Nitrile Electrolyte Strategy for 4.9 V-Class Lithium-Metal Batteries Operating in Flame

Challenges facing high-voltage/high-capacity cathodes,in addition to the longstanding problems pertinent to lithium(Li)-metal anodes,should be addressed to develop high-energy-density Li-metal batteries.This issue mostly stems from interfacial instability between electrodes and electrolytes.Conventional carbonate-or ether-based liquid electrolytes suffer from not only volatility and flammability but also limited electrochemical stability window.Here,we report a nitrile electrolyte strategy based on concentrated nitrile electrolytes(CNEs)with co-additives.The CNE consists of high-concentration lithium bis(fluorosulfonyl)imide(LiFSI)in a solvent mixture of succinonitrile(SN)/acetonitrile(AN).The SN/AN solvent mixture is designed to ensure high oxidation stability along with thermal stability,which are prerequisites for high-voltage Li-metal cells.The CNE exhibits interfacial stability with Li metals due to the coordinated solvation structure.Lithium nitrate(LiNO_(3))and indium fluoride(InF_(3))are incorporated in the CNE as synergistic co-additives to further stabilize solid-electrolyte interphase(SEI)on Li metals.The resulting electrolyte(CNE+LiNO_(3)/InF_(3))enables stable cycling performance in Li||LiNi_(0.8)Co_(0.1)Mn_(0.1)and 4.9 V-class Li||LiNi_(0.5)Mn_(1.5)O_(4)cells.Notably,the Li||LiNi_(0.5)Mn_(1.5)O_(4)cell maintains its electrochemical activity at high temperature(100℃)and even in flame without fire or explosion.

Stepwise optimization of single-ion conducting polymer electrolytes for high-performance lithium-metal batteries

Single-ion conducting polymer electrolytes(SIPEs)are promising candidates for high-energy and highsafety lithium-metal batteries(LMBs).However,their insufficient ionic conductivity and electrochemical stability hinder their practical application.Herein,three new SIPEs,i.e.,poly(1,4-phenylene ether ether sulfone)-Li(PEES-Li),polysulfone-Li(PSF-Li),and hexafluoropolysulfone-Li(6FPSF-Li),all containing covalently tethered perfluorinated ionic side chains,have been designed,synthesized,and compared to investigate the influence of the backbone chemistry and the concentration of the ionic group on their electrochemical properties and cell performance.Especially,the trifluoromethyl group in the backbone and the concentration of the ionic function appear to play an essential role for the charge transport and stability towards oxidation,and the combination of both yields the best-performing SIPE with high ionic conductivity of ca.2.5×10^(-4)S cm^(-1),anodic stability of more than 4.8 V,and the by far highest capacity retention in Li‖LiNi0.6Co0.2Mn0.2O2cells.

A versatile nano-TiO_(2) decorated gel separator with derived multi-scale nanofibers towards dendrite-blocking and polysulfide-inhibiting lithium-metal batteries

In this study,a versatile fluorine-bearing gel membrane with multi-scale nanofibers was rationally designed and synthesized via facile one-step blend electrospinning of nano-titanium dioxide(TiO_(2))particles and fluorinated poly-m-phenyleneisophthalamide(PMIA)polymer solution.The prepared multiscale TiO_(2)-assisted gel separator presented relatively high porosity,small aperture,giving rise to superior affinity to electrolyte and sufficient active sites to accelerate lithium ions migration.Meanwhile,the asfabricated multifunctional GPE also rendered outstanding heat-resistance and well-distributed lithiumions flux,and the mutual overlaps between the coarse fibers and the fine fibers within the multi-scale nanofiber membrane provided a strong skeleton support,which in turn laid a solid footing stone for high-security and dendrite-proof batteries.Particularly,the nano-TiO_(2) particles within PMIA membrane acted as"gatekeepers",which can not only resist the growth of lithium dendrites,but also intercept the dissolved polysulfide on cathode side.Based on these merits,the gel PMIA-based lithium cobalt(LCO)/lithium battery obtained the remarkably improved rate capability and cycle performances on account of superior ionic conductivity,steady anodic stability window and weakened polarization behavior.Meanwhile,the resultant lithium-sulfur cell also delivered the outstanding cycling stability with the aid of the greatly prevented"shuttle effect"of dissolved lithium polysulfides based on the physical trapping and chemical binding of the prepared GPE to polysulfides species.This work proved that the addition of functional inorganic nanoparticles similar with TiO_(2) in multi-scale gel PMIA membrane can enhance the lithium ions transport capability,resist the growth of lithium dendrites as well as inhibit the shuttle effect of polysulfides,which would prompt a great development for dendrite-blocking and polysulfideinhibiting lithium-metal cells.

