In-situ interfacial passivation and self-adaptability synergistically stabilizing all-solid-state lithium metal batteries

The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.

Lithiophilic Li-Si alloy-solid electrolyte interface enabled by high-concentration dual salt-reinforced quasi-solid-state electrolyte

Solid polymer electrolytes(SPEs)are urgently required to achieve practical solid-state lithium metal batteries(LMBs)and lithium-ion batteries(LIBs),Herein,we proposed a mechanism for modulating interfacial conduction and anode interfaces in high-concentration SPEs by LiDFBOP.Optimized electrolyte exhibits superior ionic conductivity and remarkable interface compatibility with salt-rich clusters:(1)polymer-plastic crystal electrolyte(P-PCE,TPU-SN matrix)dissociates ion pairs to facilitate Li+transport in the electrolyte and regulates Li^(+)diffusion in the SEI.The crosslinking structure of the matrix compensates for the loss of mechanical strength at high-salt concentrations;(2)dual-anion TFSI^(-)_(n)-DFBOP^(-)_(m)in the Li^(+)solvation sheath facilitates facile Li^(+)desolvation and formation of salt-rich clusters and is conducive to the formation of Li conductive segments of TPU-SN matrix;(3)theoretical calculations indicate that the decomposition products of LiDFBOP form SEI with lower binding energy with LiF in the SN system,thereby enhancing the interfacial electrochemical redox kinetics of SPE and creating a solid interface SEI layer rich in LiF.As a result,the optimized electrolyte exhibits an excellent ionic conductivity of9.31×10^(-4)S cm^(-1)at 30℃and a broadened electrochemical stability up to 4.73 V.The designed electrolyte effectively prevents the formation of Li dendrites in Li symmetric cells for over 6500 h at0.1 mA cm^(-2).The specific Li-Si alloy-solid state half-cell capacity shows 711.6 mAh g^(-1)after 60 cycles at 0.3 A g^(-1).Excellent rate performance and cycling stability are achieved for these solid-state batteries with Li-Si alloy anodes and NCM 811 cathodes.NCM 811‖Prelithiated silicon-based anode solid-state cell delivers a discharge capacity of 195.55 mAh g^(-1)and a capacity retention of 97.8%after 120 cycles.NCM 811‖Li solid-state cell also delivers capacity retention of 84.2%after 450 cycles.

High-performance solid-state lithium metal batteries achieved by interface modification

Garnet-structured ceramic electrolyte Li_(6.75)La_(3)Zr_(1.75)Ta_(0.25)O_(12)(LLZTO)attracts significant consideration in solid-state Li metal batteries due to its wide electrochemical window and favorable compatibility with Li metal.However,the deployment of LLZTO is severely hampered by poor contact between LLZTO and Li metal anode.In this paper,an ultra-thin Al-Si interface buffer layer(10 nm)is constructed on LLZTO by a magnetron sputtering method,which allows superior wetting of Li onto the LLZTO surface due to the alloying reaction between the Al-Si layer and Li metal.The resulting Li/Al-Si coated LLZTO(ASL)/Li symmetrical cell delivers an interfacial resistance of 15.0Ωcm^(-2),which is much lower than that of 1140.3Ωcm^(-2)for the bare LLZTO symmetrical cell.Moreover,the Li/ASL/Li symmetrical cells exhibit stable plating/striping performance(800 h)with small voltage hysteresis at 1.0 mA cm^(-2).Besides,the full cell with LiFePO_(4)cathode reveals a high capacity of 124.1 mA h g^(-1)after 600 cycles at 0.5C with a lowcapacity decay of 0.032%per cycle.We believe this work will facilitate the development of solid-state rechargeable batteries.

