Functional Separator Enabled by Covalent Organic Frameworks for High-Performance Li Metal Batteries

Uncontrolled ion transport and susceptible SEI films are the key factors that induce lithium dendrite growth, which hinders the development of lithium metal batteries (LMBs). Herein, a TpPa-2SO₃H covalent organic framework (COF) nanosheet adhered cellulose nanofibers (CNF) on the polypropylene separator (COF@PP) is successfully designed as a battery separator to respond to the aforementioned issues. The COF@PP displays dual-functional characteristics with the aligned nanochannels and abundant functional groups of COFs, which can simultaneously modulate ion transport and SEI film components to build robust lithium metal anodes. The Li//COF@PP//Li symmetric cell exhibits stable cycling over 800 h with low ion diffusion activation energy and fast lithium ion transport kinetics, which effectively suppresses the dendrite growth and improves the stability of Li+ plating/stripping. Moreover, The LiFePO4//Li cells with COF@PP separator deliver a high discharge capacity of 109.6 mAh g⁻¹ even at a high current density of 3 C. And it exhibits excellent cycle stability and high capacity retention due to the robust LiF-rich SEI film induced by COFs. This COFs-based dual-functional separator promotes the practical application of lithium metal batteries.     

Minimization of Ion–Solvent Clusters in Gel Electrolytes Containing Graphene Oxide Quantum Dots for Lithium‐Ion Batteries

This study uses graphene oxide quantum dots (GOQDs) to enhance the Li⁺‐ion mobility of a gel polymer electrolyte (GPE) for lithium‐ion batteries (LIBs). The GPE comprises a framework of poly(acrylonitrile‐co‐vinylacetate) blended with poly(methyl methacrylate) and a salt LiPF₆ solvated in carbonate solvents. The GOQDs, which function as acceptors, are small (3?11 nm) and well dispersed in the polymer framework. The GOQDs suppress the formation of ion?solvent clusters and immobilize anions, affording the GPE a high ionic conductivity and a high Li⁺‐ion transference number (0.77). When assembled into Li|electrolyte|LiFePO₄ batteries, the GPEs containing GOQDs preserve the battery capacity at high rates (up to 20 C) and exhibit 100% capacity retention after 500 charge?discharge cycles. Smaller GOQDs are more effective in GPE performance enhancement because of the higher dispersion of QDs. The minimization of both the ion?solvent clusters and degree of Li⁺‐ion solvation in the GPEs with GOQDs results in even plating and stripping of the Li‐metal anode; therefore, Li dendrite formation is suppressed during battery operation. This study demonstrates a strategy of using small GOQDs with tunable properties to effectively modulate ion?solvent coordination in GPEs and thus improve the performance and lifespan of LIBs.     

A High-Performance Carbonate-Free Lithium|Garnet Interface Enabled by a Trace Amount of Sodium

Garnet-type solid-state electrolytes (SSEs) are promising for the realization of next-generation high-energy-density Li metal batteries. However, a critical issue associated with the garnet electrolytes is the poor physical contact between the Li anode and the garnet SSE and the resultant high interfacial resistance. Here, it is reported that the Li|garnet interface challenge can be addressed by using Li metal doped with 0.5 wt% Na (denoted as Li*) and melt-casting the Li* onto the garnet SSE surface. A mechanistic study, using Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) as a model SSE, reveals that Li₂CO₃ resides within the grain boundaries of newly polished LLZTO pellet, which is difficult to remove and hinders the wetting process. The Li* melt can phase-transfer the Li₂CO₃ from the LLZTO grain boundary to the Li*’s top surface, and therefore facilitates the wetting process. The obtained Li*|LLZTO demonstrates a low interfacial resistance, high rate capability, and long cycle life, and can find applications in future all-solid-state batteries (e.g., Li*|LLZTO|LiFePO₄).     

Reversible Deposition of Lithium Particles Enabled by Ultraconformal and Stretchable Graphene Film for Lithium Metal Batteries

Originating from inhomogeneous Li deposition and dissolution, the formation of dendritic and/or dead Li lies as a fundamental barrier to the practical implementation of Li metal anodes for high-energy Li-ion batteries. Here, an ultraconformal and stretchable solid-electrolyte interphase (SEI) composed of parallelly stacked few-layer defect-free graphene nanosheets, which can deform to remain ultraconformal during the expansion and shrinkage of micro-sized Li metal particles is reported. The shape-adaptive graphene protective skin is prepared via a facile mechanical method followed by Li stripping, which enables fast Li-ion diffusion, and inhibits Li dendrites and Li pulverization. The interlayer slips and wrinkles of the graphene film endow the robust protective skin with high stretchability. This work represents a unique strategy of building ultraconformal and stretchable 2D-materials-based protective skins on the surface of Li metal toward high-energy, long-life, and safe Li metal batteries.     