Quasi-solid electrolyte membranes with percolated metal–organic frameworks for practical lithium-metal batteries

High-energy Li-metal batteries (LMBs) suffer from short cycle life and safety issues due to severe parasitic reactions and dendrite growth of Li metal anode (LMA) in liquid electrolytes [1–3].It is generally believed that replacing liquid electrolytes with solidstate electrolytes (SSEs) would be a feasible approach for practical LMBs [4,5]. Conventional SSEs including ceramic and polymer electrolytes have been studied for decades.

A Stretchable Ionic Conductive Elastomer for High-Areal-Capacity Lithium-Metal Batteries

Developing high-areal-capacity and dendrite-free lithium(Li)anodes is of significant importance for the practical applications of the Li-metal secondary batteries.Herein,an effective strategy to stabilize the high-arealcapacity Li electrodeposition by modifying the Li metal with a stretchable ionic conductive elastomer(ICE)is demonstrated.The ICE layer prepared via an instant photocuring process shows a promising Li^(+)-ion conductivity at room temperature.When being used in Li-metal batteries,the thin ICE coating(~0.27μm)acts as both a stretchable constraint to minimize the Li loss and a protective layer to facilitate the uniform flux of Li ions.With this ICE-modifying strategy,the reversibility and cyclability of the Li anodes under high-areal-capacity condition in carbonate electrolyte are significantly improved,leading to a stable Li stripping/plating for 500 h at an ultrahigh areal capacity of 20 mAh cm^(-2)in commercial carbonate electrolyte.When coupled with industry-level thick LiFePO;electrodes(20.0 mg cm^(-2)),the cells with ICE-Li anodes show significantly enhanced rate and cycling capability.

Thiol-ene crosslinked cellulose-based gel polymer electrolyte with good structural integrity for high cycling performance lithium-metal battery

Gel polymer electrolytes(GPEs) are considered to be one most promising alternative to liquid electrolytes due to their suitability for creating safe and durable solid-state lithium-metal batteries. However, the mechanical properties of GPEs usually deteriorate dramatically when polymer matrices are plasticized by a liquid electrolyte, which leads to significant loss of battery performance. Therefore, the long-term structural integrity and good mechanical strength are critical characteristics of GPEs designed for highperformance batteries. Here, an ecologically compatible cellulose-based GPE with a crosslinked structure is synthesized via a facile and effective thiol-ene click chemistry method. The prepared thiol-ene crosslinked GPE possesses enhanced mechanical strength(10.95 MPa) and rigid structure, which enabled us to fabricate Li Fe PO_(4)|Li batteries with ultra-long cycling performance. The capacity retention of the crosslinked cellulose-based GPE can be up to 84% at 0.5 C, even after 350 cycles, which is considerably higher than that of non-crosslinked GPE for which rapid decline in capacity occurs after 200 cycles. In addition, a GPE preparation method described in this work compares favorably well with existing commercial electrolytes for lithium metal batteries.