Robust interface layers with redox shuttle reactions suppress the dendrite growth for stable solid-state Li metal batteries

Designing a durable lithium metal anode for solid state batteries requires a controllable and uniform deposition of lithium, and the metal lithium layer should maintain a good interface contact with solid state electrolyte during cycles. In this work, we construct a robust functional interface layer on the modified LiB electrode which considerably improves the electrochemical stability of lithium metal electrode in solid state batteries. It is found that the functional interface layer consisting of polydioxolane, polyiodide ion and Li TFSI effectively restrains the growth of lithium dendrites through the redox shuttle reaction of I-/I3-and maintains a good contact between lithium anode and solid electrolyte during cycles. Benefit from these two advantages, the modified Li-B anode exhibits a remarkable cyclic performance in comparison with those of the bare Li-B anode.

Review of the electrochemical performance and interfacial issues of high-nickel layered cathodes in inorganic all-solid-state batteries

All-solid-state batteries potentially exhibit high specific energy and high safety,which is one of the development directions for nextgeneration lithium-ion batteries.The compatibility of all-solid composite electrodes with high-nickel layered cathodes and inorganic solid electrolytes is one of the important problems to be solved.In addition,the interface and mechanical problems of high-nickel layered cathodes and inorganic solid electrolyte composite electrodes have not been thoroughly addressed.In this paper,the possible interface and mechanical problems in the preparation of high-nickel layered cathodes and inorganic solid electrolytes and their interface reaction during charge–discharge and cycling are reviewed.The mechanical contact problems from phenomena to internal causes are also analyzed.Uniform contact between the high-nickel cathode and solid electrolyte in space and the ionic conductivity of the solid electrolyte are the prerequisites for the good performance of a high-nickel layered cathode.The interface reaction and contact loss between the high-nickel layered cathode and solid electrolyte in the composite electrode directly affect the passage of ions and electrons into the active material.The buffer layer constructed on the high-nickel cathode surface can prevent direct contact between the active material and electrolyte and slow down their interface reaction.An appropriate protective layer can also slow down the interface contact loss by reducing the volume change of the high-nickel layered cathode during charge and discharge.Finally,the following recommendations are put forward to realize the development vision of high-nickel layered cathodes:(1)develop electrochemical systems for high-nickel layered cathodes and inorganic solid electrolytes;(2)elucidate the basic science of interface and electrode processes between high-nickel layered cathodes and inorganic solid electrolytes,clarify the mechanisms of the interfacial chemical and electrochemical reactions between the two materials,and address the intrinsic safety issues;(3)strengthen the development of research and engineering technologies and their preparation methods for composite electrodes with high-nickel layered cathodes and solid electrolytes and promote the industrialization of all-solid-state batteries.

Solid electrolyte-electrode interface based on buffer therapy in solid-state lithium batteries

In the past few years,the all-solid lithium battery has attracted worldwide attentions,the ionic conductivity of some all-solid lithium-ion batteries has reached 10^(-3)-10^(-2) S/cm,indicating that the transport of lithium ions in solid electrolytes is no longer a major problem.However,some interface issues become research hotspots.Examples of these interfacial issues include the electrochemical decomposition reaction at the electrode-electrolyte interface;the low effective contact area between the solid electrolyte and the electrode etc.In order to solve the issues,researchers have pursued many different approaches.The addition of a buffer layer between the electrode and the solid electrolyte has been at the center of this endeavor.In this review paper,we provide a systematic summarization of the problems on the electrode-solid electrolyte interface and detailed reflection on the latest works of buffer-based therapies,and the review will end with a personal perspective on the improvement of buffer-based therapies.

Preparation of Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2 powders for cathode material in secondary battery by solid-state method

Employing Li2CO3, NiO, Co3O4, and MnCO3 powders as starting materials, Li[Ni1/3Co1/3Mn1/3]O2 was synthesized by solid-state reaction method. Various grinding aids were applied during milling in order to optimize the synthesis process. After successive heat treatments at 650 and 950 ℃, the prepared powders were characterized by X-ray diffraction (XRD) analysis, scanning electron microscopy, and transmission electron microscopy. The powders prepared by adding salt (NaCl) as grinding aid exhibit a clear R3m layer structure. The powders by other grinding aids like heptane show some impurity peaks in the XRD pattern. The former powders show a uniform particle size distribution of less than 1 μm average size while the latter shows a wide distribution ranging from 1 to 10 μm. Energy dispersive X-ray (EDX) analysiss show that the ratio of Ni, Co, and Mn content in the powder is approximately 1/3, 1/3, and 1/3, respecively. The EDX data indicate no incorporation of sodium or chlorine into the powders. Charge-discharge tests gave an initial discharge capacity of 160 mAh·g-1 for the powders with NaCl addition while 70 mAh·g-1 for the powders with heptane.