纳滤法提锂氢氧化镁废渣制取碳酸锂的研究

以含锂氢氧化镁废渣为原料,采用碳酸氢铵碳化法提取锂,恒温热分解法制备高纯碳酸锂.最优碳化条件为:反应温度40℃、反应时间120 min、NH4HCO3/Mg(OH)2物质的量比1∶0.8、液固比20,锂提取率高达97.5％.母液循环10次后,锂质量浓度由0.7 mg/L富集至5.5 g/L.80℃恒温分解母液60 min,制得产率为81.7％,纯度为99.3％的工业级碳酸锂.同时,推导出碳酸锂结晶符合准二级反应动力学,0～30 min和40～125min两个阶段的活化能分别为140.67 kJ/mol和107.56 kJ/mol.表明碳酸锂的结晶决定步骤是由化学反应控制的.     

High-Performance Solid Lithium Metal Batteries Enabled by LiF/LiCl/LiIn Hybrid SEI via InCl3-Driven In Situ Polymerization of 1,3-Dioxolane

The use of poly(1,3-dioxolane) (PDOL) electrolyte for lithium batteries has gained attention due to its high ionic conductivity, low cost, and potential for large-scale applications. However, its compatibility with Li metal needs improvement to build a stable solid electrolyte interface (SEI) toward metallic Li anode for practical lithium batteries. To address this concern, this study utilized a simple InCl₃-driven strategy for polymerizing DOL and building a stable LiF/LiCl/LiIn hybrid SEI, confirmed through X-ray photoelectron spectroscopy (XPS) and cryogenic-transmission electron microscopy (Cryo-TEM). Furthermore, density functional theory (DFT) calculations and finite element simulation (FES) verify that the hybrid SEI exhibits not only excellent electron insulating properties but also fast transport properties of Li⁺. Moreover, the interfacial electric field shows an even potential distribution and larger Li⁺ flux, resulting in uniform dendrite-free Li deposition. The use of the LiF/LiCl/LiIn hybrid SEI in Li/Li symmetric batteries shows steady cycling for 2000 h, without experiencing a short circuit. The hybrid SEI also provided excellent rate performance and outstanding cycling stability in LiFePO₄/Li batteries, with a high specific capacity of 123.5 mAh g⁻¹ at 10 C rate. This study contributes to the design of high-performance solid lithium metal batteries utilizing PDOL electrolytes.     

锂离子电池玻璃态电解质导电机理的研究进展

锂离子电池玻璃态电解质同晶体型电解质相比较具有导电性各向同性、锂离子电导率高等诸多优点, 开发在室温下具有较高的离子电导率及良好的化学、电化学稳定性的玻璃态电解质材料已经成为锂离子电池领域的重要研究方向之一。本文介绍了各种玻璃态电解质体系的导电特性及导电机理, 并重点分析与讨论混合网络形成体效应在一些典型玻璃态电解质体系中的微观作用机理。本文还总结了混合网络形成体效应在玻璃态电解质中发生的前提条件, 并指出深入研究玻璃态电解质的导电机理对开发出具有优异电化学性能的无机非晶固态电解质体系具有重要的指导意义。     

Self‐Suppression of Lithium Dendrite in All‐Solid‐State Lithium Metal Batteries with Poly(vinylidene difluoride)‐Based Solid Electrolytes

Polymer‐based electrolytes have attracted ever‐increasing attention for all‐solid‐state lithium (Li) metal batteries due to their ionic conductivity, flexibility, and easy assembling into batteries, and are expected to overcome safety issues by replacing flammable liquid electrolytes. However, it is still a critical challenge to effectively block Li dendrite growth and improve the long‐term cycling stability of all‐solid‐state batteries with polymer electrolytes. Here, the interface between novel poly(vinylidene difluoride) (PVDF)‐based solid electrolytes and the Li anode is explored via systematical experiments in combination with first‐principles calculations, and it is found that an in situ formed nanoscale interface layer with a stable and uniform mosaic structure can suppress Li dendrite growth. Unlike the typical short‐circuiting that often occurs in most studied poly(ethylene oxide) systems, this interface layer in the PVDF‐based system causes an open‐circuiting feature at high current density and thus avoids the risk of over‐current. The effective self‐suppression of the Li dendrite observed in the PVDF–LiN(SO₂F)₂ (LiFSI) system enables over 2000 h cycling of repeated Li plating–stripping at 0.1 mA cm^?2 and excellent cycling performance in an all‐solid‐state LiCoO₂||Li cell with almost no capacity fade after 200 cycles at 0.15 mA cm^?2 at 25 °C. These findings will promote the development of safe all‐solid‐state Li metal batteries.     