Hybrid diluents enable localized high-concentration electrolyte with balanced performance for high-voltage lithium-metal batteries

Localized high-concentration electrolytes(LHCE) have shown good compatibility with high-voltage lithium(Li)-metal batteries, but their practicality is yet to be proved in terms of cost and safety. Here we develop a hybrid-LHCE with favorable integrated properties by combining the merits of two representative diluents, fluorobenzene(FB) and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether(TFE). Specifically,the extremely cheap and lightweight FB significantly reduces the cost and density of electrolyte, while the fire-retardant TFE circumvents the flammable nature of FB and thus greatly improves the safety of electrolyte. Moreover, the FB–TFE mixture enhances the thermodynamic stability of hybrid-LHCE and renders a controllable defluorination of FB, contributing to the formation of a thin and durable inorganic-rich solid electrolyte interphase(SEI) with rapid ion-transport kinetics. Benefiting from the designed hybridLHCE, a Li|NCM523 battery demonstrates excellent cycling performance(215 cycles, 91% capacity retention) under challenging conditions of thin Li-anode(30 μm) and high cathode loading(3.5 m Ah/cm^(2)).

Designing solid-state interfaces on lithium-metal anodes: a review

Li-metal anodes are one of the most promising energy storage systems that can considerably exceed the current technology to meet the ever-increasing demand of power applications. The apparent cycling performances and dendrite challenges of Li-metal anodes are highly influenced by the interface layer on the Li-metal anode because the intrinsic high reactivity of metallic Li results in an inevitable solid-state interface layer between the Li-metal and electrolytes. In this review, we summarize the recent progress on the interfacial chemistry regarding the interactions between electrolytes and ion migration through dynamic interfaces. The critical factors that affect the interface formation for constructing a stable interface with a low resistance are reviewed. Moreover, we review emerging strategies for rationally designing multiple-structured solid-state electrolytes and their interfaces, including the interfacial properties within hybrid electrolytes and the solid electrolyte/electrode interface. Finally, we present scientific issues and perspectives associated with Li-metal anode interfaces toward a practical Li-metal battery.

Janus Quasi‑Solid Electrolyte Membranes with Asymmetric Porous Structure for High‑Performance Lithium‑Metal Batteries

Quasi-solid electrolytes(QSEs)based on nanoporous materials are promising candidates to construct high-performance Limetal batteries(LMBs).However,simultaneously boosting the ionic conductivity(σ)and lithium-ion transference number(t^(+)) of liquid electrolyte confined in porous matrix remains challenging.Herein,we report a novel Janus MOFLi/MSLi QSEs with asymmetric porous structure to inherit the benefits of both mesoporous and microporous hosts.This Janus QSE composed of mesoporous silica and microporous MOF exhibits a neat Li^(+) conductivity of 1.5.10^(–4)S cm^(−1) with t^(+) of 0.71.A partially de-solvated structure and preference distribution of Li^(+)near the Lewis base O atoms were depicted by MD simulations.Meanwhile,the nanoporous structure enabled efficient ion flux regulation,promoting the homogenous deposition of Li^(+).When incorporated in Li||Cu cells,the MOFLi/MSLi QSEs demonstrated a high Coulombic efficiency of 98.1%,surpassing that of liquid electrolytes(96.3%).Additionally,NCM 622||Li batteries equipped with MOFLi/MSLi QSEs exhibited promising rate performance and could operate stably for over 200 cycles at 1 C.These results highlight the potential of Janus MOFLi/MSLi QSEs as promising candidates for next-generation LMBs.

