

本文利用基于密度泛函理论的第一性原理计算方法,研究了过渡金属碲化物XTe_(2)(X=Ti,Zr,Hf,V)的力学性质.声子色散曲线和弹性常数的计算结果表明,4种材料在大气压下是稳定的.弹性性质的计算表明,增加压力可以显著提高这些材料的抗压缩能力和延展性.4种材料的各向异性指数均大于零,表明这些材料都是各向异性的.同时,我们预测Zr Te_(2)和VTe_(2)材料在20 GPa内会发生结构相变.

钠离子电池过渡金属硒化物负极材料的研究进展

钠离子电池(SIBs)因其原材料来源丰富,在大规模储能领域具有较强的竞争力,有望成为锂离子电池的重要补充。负极材料是制约钠离子电池发展的关键问题。在众多的钠离子电池负极材料中,过渡金属硒化物(TMSs)有着高理论容量、低成本和环境友好的优点,被认为是有希望的候选材料。首先,阐明了TMSs的钠储存机制。然后,阐述了TMSs目前存在的首次库仑效率低、体积膨胀大、导电性差和多硒化物穿梭效应等问题。随后,讨论了相应的改进策略,并详细介绍了TMSs在纳米结构设计、碳包覆、构建异质结和其他方面的最新研究进展。最后,进行了对TMSs的总结和展望。

高性能棒状复合催化剂用于锂氧气电池性能研究

锂氧气电池的正极氧还原反应(ORR)和析氧反应(OER)的缓慢动力学过程严重影响了电池性能。因此,设计制备了一种一维纳米棒状CoSe_(2)@Co_(0.85)Se复合材料作为锂氧气电池正极催化剂。结果表明,独特的多孔棒状结构使材料具有高比表面积和丰富的催化活性位点,复合材料界面上的电子相互作用优化了界面电子结构,有利于电荷转移和反应中间体的吸脱附,从而提高了ORR/OER反应动力学。当该复合材料用于锂氧气电池正极催化剂时表现出优异的放电比容量(14 748 mAh/g)和循环稳定性(231圈)。

金属硒化物负极材料在钠离子电池中的应用

随着人们环境保护意识的日益增强和能源危机的不断加剧,环保、可持续性的可再生能源已引起人们广泛的关注。钠与锂是同主族元素,具有相似的物理、化学性质,并且钠的自然储量丰富、价格低廉。因此钠离子电池(sodium-ion batteries,SIBs)得到了广泛关注,已迅速发展成为锂离子电池(lithium-ion batteries,LIBs)最有效的替代品。作为SIBs负极材料的金属硒化物(MSe_(x))比其他金属化合物表现出了更高的理论容量,在SIBs中显示出良好的电化学性能。然而,在电池充放电循环过程中,MSe_(x)会出现体积变化巨大、结构粉碎、“穿梭效应”等一系列问题。这些问题都限制了MSe_(x)在SIBs中的进一步发展与应用。该研究从储钠机制的角度出发,对不同反应类型的MSe_(x)负极材料在SIBs中的研究现状进行了综述,详述了不同改性策略对其电化学性能的影响,并对MSe_(x)负极材料在SIBs中面临的挑战及其未来发展进行了总结与展望。

Bi_(2)Se_(3)/WSe_(2)异质结构花球的制备与储钠性能研究

钠离子电池(SIBs)由于在成本、资源和安全性方面具有显著优势,被认为是一种有前途的锂离子电池替代方案。然而,它的实际应用受到容量低、倍率性能差和寿命短等问题的限制。本文采用一步水热法合成了Bi_(2)Se_(3)/WSe_(2)花球异质结构,其中存在着丰富的孔隙。该结构可以在充放电过程中缓解体积效应,并且异质界面处的内建电场可以增强离子扩散反应,从而提高电化学性能。组装的Bi_(2)Se_(3)/WSe_(2)半电池具有较高的初始库仑效率、循环稳定性和较强倍率能力。经过100次循环,钠离子电池(SIBs)在0.1 A·g^(-1)下放电容量为402.6 mAh·g^(-1),在1 A·g^(-1)下进行500次循环后,总量可达298.3 mAh·g^(-1),而在高倍率下(5 A·g^(-1)),其容量仍能维持在259.1 mAh·g^(-1)。

过渡金属碲化物(TMTs)电解水催化剂的应用与研究进展

可再生能源驱动的电化学水分解,已被认为是一种可持续和环保的生产绿氢的方式,是交通运输部门和难以减排的行业脱碳的重要载体,能够为实现全球碳中和做出贡献。为了大规模部署水电解槽,开发高效耐用的电催化剂至关重要。过渡金属碲化物(TMTs)具有成本低、稳定性好、过电位低、电子相互作用强、导电性好、活性位点多等优点,是在析氢反应(HER)和析氧反应(OER)中,传统铂族金属的有希望的替代品,已成为极具发展前景的电催化剂。本文综述了基于TMTs的HER和OER催化剂的最新研究进展,重点介绍了异质结构、掺杂、纳米结构工程等用于提高催化剂性能的各种策略,展望了未来基于TMTs催化剂的研究方向。