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.

Low-temperature characteristicsof rubbers and performance testsof type 120 emergencyvalve diaphragms

Purpose–The type 120 emergency valve is an essential braking component of railway freight trains,butcorresponding diaphragms consisting of natural rubber(NR)and chloroprene rubber(CR)exhibit insufficientaging resistance and low-temperature resistance,respectively.In order to develop type 120 emergency valverubber diaphragms with long-life and high-performance,low-temperatureresistant CR and NR were processed.Design/methodology/approach–The physical properties of the low-temperature-resistant CR and NRwere tested by low-temperature stretching,dynamic mechanical analysis,differential scanning calorimetryand thermogravimetric analysis.Single-valve and single-vehicle tests of type 120 emergency valves werecarried out for emergency diaphragms consisting of NR and CR.Findings–The low-temperature-resistant CR and NR exhibited excellent physical properties.The elasticityand low-temperature resistance of NR were superior to those of CR,whereas the mechanical properties of thetwo rubbers were similar in the temperature range of 0℃–150℃.The NR and CR emergency diaphragms metthe requirements of the single-valve test.In the low-temperature single-vehicle test,only the low-temperaturesensitivity test of the NR emergency diaphragm met the requirements.Originality/value–The innovation of this study is that it provides valuable data and experience for futuredevelopment of type 120 valve rubber diaphragms.

Boosting oxygen reduction activity and CO_(2) resistance on bismuth ferrite-based perovskite cathode for low-temperature solid oxide fuel cells below 600℃

Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.

Advances in sodium-ion batteries at low-temperature: Challenges and strategies

With the continuing boost in the demand for energy storage,there is an increasing requirement for batteries to be capable of operation in extreme environmental conditions.Sodium-ion batteries(SIBs) have emerged as a highly promising energy storage solution due to their promising performance over a wide range of temperatures and the abundance of sodium resources in the earth's crust.Compared to lithiumion batteries(LIBs),although sodium ions possess a larger ionic radius,they are more easily desolvated than lithium ions.Fu rthermore,SIBs have a smaller Stokes radius than lithium ions,resulting in improved sodium-ion mobility in the electrolyte.Nevertheless,SIBs demonstrate a significant decrease in performance at low temperatures(LT),which constrains their operation in harsh weather conditions.Despite the increasing interest in SIBs,there is a notable scarcity of research focusing specifically on their mechanism under LT conditions.This review explores recent research that considers the thermal tolerance of SIBs from an inner chemistry process perspective,spanning a wide temperature spectrum(-70 to100℃),particularly at LT conditions.In addition,the enhancement of electrochemical performance in LT SIBs is based on improvements in reaction kinetics and cycling stability achieved through the utilization of effective electrode materials and electrolyte components.Furthermore,the safety concerns associated with SIBs are addressed and effective strategies are proposed for mitigating these issues.Finally,prospects conducted to extend the environmental frontiers of commercial SIBs are discussed mainly from three viewpoints including innovations in materials,development and research of relevant theoretical mechanisms,and intelligent safety management system establishment for larger-scale energy storage SIBs.

Temperature inversion enables superior stability for low-temperature Zn-ion batteries

It is challenging for aqueous Zn-ion batteries(ZIBs)to achieve comparable low-temperature(low-T)performance due to the easy-frozen electrolyte and severe Zn dendrites.Herein,an aqueous electrolyte with a low freezing point and high ionic conductivity is proposed.Combined with molecular dynamics simulation and multi-scale interface analysis(time of flight secondary ion mass spectrometry threedimensional mapping and in-situ electrochemical impedance spectroscopy method),the temperature independence of the V_(2)O_(5)cathode and Zn anode is observed to be opposite.Surprisingly,dominated by the solvent structure of the designed electrolyte at low temperatures,vanadium dissolution/shuttle is significantly inhibited,and the zinc dendrites caused by this electrochemical crosstalk are greatly relieved,thus showing an abnormal temperature inversion effect.Through the disclosure and improvement of the above phenomena,the designed Zn||V_(2)O_(5)full cell delivers superior low-T performance,maintaining almost 99%capacity retention after 9500 cycles(working more than 2500 h)at-20°C.This work proposes a kind of electrolyte suitable for low-T ZIBs and reveals the inverse temperature dependence of the Zn anode,which might offer a novel perspective for the investigation of low-T aqueous battery systems.

