Enhancing Li-S battery performance via functional polymer binders for polysulfide inhibition

The commercialization of lithium-sulfur(Li-S)batteries faces several challenges,including poor conductivity,unexpected volume expansion,and continuous sulfur loss from the cathode due to redox shuttling.In this study,we introduce a novel polymer via a simple cross-linking between poly(ether-thioureas)(PETU)and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS)as a bifunctio nal binder for Li-S batteries(devotes as"PPTU").Compared to polyvinylidene fluoride(PVDF),as-prepared PPTU exhibits significantly higher electrical conductivity,facilitating electrochemical reactions.Additionally,PPTU demonstrates effective adsorption of lithium polysulfides,leading to improved cycling stability by suppressing the shuttling effect.We investigate this behavior by monitoring morphological changes at the cell interface using synchrotron X-ray tomography.Cells with PPTU binders exhibit remarkable rate performance,desired reversibility,and excellent cycling stability even under stringent bending and twisting conditions.Our work represents promising progress in functional polymer binder development for Li-S batteries.

NbN quantum dots anchored hollow carbon nanorods as efficient polysulfide immobilizer and lithium stabilizer for Li-S full batteries

The shuttle effect of lithium polysulfides(LiPSs)and uncontrollable lithium dendrite growth seriously hinder the practical application of lithium-sulfur(Li-S)batteries.To simultaneously address such issues,monodispersed Nb N quantum dots anchored on nitrogen-doped hollow carbon nanorods(NbN@NHCR)are elaborately developed as efficient Li PSs immobilizer and Li stabilizer for high-performance Li-S full batteries.Density functional theory(DFT)calculations and experimental characterizations demonstrate that the sulfiphilic and lithiophilic NbN@NHCR hybrid can not only efficiently immobilize the soluble Li PSs and facilitate diffusion-conversion kinetics for alleviating the shuttling effect,but also homogenize the distribution of Li+ions and regulate uniform Li deposition for suppressing Li-dendrite growth.As a result,the assembled Li-S full batteries(NbN@NHCR-S||Nb N@NHCR-Li)deliver excellent long-term cycling stability with a low decay rate of 0.031%per cycle over 1000 cycles at high rate of 2 C.Even at a high S loading of 5.8 mg cm^(-2)and a low electrolyte/sulfur ratio of 5.2μL mg^(-1),a large areal capacity of 6.2 mA h cm^(-2)can be achieved in Li-S pouch cell at 0.1 C.This study provides a new perspective via designing a dual-functional sulfiphilic and lithiophilic hybrid to address serious issues of the shuttle effect of S cathode and dendrite growth of Li anode.

Ten-Minute Synthesis of a New Redox-Active Aqueous Binder for Flame-Retardant Li-S Batteries

As a critical role in battery systems,polymer binders have been shown to efficiently suppress the lithium polysulfide shuttling and accommodate volume changes in recent years.However,preparation processes and safety,as the key criterions for Li-S batteries'practical applications,still attract less attention.Herein,an aqueous multifunction binder(named PEI-TIC)is prepared via an easy and fast epoxy-amine ring-opening reaction(10 min),which can not only give the sulfur cathode a stable mechanical property,a strong chemical adsorption and catalytic conversion ability,but also a fire safety improvement.The Li-S batteries based on the PEI-TIC binder display a high discharge capacity(1297.8 mAh g^(-1)),superior rate performance(823.0 mAh g^(-1)at 2 C),and an ultralow capacity decay rate of 0.035%over more than 800 cycles.Even under 7.1 mg cm^(-2)S-loaded,the PEI-TIC electrode can also achieve a high areal capacity of 7.2 mA h g^(-1)and excellent cycling stability,confirming its application potential.Moreover,it is also noted that TG-FTIR test is performed for the first time to explore the flame-retardant mechanism of polymer binders.This work provides an economically and environmentally friendly binder for the practical application and inspires the exploration of the flame-retardant mechanism of all electrode components.