建筑设计二维CAD协同制图的原理及操作要点

文章从二维建筑图的本质出发,分析了二维CAD图设计方法的局限性和优势。通过对比二维CAD图设计方法和三维建筑信息模型、建筑参数化设计方法的区别和各自的优缺点,从原理上分析了采用协同制图的优势,即通过参照制图方法构建起图形对象的关联性和唯一性,从而提高制图效率,降低失误率。文章还介绍了二维CAD制图的一些操作要点,以平面图为例,阐述了拆分零件图的基本方法,分析了参照、块和图层几种制图工具的各自特点和适用对象。

极区电离层N_(m)F_(2)观测与国际参考电离层对比研究

利用南北极极隙区与极光带纬度3个台站对电离层F2层峰值电子密度(N_(m)F_(2))长达1个太阳活动周的观测数据,对国际参考电离层IRI-2016模型在极区的适用性进行系统的定量研究。结果表明,在极光带纬度的北极Tromsø站,IRI预测与观测符合最好,大部分季节相对误差在40%以内,在太阳活动高年略好于太阳活动低年。在极隙区纬度的南极中山站和Longyearbyen站,IRI预测精度在太阳活动低年高于太阳活动高年。在中山站和北极Longyearbyen站仅个别月份相对误差在20%以内,大部分月份相对误差超过40%,冬季相对误差接近100%,特别是Longyearbyen站,在太阳活动高年冬季相对误差超过100%。从季节上看,3个台站都是冬季符合最差,夏季符合最好。IRI-2016模型对极区电离层进行预测时,难以如实反映极区等离子体对流和能量粒子沉降等极区特有的物理过程对极区电离层N_(m)F_(2)的影响。

大桩距刚性桩复合地基压板试验预制承压板设计

针对刚性桩复合地基压板试验承压板尺寸大,采用传统钢制承压板存在制作成本高、易变形、各尺寸适用灵活度低等缺陷,本文结合工程实际中各承压板所需尺寸,采用单、双层预制钢筋混凝土板代替钢板。试验前采用‘理正’结构计算软件验算承压板厚度和配筋。提出以双层预制钢筋混凝土承压板代替单层板,可进一步降低造价,便于安装,并满足压板刚度,提高试验精度,为大尺寸承压板设计提供参考。

Transformation of Undesired Li_(2)CO_(3)into Lithiophilic Layer Via Double Replacement Reaction for Garnet Electrolyte Engineering

Garnet-type solid-state electrolytes(SSEs)are a remarkable Li-ion electrolyte for the realization of next-generation all-solid-state lithium batteries due to their excellent stability against Li metal as well as high ionic conductivities at room temperature.However,garnet electrolytes always contain undesired and hardly removable Li_(2)CO_(3) contaminations that have persistently large resistance and unstable interface contact with Li metal.This is a critical bottleneck for the practical application of garnet electrolytes.Here,we design a novel strategy to completely root out Li_(2)CO_(3) both inside and on the surface of garnet.This is achieved by a so-called double replacement reaction between Li_(2)CO_(3) and SiO_(2) during one-step hot press process for garnet electrolyte densification.It leads to in-situ transformation of LixSiOy(LSO)mostly locating around the grain boundaries of garnet.Due to the higher ion conductivity and better electrochemistry stability of LSO than Li_(2)CO_(3),the modified garnet electrolyte shows much improved electrochemical performance.Moreover,the wettability between modified garnet electrolyte and lithium metals was significantly enhanced in the absence of surface Li_(2)CO_(3).As a proof of concept,an assembled Li symmetric cell with modified garnet electrolyte displays a high critical current density(CCD)of 0.7 mA cm^(-2)and a low interfacial impedance(5Ωcm^(2))at 25℃.These results indicate that the upcycling of Li_(2)CO_(3)is a promising strategy to well-address the degradation and interfacial issue associated with garnet electrolytes.