新疆阿尔金西段瓦石峡南锂铍稀有金属矿成矿背景与勘查进展

锂、铍等稀有金属矿产是重要的战略矿产资源。近年来,在阿尔金地区发现了多处稀有金属伟晶岩型矿床,已成为我国一处新的稀有金属成矿带,但调查研究水平总体较低。通过对阿尔金造山带的成矿动力背景的讨论,得出阿尔金造山带的稀有金属成矿作用涵盖了多个不同的造山运动构造演化阶段,证明该区域具备良好的稀有金属成矿条件,并具有巨大的找矿潜力。通过对位于阿尔金西段的瓦石峡南锂铍稀有金属矿进行勘查评价,发现其具有大型远景:瓦石峡南锂铍稀有金属矿体主要赋存于绿片岩相-角闪岩相变质岩系中的伟晶岩脉中,矿床类型为花岗伟晶岩型稀有金属矿床;已有勘查成果显示此矿床目前推断的稀有金属资源量达到中型以上矿床规模,并且随着勘查工作的进行,在深部及外围还有极大增储空间。研究成果对在阿尔金造山带内寻找同类型矿床具有借鉴意义。

废锂离子电池的冶金回收工艺研究进展

回收废锂离子电池对资源可持续性和人类健康至关重要。废锂离子电池需要经过预处理拆解为各种组分,其中正极材料是各种组分中最具回收价值和意义的部分。目前,冶金工艺是废锂离子电池正极材料回收的主要方法,该工艺主要包括废锂离子电池的预处理、有价金属的提取、产品的回收3个阶段。总结了各阶段的主要方法和进展,并对比了各种方法的优缺点。经对比发现在废锂离子电池的预处理阶段中,机械化的处理方式是未来的发展方向;在有价金属的提取和产品回收的2个阶段中,将各种工艺相耦合来开发绿色、低成本、高效率的组合工艺将是今后的发展趋势。

嵌段共聚物电解质的制备及其电化学性能

通过设计聚合物分子结构,采用热引发自由基聚合方法合成聚乙二醇甲醚甲基丙烯酸酯(PEGMEMA)和甲基丙烯酸缩水甘油酯(GMA)的二嵌段共聚物电解质PEGMEMAm-GMAn-Br(PGA-Br),并研究其电化学性能。结果表明:将PGA嵌段或接枝到聚合物电解质上,可提高聚合物电解质的离子电导率,室温下的离子电导率达1.05×10^(−4)S·cm^(−1)。同时,PGA-Br嵌段共聚物电解质具有较低的玻璃化转变温度(-65℃)、较高的热分解温度、较宽的电化学稳定窗口(5.1 V)和阻燃特性。PGA-Br共聚物电解质组装下的固态Li|Li对称电池具有增强的电极/电解质固-固界面,可实现金属锂均匀沉积,有效抑制锂枝晶的生长。在0.1 C倍率下,基于PGA-Br嵌段共聚物电解质组装的LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)|PGA-Br|Li固态全电池可实现较高的首周放电比容量(160.1 mAh·g^(−1)),且循环100周次后容量保持率高达91.5%,库仑效率稳定在98.5%以上。

树枝状磺化聚醚砜纤维基复合固态电解质的制备及其性能

为解决应用于全固态锂金属电池中固态有机电解质离子电导率较低和力学性能较弱的问题,采用静电纺丝技术制备了树枝状磺化聚醚砜(SPES)纳米纤维膜,将其与聚氧化乙烯(PEO)结合制备复合固态电解质,并应用于全固态锂金属电池中。探讨了纺丝工艺对纳米纤维形貌的影响,在最佳的静电纺丝工艺参数下,研究了SPES纳米纤维膜对复合固态电解质结晶度、离子电导率、力学性能以及电化学性能的影响。结果表明:在四丁基六氟磷酸铵质量分数为2%,静电纺丝电压为30 kV,接收距离为15 cm时,制备的树枝状SPES纳米纤维膜具有最好的形貌,将PEO浇筑在该纳米纤维膜上获得的复合固态电解质其离子电导率为8.13×10^(-5)S/cm(30℃),断裂强度为5.1 MPa,且可使对称电池在0.1 mA·h/cm^(2)下稳定循环198 h,使LiFePO_(4)/Li电池在循环400圈后仍保持着128.6 mA·h/g的放电比容量;SPES纳米纤维膜因破坏PEO的结晶区且能构成三维离子传输路径,不仅提高了复合固态电解质的离子电导率,还使复合固态电解质具有优异的力学强度,可满足高性能全固态锂金属电池的应用需求。