Effect of samarium doping on the activity and sulfur resistance of Ce/MnFeO_(x) catalyst for low-temperature selective catalytic reduction of NO_(x) by ammonia

The self-made MnFeO_(x) catalysts doped with cerium and samarium were prepared by impregnation method for low-temperature selective catalytic reduction(SCR)by NH3.In this work,the surface properties of the series of MnFe-based catalysts were studied.The results indicate Sm-modified catalyst have superior low-temperature SCR activity;NO_(x) conversion maintained at nearby to 100%at 90℃ to 240℃.In addition,The N_(2) selectivity of Sm doping remains above 80%in the range of 60℃ to 150℃.In SO_(2) poisoning test,the NO_(x) conversion can be remained>90%after 10 h of reaction.The XPS,NH_(3)-TPD and H_(2)-TPR results show the catalyst with Sm doping enhances the acid sites and oxidation catalytic sites of mixed oxides serves for improving oxygen vacancies and transfer electrons.In situ diffuse reflaxions infrared Fourier transformations spectroscopy(DRIFTS)results show that NO_(x) is more easily adsorbed on the surface after Sm doping,which provided favorable conditions for the NH_(3)-SCR reaction to proceed.The reaction at the catalyst surface will follow the L-H reaction mechanism by transient reaction test.

Screening non-noble metal oxides to boost the low-temperature combustion of polyethylene waste in air

Globally,the efficient utilization of polymer wastes is one of the most important issues for current sustainable development topics.Herein,a green and efficient low-temperature combustion approach is proposed to deal with polymer wastes and recover heat energy,simultaneously alleviating the environment and energy crisis.Non-noble metal oxides(Al_(2)O_(3),Fe_(2)O_(3),NiO_(2),ZrO_(2),La_(2)O_(3)and CeO_(2)) were prepared,characterized and screened to boost the low-temperature combustion of polyethylene waste at 300℃ in air.The mass change,heat release and CO_(x) formation were studied in details and employed to evaluate the combustion rate and efficiency.It was found that CeO_(2)significantly enhanced the combustion rate and efficiency,which was respectively 2 and 7 times that of non-catalytic case.An interesting phenomenon was observed that the catalytic performance of CeO_(2) in polyethylene low-temperature combustion was significantly improved by the 7-day storage in the room environment or water treatment.XPS analysis confirmed the co-existence of Ce^(3+) and Ce^(4+) in CeO_(2),and the 7-day storage and water treatment promoted the amount of Ce^(3+),which facilitated the formation of the oxygen vacancies.That may be the reason why CeO_(2) exhibited excellent catalytic performance in polyethylene low-temperature combustion.

Impact of Low-temperature Storage on Volatile Flavor Compounds in Prepared Pork Products

[Objectives]This study was conducted to explore the dynamic changes of volatile flavor compounds in prepared pork during storage at different low-temperature conditions.[Methods]Prepared pork was stored at 4,-4 and-18℃.The volatile flavor compounds of prepared pork were determined by solid-phase microextraction-gas chromatography-mass spectrometry(SPME-GC-MS)at days 0,7,14,21 and 28,and relative odor activity value(OAV),principal component analysis(PCA)and cluster analysis(CA)were combined to analyze changes in volatile flavor compounds of prepared pork during storage.[Results]The total number of volatile flavor compounds gradually decreased with the prolongation of the storage period,and OAV analysis identified 22 key flavor compounds(OAV≥1).The results of PCA and CA showed that 2-methyl-1-butanol,1-octen-3-ol,linalool,cineole,hexanal and nonanal were the main key flavor components,and the degree of flavor degradation was low under both superchilling and freezing conditions.After 28 days of storage,the alcohol content in the chilling group was significantly higher than other two groups,and the overall content of volatile flavor compounds was also significantly higher than other two groups,indicating that the-4℃chilling storage was more favorable for maintaining the overall flavor of prepared pork.[Conclusions]This study provides a theoretical basis for finding a better storage method for prepared meat products.