Peak of Electron Density in F2-Layer Parameters Variability at Quiet Days on Solar Minimum

This study deals with Peak of electron density in F2-layer sensibility scale during quiet time on solar minimum. Peaks of electron density in F2-layer (NmF2) values at the quietest days are compared to those carried out from the two nearest days (previous and following of quietest day). The study uses International Reference Ionosphere (IRI) for ionosphere modeling. The located station is Ouagadougou, in West Africa. Solar minimum of phase 22 is considered in this study. Using three core principles of ionosphere modeling under IRI running conditions, the study enables to carry out Peak of electron density in F2-layer values during the quietest days of the characteristic months for the four different seasons. These parameters are compared to those of the previous and the following of the quietest days (the day before and following each quietest selected day) at the same hour. The knowledge of NmF2 values at the quietest days and at the two nearest days enables to calculate the relative error that can be made on this parameter. This calculation highlights insignificant relative errors. This means that NmF2 values at the two nearest days of each quietest day on solar minimum can be used for simulating the quietest days’ behavior. NmF2 values obtained by running IRI model have good correlation with those carried out by Thermosphere-Ionosphere-Electrodynamics-General Circulation Model (TIEGCM).

A green route for the preparation of layered double hydroxides from basic magnesium carbonate

Layered double hydroxides(LDHs)have received extensive attention in many fields such as catalysis,environmental management and medical applications.Typically,expensive soluble metal salts are commonly used as the starting materials for the synthesis of LDHs.Here,we report a novel synthesis route for Mg/Al-LDH by using inexpensive basic magnesium carbonate as the starting material.X-ray diffraction(XRD)and solid-state nuclear magnetic resonance(ssNMR)data show that LDHs with rich defects are formed rapidly at room temperature and good crystallinity can be obtained after further hydrothermal treatment.These results provide a simple,rapid and green preparation method for LDHs.

Electron Bulk Surface Density Effect on Critical Frequency in the F2-Layer

Ionosphere layer is the atmosphere region which reflects radio waves for telecommunication. The density in particles in this layer influences the quality of communication. This study deals with the effects of Total Electron Contents (TEC) on the critical frequency of radio waves in the F2-layer. Total Electron Contents parameter symbolizes electron bulk surface density in ionosphere layer. Above critical frequency value in F2 layer (foF2), radio waves pass through ionosphere. The knowledge of this value enables to calibrate transmission frequencies. In this study, we consider TEC effects on foF2 under quiet time conditions during the maximum and the minimum of solar cycle 22, at Ouagadougou station, in West Africa. The study also considers the effects of seasons and the hourly variability of TEC and foF2. This work shows winter anomaly on foF2 and TEC on minimum and maximum of solar cycle phase respectively. Running International Reference Ionosphere (IRI) model enables to carry out the effects of TEC on foF2 by use of their monthly average values. This leads to a new approach to calibrate radio transmitters.

基于BP双层神经网络MRAS下PMSM的转速辨识研究

针对无速度传感器下传统模型参考自适应(MRAS)方法在低速区转速负载发生突变后速度估计准确度下降的问题,利用双层神经网络超强的在线估计以及自适应能力,提出一种基于误差反向传播(BP)双层人工神经网络(ANN)与MRAS相结合的转速辨识方法,实现了对低速范围下转速响应动态性能的改善。通过Matlab仿真以及PMSM驱动控制实物平台,对ANN-MRAS观测器与传统MRAS观测器进行对比分析,结果表明:在转速及负载转矩发生突变后,该方法仍能保持较好动态性能,具有较强的鲁棒性。