MoS_(2)纳米片功能化PAN锂金属电池隔膜的制备及锂枝晶抑制作用

引导锂离子流的均匀分布可以有效抑制锂枝晶的形成-生长,推动锂金属电池的产业化应用.本文采用化学插层法制备出单层或少层、结构完整的MoS_(2)纳米片,将二维MoS_(2)纳米片喷涂到静电纺聚丙烯腈(PAN)纤维膜上,制得MoS_(2)@PAN复合隔膜.MoS_(2)涂层的引入不仅提高了离子电导率(1.02 mS/cm)、Li+迁移数(0.59)和电解液亲和性,而且降低了复合隔膜的孔径,使其孔径分布均一.这些特性协同作用,调控了通过MoS_(2)@PAN复合隔膜的Li+流分布,促进了Li+在锂金属表面的均匀沉积,抑制了锂枝晶的形成-生长.因此,MoS_(2)@PAN复合隔膜组装的Li/Li电池在1 mA/cm^(2)电流密度下以14 mV的超低过电位可稳定循环长达500 h,循环后的锂金属表面没有明显的枝晶生长.此外,MoS_(2)@PAN复合隔膜组装的LiFePO_(4)/Li电池在2C倍率下循环550次后保持92%的初始容量,表现出更稳定的循环性能.通过隔膜调节Li+通量实现了锂的均匀沉积,为抑制锂枝晶的形成-生长提供了一种可行的策略.

NiCuCoMn电极材料的制备及其储锂性能研究

采用熔炼甩带和化学脱合金相结合的方法制备纳米多孔NiCuCoMn过渡金属氧化物(NiCuCoMn@TMOs),并通过热处理进一步制备R-NiCuCoMn@TMOs。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等测试对材料进行结构表征并对其进行电化学性能测试。作为锂离子电池负极材料,R-NiCuCoMn@TMOs在0.1 A/g的电流密度下,经过200次循环后具有394.9 mAh/g的高比容量,并且表现出97.53%的优异容量保持率。与热处理前相比,热处理后的材料具有更丰富的氧空位、更低的电荷转移电阻(38Ω)和更优异的倍率性能(在2 A/g的电流密度下,比容量为141.1 mAh/g)。其独特的纳米多孔结构提供了丰富的反应活性位点;不同半径、价态和反应电位的多种金属阳离子的协同效应使得该材料有很好的体积容忍度以适应脱嵌锂过程中的体积变化,表现出优异的电化学性能。此外,该电极材料原料储量丰富,价格低廉,易于实现批量化制备。该工作为设计多组元过渡金属氧化物负极材料提供了新的思路。

聚合物人工固体电解质界面层的研究进展

锂金属负极因具有极高的比容量(3860 mAh/g)和低电化学电势(-3.04 V),成为可充电电池领域的研究热点。然而,锂金属的不稳定性会促使枝晶形成,在充放电过程中发生不可控的界面反应,导致生成的固体电解质界面(solid electrolyte interphase,SEI)层不稳定,进而影响电池循环寿命。通过锂金属负极表面引入聚合物人工SEI(ASEI),改善机械性能和电化学性能,从而制备长循环寿命和高能量密度的锂金属电池(LMBs)。聚合物具有灵活度高及结构可设计等特点,是人工SEI的理想材料。概述了人工SEI的性质及作用,根据聚合物官能团类型和所起作用,系统总结了聚合物人工SEI的研究进展,并对未来的研究方向和发展前景作出展望。