Enhancing performance of low-temperature processed CsPbI2Br all-inorganic perovskite solar cells using polyethylene oxide-modified TiO_(2)

CsPbX_(3)-based(X=I,Br,Cl)inorganic perovskite solar cells(PSCs)prepared by low-temperature process have attracted much attention because of their low cost and excellent thermal stability.However,the high trap state density and serious charge recombination between low-temperature processed TiO_(2)film and inorganic perovskite layer interface seriously restrict the performance of all-inorganic PSCs.Here a thin polyethylene oxide(PEO)layer is employed to modify TiO_(2)film to passivate traps and promote carrier collection.The impacts of PEO layer on microstructure and photoelectric characteristics of TiO_(2)film and related devices are systematically studied.Characterization results suggest that PEO modification can reduce the surface roughness of TiO_(2)film,decrease its average surface potential,and passivate trap states.At optimal conditions,the champion efficiency of CsPbI_(2)Br PSCs with PEO-modified TiO_(2)(PEO-PSCs)has been improved to 11.24%from 9.03%of reference PSCs.Moreover,the hysteresis behavior and charge recombination have been suppressed in PEO-PSCs.

Ca and Sr co-doping induced oxygen vacancies in 3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts for boosting low-temperature oxidative coupling of methane

It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.

Low-temperature Denitration Mechanism of NH_(3)-SCR over Fe/AC Catalyst

To study the modification mechanism of activated carbon(AC)by Fe and the low-temperature NH_(3)-selective catalytic reduction(SCR)denitration mechanism of Fe/AC catalysts,Fe/AC catalysts were prepared using coconut shell AC activated by nitric acid as the support and iron oxide as the active component.The crystal structure,surface morphology,pore structure,functional groups and valence states of the active components of Fe/AC catalysts were characterised by X-ray diffraction,scanning electron microscopy,nitrogen adsorption and desorption,Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy,respectively.The effect of Fe loading and calcination temperature on the low-temperature denitration of NH_(3)-SCR over Fe/AC catalysts was studied using NH_(3)as the reducing gas at low temperature(150℃).The results show that the iron oxide on the Fe/AC catalyst is spherical and uniformly dispersed on the surface of AC,thereby improving the crystallisation performance and increasing the number of active sites and specific surface area on AC in contact with the reaction gas.Hence,a rapid NH_(3)-SCR reaction was realised.When the roasting temperature remains constant,the iron oxide crystals formed by increasing the amount of loading can enter the AC pore structure and accumulate to form more micropores.When the roasting temperature is raised from 400 to 500℃,the iron oxide is mainly transformed fromα-Fe_(2)O_(3)toγ-Fe_(2)O_(3),which improves the iron oxide dispersion and increases its denitration active site,allowing gas adsorption.When the Fe loading amount is 10%,and the roasting temperature is 500℃,the NO removal rate of the Fe/AC catalyst can reach 95%.According to the study,the low-temperature NH_(3)-SCR mechanism of Fe/AC catalyst is proposed,in which the redox reaction between Fe~(2+)and Fe~(3+)will facilitate the formation of reactive oxygen vacancies,which increases the amount of oxygen adsorption on the surface,especially the increase in surface acid sites,and promotes and adsorbs more reaction gases(NH_(3),O_(2),NO).The transformation from the standard SCR reaction to the fast SCR reaction is accelerated.