Early Lithium Plating Behavior in Confined Nanospace of 3D Lithiophilic Carbon Matrix for Stable Solid‐State Lithium Metal Batteries

Considerable efforts are devoted to relieve the critical lithium dendritic and volume change problems in the lithium metal anode. Constructing uniform Li⁺ distribution and lithium “host” are shown to be the most promising strategies to drive practical lithium metal anode development. Herein, a uniform Li nucleation/growth behavior in a confined nanospace is verified by constructing vertical graphene on a 3D commercial copper mesh. The difference of solid‐electrolyte interphase (SEI) composition and lithium growth behavior in the confined nanospace is further demonstrated by in‐depth X‐ray photoelectron spectrometer (XPS) and line‐scan energy dispersive X‐ray spectroscopic (EDS) methods. As a result, a high Columbic efficiency of 97% beyond 250 cycles at a current density of 2 mA cm^?2 and a prolonged lifespan of symmetrical cell (500 cycles at 5 mA cm^?2) can be easily achieved. More meaningfully, the solid‐state lithium metal cell paired with the composite lithium anode and LiNi_0.5Co_0.2Mn_0.3O₂ (NCM) as the cathode also demonstrate reduced polarization and extended cycle. The present confined nanospace–derived hybrid anode can further promote the development of future all solid‐state lithium metal batteries.     

循环氢化对电池级碳酸锂制备中钙镁去除的影响

以工业级Li2CO3为原料,采用氢化分解法提纯制备电池级Li2CO3,研究了母液循环、干料产品循环、湿料产品循环、干料产品和母液循环、湿料产品和母液循环5种循环氢化过程对电池级Li2CO3制备中Ca、Mg去除的影响.结果表明,母液循环氢化3次、干料循环氢化1次、湿料循环氢化3次、干料和母液循环氢化3次、湿料和母液循环4次均可使Ca、Mg杂质有效降低,且Mg含量均控制在电池级Li2CO3行业标准以下;适当次数的湿料循环、干料和母液循环、湿料和母液循环均可以将Ca含量降低到电池级Li2CO3行业标准以下.     

An Inorganic-Rich SEI Layer by the Catalyzed Reduction of LiNO3 Enabled by Surface-Abundant Hydrogen Bonding for Stable Lithium Metal Batteries

Lithium (Li) metal anodes (LMAs) are promising anode candidates for realizing high-energy-density batteries. However, the formation of unstable solid electrolyte interphase (SEI) layers on Li metal is harmful for stable Li cycling; hence, enhancing the physical/chemical properties of SEI layers is important for stabilizing LMAs. Herein, thiourea (TU, CH₄N₂S) is introduced as a new catalyzing agent for LiNO₃ reduction to form robust inorganic-rich SEI layers containing abundant Li₃N. Due to the unique molecular structure of TU, the TU molecules adsorb on the Cu electrode by forming Cu S bond and simultaneously form hydrogen bonding with other hydrogen bonds accepting species such as NO₃⁻ and TFSI⁻ through its N H bonds, leading to their catalyzed reduction and hence the formation of inorganic-rich SEI layer with abundant Li₃N, LiF, and Li₂S/Li₂S₂. Particularly, this TU-modified SEI layer shows a lower film resistance and better uniformity compared to the electrochemically and naturally formed SEI layers, enabling planar Li growth without any other material treatments and hence improving the cyclic stability in Li/Cu half-cells and Li@Cu/LiFePO₄ full-cells.     

物理气相沉积制备锂离子电池正极薄膜研究进展

薄膜锂离子电池是锂离子电池发展的最新领域,正极材料的薄膜化是薄膜锂离子电池的重要部分.综述了近年来国内外物理气相沉积在薄膜锂离子电池正极薄膜方面的研究新进展,着重介绍了射频磁控溅射、脉冲激光沉积、电子束沉积等制备技术的工作原理、特点及发展,并对这些制备技术在锂离子电池正极薄膜制备中的应用进行了分析、比较和评价.     