改性PVDF-HFP基凝胶电解质的合成及锂金属电池性能研究

开发高质量的固态电解质,对制造新一代安全稳定的固态锂金属电池具有重要意义。以聚偏氟乙烯–六氟丙烯(polyvinylidene fluoride-hexafluoropropylene,PVDF-HFP)为聚合物基体,引入MOF-808作为活性填料,采用溶液浇筑法制备了新型凝胶聚合物电解质。优化后的凝胶聚合物电解质在室温下的离子电导率高达3.21 mS/cm,电化学稳定窗口可达5.0 V、具有较高的Li^(+)迁移数(0.63)、与锂金属具有良好的界面相容性。组装的磷酸铁锂全电池在0.5 C倍率下循环250次,容量保持率为86.7%。高性能凝胶聚合物电解质对提升锂金属电池的循环稳定性与安全性具有重要的应用价值。

锂金属负极界面及体相稳定化策略研究进展

随着信息化、电动化和新能源技术的快速发展,便携电子、电动汽车和储能设施需要更高能量密度的电化学储能电池,但广泛使用的锂离子电池的能量密度正逐步接近极限,难以满足上述需求。因此亟需发展更高能量密度的电化学体系。锂金属负极具有极高的理论容量(3860 mAh·g^(-1))和最低的氧化还原电势(-3.04 V vs SHE),被认为是实现下一代高能量密度电池的理想材料。然而在几十年的发展过程中,锂金属电池较低的循环寿命和安全性问题严重制约了其实用化。本文从锂金属电池的发展历程出发,分析锂金属负极反应活性高、锂枝晶、死锂和体积膨胀等问题及作用机理,并就上述问题分别从界面设计和体相设计方面综述应对策略,包括非原位/原位生成的界面层保护、合金化锂负极以及三维复合锂负极,最后针对实效电池的约束条件、电极串扰及大容量电池的失效机制等实用化锂负极未来发展进行探讨和展望。

低能耗熔盐电解金属锂电解槽的开发及研究

近年来,金属锂在全固态锂电池、铝锂合金制备中发挥着不可替代的价值,但金属锂生产成本仍然是生产企业需要解决的问题。因此,从降低能耗角度优化生产工艺及设备角度利用Solid Works三维建模电解槽结构,以及ANSYS仿真模拟软件对电解槽进行热场模拟及计算,得出最优设计方案。生产电解效率可达到91%,能耗在35 kWh/kg以下,抽氯和集锂装置可以自动运行,抽出氯气浓度90%,集锂效率可达到80%以上,且出锂量较为稳定。该设备可以更好的投入产业化生产,满足企业降低生产成本的需要,促进熔盐电解金属锂行业的发展。

滇西高黎贡山地区培里伟晶岩型锂矿化的发现及其意义

稀有金属锂矿是我国紧需的战略性矿产资源。滇西地区是我国重要的稀有金属成矿远景区,但目前区内已知的稀有金属资源主要为Be-Nb-Ta-Sn矿,鲜有锂矿的报道。本研究首次在滇西高黎贡山培里地区发现了锂辉石伟晶岩型锂矿,为云南省新增一处有潜力的锂辉石型伟晶岩锂矿床,对区域稀有金属锂矿床的找矿工作具有重要意义。6个样品的全岩主微量元素分析显示培里地区伟晶岩主要发育有Li、Be、Rb、Cs、Nb、Ta矿化。LA-ICP-MS铌钽矿U-Pb年代学结果显示培里地区锂矿伟晶岩形成于18.4±0.3Ma,这一结果与共生的锡石U-Pb年代学(17.5±1.2Ma)结果一致,表明其为新生代成岩成矿作用产物。这一成矿年代与高黎贡山地区变质年代以及淡色花岗岩成岩年代一致,暗示培里伟晶岩可能为变质重熔产物,也可能是淡色花岗岩进一步结晶分异的产物。在大区域尺度上,该成矿事件与藏南稀有金属成矿时代一致,结合区域显著的地球化学背景异常,我们认为滇西地区可能是喜马拉雅稀有金属成矿带的南延部分,具有良好的稀有金属锂矿找矿前景。