基于深度强化学习的SCR脱硝系统协同控制策略研究

针对选择性催化还原(SCR)脱硝系统大惯性、多扰动等特点,提出了一种基于多维状态信息和分段奖励函数优化的深度确定性策略梯度(DDPG)协同比例积分微分(PID)控制器的控制策略。针对SCR脱硝系统中存在部分可观测马尔可夫决策过程(POMDP),导致DDPG算法策略学习效率较低的问题,首先设计SCR脱硝系统的多维状态信息;其次,设计SCR脱硝系统的分段奖励函数;最后,设计DDPG-PID协同控制策略,以实现SCR脱硝系统的控制。结果表明:所设计的DDPG-PID协同控制策略提高了DDPG算法的策略学习效率,改善了PID的控制效果,同时具有较强的设定值跟踪能力、抗干扰能力和鲁棒性。

W火焰锅炉SCR脱硝超低排放技术及应用

截至2021年底,全国已有超过95%的燃煤火电机组实现了氮氧化物超低排放,剩余均为燃用无烟煤的W火焰锅炉,其产生的氮氧化物质量浓度高达750~1200 mg/m^(3),实现超低排放难度大,是我国实现超低排放政策的“最后一公里”。目前,选择性催化还原(SCR)脱硝流场技术主要有“SCR分区混合动态调平技术”“全烟道断面混合流场技术”“常规精准喷氨技术”等。以某设计脱硝效率需高达95%的W火焰锅炉为例,通过计算流体力学(CFD)模拟的方式对比3种技术的性能指标,“SCR分区混合动态调平技术”的各项指标明显优于其他技术。工程改造后,在脱硝系统入口氮氧化物质量浓度为1000 mg/m^(3),出口低于50 mg/m^(3)时,可实时保持氨逃逸量小于3μL/L,远超常规SCR脱硝系统最高设计效率(93%),为W火焰锅炉氮氧化物超低排放提供了新的技术路线。

基于AMESim的柴油机SCR系统NO_(X)转化率仿真与验证

为研究车用柴油机SCR系统催化转化效率的影响因素,利用AMESim软件建立SCR系统仿真模型,结合台架试验,分析了排气温度、NO_(2)/NO_(X)值以及排气流量对系统NO_(X)转化率的影响。将不同温度下SCR系统仿真输出的NO_(X)转化率数据进行了实验验证,结果表明模型预测误差小于5%。仿真结果显示:SCR系统的NO_(X)转化率会随排气温度升高而明显增大,370~450℃为系统性能的最佳温度区间,NO_(X)转化率最大值均在88%以上。NO_(X)转化率随着NO_(2)/NO_(X)值的提高而增加,且当NO_(2)/NO_(X)值为55%~60%时达到峰值。当排气温度处于400~450℃之间时,NO_(X)转化率受排气流量影响较小,转化率稳定在90%左右。确定了SCR系统在发动机不同工况条件下的工作性能,为后续的尿素喷射控制研究提供指导依据。

SCR脱硝系统的RBF条件积分滑模参数优化控制

针对选择性催化还原(SCR)脱硝系统在火电机组深度调峰下因系统特性随着机组负荷改变而难以控制的问题,提出基于径向基函数(RBF)的条件积分滑模优化控制方案,用条件积分滑模减少抖振与调节时间,用RBF实时逼近SCR脱硝系统特性改变下的未知扰动以提高系统鲁棒性。并提出一种纳什均衡量子粒子群寻优(NEQPSO)算法,以获得RBF条件积分滑模控制方案的最优参数,并在20%~100%的机组负荷下进行仿真实验。结果表明:优化后的RBF条件积分滑模控制与传统控制方案相比超调量降低50.26%、调节时间缩短13.55%,在干扰信号下超调量仅有1.50%,其响应速度更快、抗干扰能力更强、鲁棒性更好。