Three-in-one LaNiO_(3) functionalized separator boosting electrochemical stability and redox kinetics for high-performance Li-S battery

The lithium-sulfur(Li-S)battery,as one of the energy storage devices,has been in the limelight due to its high theoretical energy density.However,the poor redox kinetics and the"shuttle effect"of polysulfides severely restrict the use of Li-S batteries in practical applications.Herein,a novel bimetallic LaNiO_(3) functional material with high electrical conductivity and catalytic property is prepared to act as a high-efficiency polysulfide shuttling stopper.The three LaNiO_(3) samples with different physical/chemical characteristics are obtained by controlling the calcination temperature.In conjunction with the high electrical conductivity and excellent catalytic properties of the as-prepared materials,the appropriate chemisorption toward polysulfides offers great potential to enhance electrochemical stability for highperformance Li-S batteries.Particularly,the Li-S cell with the separator modified by such functional material gives a specific capacity of 658 mA h g^(-1) after 500 cycles at a high current density of 2 C.Even with high sulfur loading of 6.05 mg cm^(-2),the Li-S battery still exhibits an areal specific capacity of 2.81 m A h cm^(-2)after 150 cycles.This work paves a new avenue for the rational design of materials for separator modification in high-performance Li-S batteries.

Tuning dual-atom mediator toward high-rate bidirectional polysulfide conversion in Li-S batteries

An emerging practice in the realm of Li-S batteries lies in the employment of single-atom catalysts(SACs)as effective mediators to promote polysulfide conversion,but monometallic SACs affording isolated geometric dispersion and sole electronic configuration limit the catalytic benefits and curtail the cell performance.Here,we propose a class of dual-atom catalytic moieties comprising hetero-or homo-atomic pairs anchored on N-doped graphene(NG)to unlock the liquid–solid redox puzzle of sulfur,readily realizing Li-S full cell under high-rate-charging conditions.As for Fe-Ni-NG,in-depth experimental and theoretical analysis reveal that the hetero-atomic orbital coupling leads to altered energy levels,unique electronic structures,and varied Fe oxidation states in comparison with homo-atomic structures(FeFe-NG or Ni-Ni-NG).This would weaken the bonding energy of polysulfide intermediates and thus enable facile electrochemical kinetics to gain rapid liquid-solid Li_(2)S_(4)?Li_(2)S conversion.Encouragingly,a Li-S battery based on the S@Fe-Ni-NG cathode demonstrates unprecedented fast-charging capability,documenting impressive rate performance(542.7 mA h g^(-1)at 10.0 C)and favorable cyclic stability(a capacity decay of 0.016%per cycle over 3000 cycles at 10.0 C).This finding offers insights to the rational design and application of dual-atom mediators for Li-S batteries.

A semi-immobilized sulfur-rich copolymer backbone with conciliatory polymer skeleton and conductive substrates for high-performance Li-S batteries

Sulfur-rich polymers have gained a great deal of attention as the next-generation active materials in lithium-sulfur(Li-S)batteries due to their low cost,environmental compatibility,naturally sulfur uniform dispersion,and distinctive structure covalently bonding with sulfur atoms.However,the poor electrical conductivity and undesirable additional shuttle effect still hinder the commercial application of sulfur-rich polymers.Herein,we report a flexible semi-immobilization strategy to prepare allylterminated hyperbranched poly(ethyleneimine)-functionalized reduced graphene oxide(A-PEI-EGO)as sulfur-rich copolymer backbone.The semi-immobilization strategy can effectively reconcile the demand for polymer skeleton and conductive substrates through forming quaternary ammonium groups and reducing oxygen-containing functional groups,resulting in enhanced skeleton adsorption capacity and substrate electronic conductivity,respectively.Furthermore,the stable covalent bonding connection based on polymer molecules(A-PEI)not only completely prevents the additional shuttle effect of lithiation organic molecules and even sulfur-rich oligomers,but provides more inverse vulcanization active sites.As a result,the as-prepared A-PEI-EGO-S cathodes display an initial discharge capacity of1338 m A h g^(-1)at a rate of 0.1 C and an outstanding cycling stability of 0.046%capacity decay per cycle over 600 cycles.Even under 6.2 mg cm^(-2)S-loaded and sparing electrolyte of 6μL mg^(-1),the A-PEI-EGO-S cathode can also achieve a superior cycling performance of 98%capacity retention after 60 cycles,confirming its application potential.

Towards Practical Application of Li-S Battery with High Sulfur Loading and Lean Electrolyte:Will Carbon-Based Hosts Win This Race?