熔融盐法合成锂离子电池正极材料的研究进展

熔融盐法是利用熔融盐作反应物或兼作熔剂,在固液态间进行反应,可以有效降低反应温度和缩短反应时间,合成出符合计量比以及结晶发育良好的正极材料,是一种合成锂离子正极插层材料的新的有效方法.就国内外采用熔融盐法合成锂离子电池正极材料的现状,结合我们的研究情况进行了综述.     

镍铁合金镀液中硫酸镍含量的自动电位滴定

以紫脲酸铵作指示剂的EDTA滴定法在测量镍铁合金镀液中硫酸镍含量时肉眼观察易产生误差.为此,采用自动电位滴定法测定镍铁合金镀液中的硫酸镍含量,用H<,2>O<,2>将镀液中的Fe<'2+>转化为Fe<'3+>,再用三乙醇胺掩蔽Fe<'3+>,以pCa-1型钙离子选择性电极为指示电极,以212型电极为参比电极,在Ca-E...     

双波长K系数分光光度法测定镍钨合金镀液中的钨含量

以NH4SCN方法测定镍钨合金镀液中的钨含量,镀液中的Ni^2＋会对其产生干扰。应用双波长K系数分光光度法有效消除了共存Ni^2＋的影响。测定镍钨合金镀液中的钨时以X420nm为测量波长、370nm为参比波长,钨的线性回归方程为Y=0．4260x＋0．9823,相对标准偏差为1．2％,加标回收率为96．89％～106．10％。此法用于镍钨合金镀液中钨含量的测定,结果准确。     

用标准加入原子吸收分光光度法测定铅锡合金镀液中铅的浓度

采用标准加入原子吸收分光光度法测定铅锡合金镀液中铅的浓度,试验确定了最佳的测定条件。结果表明,该方法简便、快速、干扰小,测定的准确度和精密度高,适用于电镀过程中铅浓度的跟踪测定。     

Characteristics of a Graphene Nanoplatelet Anode in Advanced Lithium‐Ion Batteries Using Ionic Liquid Added by a Carbonate Electrolyte

A Cu‐supported, graphene nanoplatelet (GNP) electrodes are reported a as high performance anode in lithium ion battery. The electrode precursor is an easy‐to‐handle aqueous ink cast on cupper foil and following dried in air. The scanning electron microscopy evidences homogeneous, micrometric flakes‐like morphology. Electrochemical tests in conventional electrolyte reveal a capacity of about 450 mAh g⁻¹ over 300 cycles, delivered at a current rate as high as 740 mA g⁻¹. The graphene‐based electrode is characterized using a N‐butyl‐N‐methyl‐pyrrolidiniumbis (trifluoromethanesulfonyl) imide, lithium‐bis(trifluoromethanesulfonyl)imide (Py_1,4TFSI–LiTFSI) ionic liquid‐based solution added by ethylene carbonate (EC): dimethyl carbonate (DMC). The Li‐electrolyte interface is investigated by galvanostatic and potentiostatic techniques as well as by electrochemical impedance spectroscopy, in order to allow the use of the graphene‐nanoplatelets as anode in advanced lithium‐ion battery. Indeed, the electrode is coupled with a LiFePO₄ cathode in a battery having a relevant safety content, due to the ionic liquid‐based electrolyte that is characterized by an ionic conductivity of the order of 10⁻² S cm⁻¹, a transference number of 0.38 and a high electrochemical stability. The lithium ion battery delivers a capacity of the order of 150 mAh g⁻¹ with an efficiency approaching 100%, thus suggesting the suitability of GNPs anode for application in advanced configuration energy storage systems.     

磁场凝固法制备过共晶MnBi/Bi磁性功能复合材料

Bi-Mn过共晶合金分别从3个不同状态凝固．合金中MnBi析出相均在磁场作用下以晶体的C轴平行磁场取向。形成规则排列组织，并且所得材料的剩磁都具有明显的各向异性。合金从低于355℃的固液两相区凝固时，铁磁性MnBi析出相在1．0T磁场中迅速形成均布的织构组织，并能在无磁场条件下保持稳定，材料无需热处理就有很好的剩磁性能。因此，磁场凝固技术能够高效率地、直接制备出性能优良的MnBi／Bi磁性功能复合材料。