中、美、欧药典药材薄层鉴别差异与特征图谱的应用

目的 比较中、美、欧药典对药材薄层鉴别的要求与结果判定的差异,探究特征图谱在药材薄层色谱鉴别中的应用。方法 参照《中国药典》、《美国药典》和《欧洲药典》药材薄层色谱鉴别的方法,选取大蒜粉、甘草浸膏、胡芦巴和小茴香4味药材进行实验研究,选取人参和银杏叶两味药材进行案例分析,对不同药典药材薄层鉴别中对照品的选择和结果分析方法进行比较。结果 大蒜粉薄层鉴别中,《美国药典》采用2个对照品控制了6个成分;《欧洲药典》采用了替代对照品丙氨酸进行鉴别。甘草浸膏薄层鉴别中,《中国药典》选择甘草酸铵对照品进行鉴别;《美国药典》中选择甘草酸为对照品,鉴别甘草酸及其余成分;《欧洲药典》中选择甘草次酸对照品和百里酚替代对照品鉴别了2个成分。胡芦巴薄层鉴别中,《中国药典》选择葫芦巴碱对照品进行鉴别;《美国草药纲目》选择4-羟基异亮氨酸对照品控制了11个成分。小茴香薄层鉴别中,《中国药典》采用了茴香醛对照品进行鉴别;《欧洲药典》以茴香脑为对照品控制了2个成分。人参薄层鉴别中,《中国药典》采用4个对照品和对照药材进行鉴别;《美国药典》中采用2个替代对照品控制了4个成分;《欧洲药典》中采用2个对照品,并直接给出薄层色谱示意图,控制了9个成分。银杏叶薄层鉴别中,《中国药典》采用4个对照品和对照药材进行鉴别;《美国药典》中采用3个对照品控制了8个成分;《欧洲药典》中采用2个对照品,并直接给出薄层色谱示意图,控制了10个成分。《美国药典》和《欧洲药典》多采用替代对照品和相对比移值控制药材中的多个成分,通常采用详细的文字描述或标准色谱示意图进行结果分析。结论 不同药典薄层色谱鉴别中对照品的选择和结果分析方法不同,导致鉴别成本和效率上存在较大差异。充分利用薄层色谱信息,建立薄层鉴别特征图谱,可以从整体上评价药材的质量。

One step hot-pressing method for hybrid Li metal anode of solid-state lithium metal batteries

Safety issues induced by infinite anode volume change and uncontrolled lithium(Li)dendrite growth have become the biggest obstacle to the practical application of Li metal batteries.In addition,the tra-ditional rolling method makes it difficult to manufacture thin Li foil with high mechanical strength and low Li content.Herein,a three-dimensional(3D)lithophilic carbon paper/copper(Cu)current collector hybrid anode with ultra-low Li metal content is prepared by a hot-pressing method.The highly re-versible and stable lithiophilic layer LiC_(x) formed in situ by heating/pressing treatment provides abun-dant nucleation sites and reduces the Li nucleation overpotential,thereby effectively suppressing Li den-drite growth.Moreover,the volume change and pulverization problems of Li metal anode during depo-sition/stripping also can be accommodated by the 3D skeleton.The optimization effect has been directly confirmed by in-situ optical and ex-situ scanning electron microscope observation.Therefore,highly sta-ble performance(158.4 mA h g^(-1) at 2 C after 200 cycles with a capacity retention of 95.24%)in Li@LCP-Cu||NCM811 coin cell can be achieved.Furthermore,the solid-state battery assembled with the hybrid anode,poly(vinylidene fluoride)(PVDF)-based polymer electrolyte and polyethylene oxide(PEO)interface functional layer also exhibits the best electrochemical and safety performance,which also proves that the Li@LCP-Cu anode has great potential for application in solid-state batteries.