As the need for high-energy–density batteries continues to grow, lithium-sulfur(Li–S) batteries have become a highly promising next-generation energy solution due to their low cost and exceptional energy density compared to commercially available Li-ion batteries. Research into carbon-based sulfur hosts for Li–S batteries has been ongoing for over two decades, leading to a significant number of publications and patents.However, the commercialization of Li–S batteries has yet to be realized. This can be attributed, in part, to the instability of the Li metal anode. However, even when considering just the cathode side, there is still no consensus on whether carbon-based hosts will prove to be the best sulfur hosts for the industrialization of Li–S batteries. Recently, there has been controversy surrounding the use of carbon-based materials as the ideal sulfur hosts for practical applications of Li–S batteries under high sulfur loading and lean electrolyte conditions. To address this question, it is important to review the results of research into carbon-based hosts, assess their strengths and weaknesses, and provide a clear perspective. This review systematically evaluates the merits and mechanisms of various strategies for developing carbon-based host materials for high sulfur loading and lean electrolyte conditions. The review covers structural design and functional optimization strategies in detail, providing a comprehensive understanding of the development of sulfur hosts. The review also describes the use of efficient machine learning methods for investigating Li–S batteries. Finally, the outlook section lists and discusses current trends, challenges, and uncertainties surrounding carbon-based hosts, and concludes by presenting our standpoint and perspective on the subject.

Dual-Functional Lithiophilic/Sulfiphilic Binary-Metal Selenide Quantum Dots Toward High-Performance Li-S Full Batteries

The commercial viability of lithium-sulfur batteries is still challenged by the notorious lithium polysulfides(Li PSs)shuttle effect on the sulfur cathode and uncontrollable Li dendrites growth on the Li anode.Herein,a bi-service host with Co-Fe binary-metal selenide quantum dots embedded in three-dimensional inverse opal structured nitrogen-doped carbon skeleton(3DIO FCSe-QDs@NC)is elaborately designed for both sulfur cathode and Li metal anode.The highly dispersed FCSe-QDs with superb adsorptive-catalytic properties can effectively immobilize the soluble Li PSs and improve diffusion-conversion kinetics to mitigate the polysulfide-shutting behaviors.Simultaneously,the 3D-ordered porous networks integrated with abundant lithophilic sites can accomplish uniform Li deposition and homogeneous Li-ion flux for suppressing the growth of dendrites.Taking advantage of these merits,the assembled Li-S full batteries with 3DIO FCSe-QDs@NC host exhibit excellent rate performance and stable cycling ability(a low decay rate of 0.014%over 2,000 cycles at 2C).Remarkably,a promising areal capacity of 8.41 mAh cm^(-2)can be achieved at the sulfur loading up to 8.50 mg cm^(-2)with an ultra-low electrolyte/sulfur ratio of 4.1μL mg^(-1).This work paves the bi-serve host design from systematic experimental and theoretical analysis,which provides a viable avenue to solve the challenges of both sulfur and Li electrodes for practical Li-S full batteries.

Nickel single atom overcoordinated active sites to accelerate the electrochemical reaction kinetics for Li-S cathode

Lithium-sulfur(Li-S)batteries with high theoretical energy density are promising advanced energy storage devices.However,shuttling of dissolute lithium polysulfide(LiPSs)and sluggish conversion kinetics impede their applications.Herein,single nickel(Ni)atoms on two-dimensional(2D)nitrogen(N)-doped carbon with Ni-N_(4)-O overcoordinated structure(SANi-N_(4)-O/NC)are prepared and firstly used as a sulfur host of Li-S batteries.Due to the efficient polysulfides traps and highly LiPSs conversion effect of SANi-N_(4)-O/NC,the electrochemical performance of Li-S batteries obviously improved.The batteries can well operate even under high sulfur loading(5.8 mg cm^(-2))and lean electrolyte(6.1μL mg^(-1))condition.Meanwhile,density functional theory(DFT)calculations demonstrate that Ni single atom’s active sites decrease the energy barriers of conversion reactions from Li_(2)S_(8)to Li2S due to the strong interaction between SANi-N_(4)-O/NC and LiPSs.Thus,the kinetic conversion of LiPSs was accelerated and the shuttle effect is suppressed on SANi-N_(4)-O/NC host.This study provides a new design strategy for a 2D structure with single-atom overcoordinated active sites to facilitate the fast kinetic conversion of LiPSs for Li-S cathode.