基于神经网络的烧结SCR脱硝系统动态建模研究

提出一种基于注意力机制的CNN-LSTM神经网络预测模型,通过CNN提取局部特征、LSTM处理时序序列数据、注意力层提取信息,最终输出预测值的方式对脱硝系统进行动态建模。利用最大信息系数法筛选出相关性高的特征,以BP、CNN、LSTM、CNN-LSTM模型作为比较,采用均方根误差(E_(RMS))、平均绝对误差(E_(MA))和平均绝对百分比误差(E_(MAP))作为评价指标,评估NO_(x)浓度预测模型的性能。研究结果表明:基于注意力机制的CNN-LSTM模型预测NO_(x)浓度的准确度最高,E_(RMS)、E_(MA)、E_(MAP)分别0.6731、0.8670、1.5201%。该模型较其他对比模型相比,具有更高的预测精度、更强的泛化能力,可以实现对SCR系统的未来时间出口NO_(x)浓度的精准预测。通过该模型预测喷氨量可实现喷氨量的精准控制和减少NO_(x)排放的要求。

基于捣固焦化项目的SCR脱硝装置流场分析

利用CFD软件对烟道和单侧SCR(Selective Catalytic Reduction,选择性催化还原法)反应器结构进行建模仿真,设置烟气在反应器中流动特性的物理模型为湍流模型,在反应器结构不同位置放置导流板从而提高流场的均匀性。利用多孔介质模型模拟催化剂首层,分析流场通过首层催化剂的分布情况。通过对初始设计方案的SCR脱硝装置结构进行CFD数值模拟优化,确定最终优化方案符合SCR脱硝流场相关技术指标,为捣固焦化项目设计、脱硝反应器运行管理提供了参考。

基于改进深度强化学习的SCR脱硝系统复合控制研究

针对选择性催化还原(Selective catalytic reduction,SCR)脱硝系统延迟大、扰动多等特点,提出了一种基于改进双延迟深度确定性策略梯度(Twin delayed deep deterministic policy gradient,TD3)的SCR脱硝系统复合控制策略。首先,提出了一种融合多步时序差分(Muti-step temporal-difference,MSTD)和优先经验回放(Prioritized experience replay,PER)的改进TD3算法。该算法在策略更新时使用MSTD计算回报,同时利用PER选择重要的经验进行学习,以此提高TD3算法的策略学习能力并加速算法的学习过程。其次,通过设计多维状态观测,综合考虑SCR脱硝系统的前馈信号和验证反馈信号来实现SCR脱硝系统的复合控制,进而维持出口NOx浓度的稳定性。最后,进行仿真实验验证,结果表明基于MSTD-PER-TD3算法的复合控制策略能更有效地克服入口NOx浓度波动对出口NOx浓度的影响,并具有优秀的抗干扰能力和鲁棒性。

钢制悬链线立管(SCR)及其焊接接头的腐蚀疲劳行为研究进展

腐蚀疲劳开裂是海洋服役管线钢及其焊接接头最为严重的失效形式之一。近年来,研究人员对管线钢焊接接头腐蚀疲劳裂纹的机理、影响因素等方面的研究正在不断深入,但还有部分现象的解释未能统一。文中对腐蚀疲劳裂纹的萌生和扩展机理进行了阐述,对影响腐蚀疲劳裂纹扩展的材料、力学、环境等因素的研究进行了总结归纳,对新的结论和模型进行了探讨,并对进一步的研究进行了展望。

高效型SCR尿素计量泵精度标定台方案设计

SCR技术已成为柴油车降低NOX排放的主流技术方法。尿素泵作为SCR系统的核心部件之一,其计量精度直接影响系统运行效率。针对传统的尿素泵标定方法的不足,提出一种基于微小椭圆齿轮流量计的尿素计量泵精度标定台,设计了气助型和非气助型尿素泵标定方案,对于无回流型尿素计量泵,可采用单流量计装在吸液管上直接测量。对于有脉动强且有回流的尿素计量泵,使用“减重”法测量,在吸液管与回液管各安装一个椭圆齿轮流量计,通过差值的办法得到尿素喷射量。经过实践,实时性强,精度高。