Universal lithiophilic interfacial layers towards dendrite-free lithium anodes for solid-state lithium-metal batteries

Solid-state lithium-metal-batteries(SSLMBs)using garnet Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)as the solid electrolyte are expected to conquer the safety concerns of high energy Li batteries with organic liquid electrolytes owing to its nonflammable nature and good mechanical strength.However,the poor interfacial contact between the Li anode and LLZTO greatly restrains the practical applications of the electrolyte,because large polarization,dendritic Li formation and penetration can occur at the interfaces.Here,an effective method is proposed to improve the wettability of the LLZTO toward lithium and reduce the interfacial resistance by engineering universal lithiophilic interfacial layers.Thanks to the in-situ formed lithiophilic and ionic conductive Co/Li_(2)O interlayers,the symmetric Li/CoO-LLZTO/Li batteries present much smaller overpotential,ultra-low areal specific resistance(ASR,12.3 X cm^(2)),high critical current density(CCD,1.1 mA cm^(-2)),and outstanding cycling performance(1696 h at a current density of 0.3 mA cm^(-2))at 25℃.Besides,the solid-state Li/CoO-LLZTO/LFP cells deliver an excellent electrochemical performance with a high coulombic efficiency of~100%and a long cycling time over 185 times.Surprisingly,the high-voltage(4.6 V)solid state Li/CoO-LLZTO/Li_(1.4)Mn_(0.6)Ni_(0.2)Co_(0.2)O_(2.4)(LMNC622)batteries can also realize an ultra-high specific capacity(232.5 mAh g-1)under 0.1 C at 25℃.This work paves an effective way for practical applications of the dendrite-free SSLMBs.

Asurvey on design and application of open-channel solid-state drives

Compared with traditional solid-state drives(SSDs),open-channel SSDs(OCSSDs)expose their internal physical layout and provide a host-based flash translation layer(FTL)that allows host-side software to control the internal operations such as garbage collection(GC)and input/output(I/O)scheduling.In this paper,we comprehensively survey research works built on OCSSDs in recent years.We show how they leverage the features of OCSSDs to achieve high throughput,low latency,long lifetime,strong performance isolation,and high resource utilization.We categorize these efforts into five groups based on their optimization methods:adaptive interface customizing,rich FTL co-designing,internal parallelism exploiting,rational I/O scheduling,and efficient GC processing.We discuss the strengths and weaknesses of these efforts and find that almost all these efforts face a dilemma between performance effectiveness and management complexity.We hope that this survey can provide fundamental knowledge to researchers who want to enter this field and further inspire new ideas for the development of OCSSDs.

Modification of solid electrolyte interface layer between PVDF-based electrolyte and lithium anode

Poly(vinylidene fluoride)(PVDF)-based polymer electrolytes(PEs)with good electrochemical performance and processability as well as low-cost advantage,have great potential applications in solid-state lithium(Li)metal batteries(SSLMBs).PVDF-based PEs are generally produced by employing a solution-casting approach with N,N-dimethylformamide(DMF)as the solvent,accompanied by the formation of[DMF-Li^(+)]complex,which facilitates the Li-ion transport.However,the residual DMF can react continuously with lithium(Li)metal,thereby deteriorating the interface layer in the middle of the PVDF-based PEs and Li anodes.Herein,we introduce propylene carbonate(PC)into the PVDF-based PEs to regulate the solvation structure and stabilize the interface layer between the PEs and Li anodes.PC accelerates the dissociation of lithium oxalyldifluoroborate(LiODFB).Consequently,“lithium propylene dicarbonate(LPDC)‒B-O”oligomer forms as the interfacial layer with high tenacity,homogeneity,and densification,which improves the interfacial contact and suppresses the continuous reaction between the residual DMF and Li anode.We further demonstrate that the PVDF-based PE prepared with DMF-PC mix-solvents shows improved room-temperature ionic conductivity(1.18×10^(-3) S/cm),enhanced stability against electrodes,and superior cycling performance in LiCoO_(2)-based SSLMBs(maintaining 84% of the initial discharge capacity after 300 cycles).