Isolated diatomic Zn-Co metal–nitrogen/oxygen sites with synergistic effect on fast catalytic kinetics of sulfur species in Li-S battery

Lithium-sulfur batteries are severely restricted by low electronic conductivity of sulfur and Li_(2)S,shuttle effect,and slow conversion reaction of lithium polysulfides(LiPSs).Herein,we report a facile and highyield strategy for synthesizing dual-core single-atom catalyst(ZnCoN_(4)O_(2)/CN)with atomically dispersed nitrogen/oxygen-coordinated Zn-Co sites on carbon nanosheets.Based on density functional theory(DFT)calculations and LiPSs conversion catalytic ability,ZnCoN_(4)O_(2)/CN provides dual-atom sites of Zn and Co,which could facilitate Li^(+)transport and Li_(2)S diffusion,and catalyze LiPSs conversion more effectively than homonuclear bimetallic single-atom catalysts or their simple mixture and previously reported singleatom catalysts.Li-S cell with ZnCoN_(4)O_(2)/CN modified separator showed excellent rate performance(789.4 mA h g^(-1)at 5 C)and stable long cycle performance(0.05%capacity decay rate at 6C with 1000cycles,outperforming currently reported single atomic catalysts for LiPSs conversion.This work highlights the important role of metal active centers and provides a strategy for producing multifunctional dual-core single atom catalysts for high-performance Li-S cells.

Minimizing Carbon Content with Three-in-One Functionalized Nano Conductive Ceramics:Toward More Practical and Safer S Cathodes of Li-S Cells

Using porous carbon hosts in cathodes of Li-S cells can disperse S actives and offset their poor electrical conductivity.However,such reservoirs would in turn absorb excess electrolyte solvents to S-unfilled regions,causing the electrolyte overconsumption,specific energy decline,and even safety hazards for battery devices.To build better cathodes,we propose to substitute carbons by In-doped SnO_(2)(ITO)nano ceramics that own three-in-one functionalities:1)using conductive ITO enables minimizing the total carbon content to an extremely low mass ratio(~3%)in cathodes,elevating the electrode tap density and averting the electrolyte overuse;2)polar ITO nanoclusters can serve as robust anchors toward Li polysulfide(LiPS)by electrostatic adsorption or chemical bond interactions;3)they offer catalysis centers for liquid–solid phase conversions of S-based actives.Also,such ceramics are intrinsically nonflammable,preventing S cathodes away from thermal runaway or explosion.These merits entail our configured cathodes with high tap density(1.54 g cm^(−3)),less electrolyte usage,good security for flame retardance,and decent Li-storage behaviors.With lean and LiNO_(3)-free electrolyte,packed full cells exhibit excellent redox kinetics,suppressed LiPS shuttling,and excellent cyclability.This may trigger great research enthusiasm in rational design of low-carbon and safer S cathodes.

Anchoring polysulfide with artificial solid electrolyte interphase for dendrite-free and low N/P ratio Li-S batteries

Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.

Mg-3Li和Mg-3Li-1Sc合金直接化学镀镍工艺研究

选用真空熔炼Mg-3Li和Mg-3Li-1Sc合金为实验材料,在以Ni2SO4为主盐的溶液中对其进行化学镀镍。以主盐和还原剂的配比、施镀温度和时间为变量,进行正交实验,对获得的化学镀镍层进行形貌观察,并用3.5%NaCl水溶液全浸实验评价镀层的耐蚀性。结果表明:主盐与还原剂配比为1∶1时两种合金镀层耐蚀性较高;最优温度与时间为:90℃/3 h(Mg-3Li)和80℃/2 h(Mg-3Li-1Sc)。

挤压变形Mg-5Li-2.6Al-1.8Zn合金的显微组织及力学性能

采用真空感应熔炼炉熔铸了Mg-5Li-2.6Al-1.8Zn合金,对该合金进行了挤压变形,采用OM、SEM、XRD、EDS等检测了挤压态合金的显微组织,室温拉伸试验测试了挤压态合金的力学性能,并观察了断口形貌。结果表明,挤压态Mg-5Li-2.6Al-1.8Zn合金由基体α-Mg和少量的AlLi相组成,晶粒尺寸细小。挤压态Mg-5Li-2.6Al-1.8Zn合金具有较高的力学性能,抗拉强度达到260 MPa,伸长率为20.7%,断口主要由韧窝组成,合金具有较好的韧性。

双相合金Mg-8Li-1Al的等通道转角挤压 Ⅰ.挤压过程中的变形方式

以X射线衍射分析术为主要分析手段,探讨了双相合金Mg-8Li-1Al(质量分数, ％)在等通道转角挤压(ECAP)变形过程中的变形方式. α相在第1道次ECAP过程中主要的变形方式是{1011}〈1012〉孪生,在随后道次的ECAP过程中主要变形方式为位错滑移,变形方式的转变主要是由于ECAP造成的组织细化效应;对于β相,各道次ECAP的主要变形方式均为位错滑移.

Effects of ultrasonic vibration on solidification structure and properties of Mg-8Li-3Al alloy

Ultrasonic vibration was introduced into the Mg-8Li-3A1 alloy melt during its solidification process. The microstructure, corrosion resistance and mechanical properties of the Mg-8Li-3A1 alloy under ultrasonic vibration were investigated. The experiment results show that the morphology of a phase is modified from coarse rosette-like structure to fine globular one with the application of ultrasonic vibration. The fine globular structure is obtained especially when the power is 170 W, and the refining effect also gets better with prolonging the ultrasonic treatment time. The corrosion resistance of the alloy with 170 W of ultrasonic vibration for 90 s is improved apparently compared with the alloy without ultrasonic vibration. The mechanical properties of alloys with ultrasonic vibration are also both improved apparently. The tensile strength and elongation of alloy improve by 9.5% and 45.7%, respectively, with 170 W of ultrasonic treatment for 90 s.

Effects of yttrium and strontium additions on as-cast microstructure of Mg-14Li-1Al alloys

Mg-14Li-1Al （LA141）, LA141-0.3Y, LA141-0.3Sr, and LA141-0.3Y-0.3Sr alloys were prepared in an induction furnace in the argon atmosphere. The microstructures of these alloys were investigated through scanning electron microscope （SEM）, X-ray diffractometer （XRD） and energy dispersive spectrometer （EDS）. The results show that yttrium and/or strontium additions produce a strong grain refining effect in LA141 alloy. The mean grain sizes of the alloys with addition of Y and/or Sr are reduced remarkably from 600 to 500, 260, 230 μm, respectively. Al 2 Y, Al 4 Sr and Mg 17 Sr 2 phases with different morphologies are verified and exist inside the grain or at the grain boundaries, thus possibly act as heterogeneous nucleation sites and pin up grain boundaries, which restrain the grain growth.

“Li-6400光合作用测定仪”在葡萄上应用的商榷

光合作用测定在植物生理特性的研究中一直占有重要地位。目前光合速率的测定方法有氧电极法、半叶法和二氧化碳变量法,其中二氧化碳变量法所测数据稳定,使用方便,测量准确,其仪器“Li-6400光合作用测定仪(Li-6400 portable photosynthesis system)”得到了广泛使用。为了给实际应用提供科学依据,对其在葡萄测量过程中各个细节及注意的问题进行了初步研究,增补了一些该仪器测量参数中没有的指标,以供科研人员、实验操作人员在实践中参考应用。

“Li-6400光合作用测定仪”在小麦上应用的商榷

光合作用测定在植物生理特性的研究中一直占有重要地位。目前光合速率的测定方法有氧电极法、半叶法和二氧化碳变量法,其中二氧化碳变量法所测数据稳定,使用方便,测量准确,其仪器"Li-6400光合作用测定仪(英文名称:Li-6400portablephotosynthesissystem)"被广泛使用。为了给实际应用提供科学依据,对其在小麦测量过程中各个细节及注意的问题进行了初步研究,增补了一些该仪器测量参数中没有的指标,以供科研人员、实验操作人员在实践中参考应用。

国内应用LI-8100开路式土壤碳通量测量系统测量土壤呼吸研究进展

土壤呼吸在全球碳收支中占据重要地位。LI-8100开路式土壤碳通量测量系统以其精确、快速等优点成为当前土壤碳通量研究的首选仪器之一。本文总结了近些年我国利用该仪器进行土壤碳通量的研究工作,重点阐述了土壤呼吸的日变化、月变化规律,分析了温度、湿度以及土地利用方式等影响土壤呼吸的因素,最后指出了目前利用该仪器进行土壤碳通量研究中存在的主要问题及今后的应用和发展方向。