氟化无机材料在金属锂负极中的应用

金属锂被认为是高能量密度电池材料的“圣杯”,具有超高的理论容量和最低的氧化还原电位。但由于锂枝晶不可控生长、固体电解质界面膜(SEI膜)不稳定以及“死锂”累积等系列问题,限制了其商业化应用。氟化材料能有效稳定金属锂/电解液界面,均匀锂离子通量和抑制锂枝晶生长,是金属锂二次电池领域的研究重点。本文综述了近年来氟化无机材料在金属锂沉积骨架、人工SEI保护层、电解液添加剂以及固态电解质等方面的研究进展,阐述了氟化无机材料稳定金属锂负极循环的内在机理,并展望了其未来的发展前景。     

金属锂电池负极界面氮化硼修饰膜的研究

金属锂负极由于具有超高的比容量(3 860 mA·h/g)与超低的还原电位(-3.04 V),其应用能够大幅提升现有锂离子电池的能量密度。然而,金属锂与电解液持续不断的副反应可导致电池的严重极化、非活性锂的增加及电池容量的迅速衰减。为了提升金属锂电池的循环性能,采用氮化硼薄膜作为金属锂表面的人工固体电解质膜(SEI膜)抑制其与电解液之间的副反应,以实现金属锂电池的长循环。采用简单易操作的喷涂沉积法,可将氮化硼薄膜均匀地沉积于金属锂表面,并通过电化学阻抗谱探索了最佳沉积次数。氮化硼SEI膜具有离子导通且电子绝缘的特性,成功地抑制了界面副反应与电池的极化增加。相比未经修饰的金属锂,经氮化硼修饰后,电池负极单位面积阻抗由4.6Ω/cm²降低至1.2Ω/cm²。所组装的锰酸锂/金属锂电池首圈库伦效率由89.2%提升至96.6%;1C条件下循环300次后,容量保持率由86.3%提升至94.6%。     

固态锂电池中的界面优化

全固态锂电池由于高安全性、高能量密度、宽电化学窗口受到研究者的关注,但是在实际应用中也存在一些问题,如固态电解质和电极材料之间为刚性接触,界面电阻大;锂金属较为活泼,与电解质接触易发生副反应导致界面不稳定;硫化物固态电解质对空气不稳定,生产成本高等.综述了电极材料与氧化物固态电解质、硫化物固态电解质、聚合物固态电解质的...     

固态薄膜电池研究进展

目前,固态薄膜电池的研究主要集中在低阻抗电极/电解质界面的构建和高离子电导率固体电解质的开发。介绍了固态薄膜电池的结构设计和离子传输机理,在此基础上讨论了负极膜、正极膜和固体电解质膜的研究进展,最后总结了电极/电解质界面问题及其改进策略。     

二次电池中金属锂负极沉脱机理研究进展

金属锂负极是下一代高比能二次电池备受关注的负极材料,以金属锂为负极的锂金属电池具备极高的理论能量密度,但其仍存在充放电循环效率低、电池寿命短等问题。要实现高能量密度高安全性的锂金属电池的合理设计和优化,需要对金属锂负极中锂金属沉积脱出过程的离子输运、电子输运、界面反应等机制机理有清晰的认识。本文针对金属锂负极中存在的枝晶生长、死锂形成、固体电解质界面膜作用等机理问题,综述了研究者们在其沉脱机理的模型与理论计算、实验研究等方面做出的诸多研究进展,为锂金属电池的合理设计提供了更全面的机理认识。     

Li+电池固态聚合物电解质研究进展

固态聚合物电解质具有高安全性、高成膜性和黏弹性等优点,并与电极具有良好的接触性和相容性,是实现高安全性和高能量密度固态Li⁺电池的重要电解质体系。然而聚合物电解质室温离子电导率较低（10^-8~10^-6 S·cm^-1）,不能满足固态聚合物电池在常温运行的需求。因此,在提高离子电导率、机械强度和电化学稳定性等本征属性的基础上,同时探究改善电解质/电极的界面处及电极内部的离子输运是研发固态聚合物Li⁺电池面临的关键问题。主要从改性聚合物电解质用以提高Li⁺电池电化学性能的角度出发,综述了凝胶聚合物电解质、全固态聚合物电解质和复合固态电解质中的离子输运机制及其关键参数,总结了近年来聚合物电解质的最新研究进展和未来的发展方向。     

NASICON型钠离子导体固态电解质研究进展

地球上有限的锂资源以及传统液态电解质的安全性问题使得开发全固态钠离子电池势在必行。钠离子固态电解质作为全固态钠电池的核心部件,对提高电池的安全性和电化学性能具有极其重要的作用。NASICON型固态电解质Na_1+xZr₂Si_xP_3–xO₁₂(0≤x≤3)因其独特的3D开放微观结构、化学/热稳定性好等优点而受到广泛关注,近几年在材料开发和性能优化方面取得长足进步。为了更好地了解该类材料的研发进展和最新动态,本文综述了近年来Na_1+xZr₂Si_xP_3–xO₁₂在晶体结构、离子传输机制、粉末制备方法以及电解质片烧结方法等关键特性方面的研究进展,深入分析了Na_1+xZr₂Si_xP_3–xO₁₂目前面临的挑战：离子电导率较低和电极–电解质界面接触差2大问题,重点介绍了其针对性...     

聚合物基镁离子固态电解质的研究进展Q

镁离子电池因其比容量高、资源丰富、环境友好、安全性高(无枝晶)等优势,在储能电池领域脱颖而出.然而,镁金属负极在液态电解质中易钝化,导致其电化学性能不佳.因此,开发高效适用的固态电解质对实现高性能、实用化镁离子电池至关重要.聚合物电解质具有优异的机械稳定性、电化学稳定性、热稳定性且离子电导率高、成本低.但镁离子较高的电荷密度和较强的溶剂化作用限制了其在固态电解质中的解离与扩散.从纯固态聚合物电解质、凝胶聚合物电解质、复合聚合物电解质3个方面综述了国内外聚合物基镁离子固态电解质的离子电导率对解决镁金属负极钝化效应的贡献及其应用研究进展,指出聚合物基镁离子固态电解质当前面临的挑战并对其研究方向进行了建议和展望.     

基于聚合物固态电解质的锂负极保护策略及研究进展

聚合物固态电解质因具有较好的柔软性和可加工性,成为一种非常具有应用前景的固态电解质。但在循环过程中,具有高反应活性的锂金属会与电解质材料和锂盐发生持续反应,生成不稳定的固态电解质界面（SEI）。这不仅导致了活性材料的损失,还可能因锂枝晶的生长而产生安全隐患。为了促进固态电解质的进一步发展,亟需解决电解质与电极之间较差的界面稳定性和兼容性等问题。基于此,本文综述了常见的几种聚合物固态电池界面的优化方法,以及最新的研究进展,对聚合物固态电解质在全固态电池中的应用进行了展望,提出了今后研究中应重点关注的技术和方向。     

Enhanced electrochemical performance of garnet-based solid-state lithium metal battery with modified anodic and cathodic interfaces

Due to high ionic conductivity and wide electrochemical window, the garnet solid electrolyte is considered as the most promising candidate electrolyte for solid-state lithium metal batteries. However, the high contact impedance between metallic lithium and the garnet solid electrolyte surface seriously hampers its further application. In this work, a Li-(ZnO)_x anode is prepared by the reaction of zinc oxide with metallic lithium and in situ coated on the surface of Li_6.8La₃Zr_1.8Ta_0.2O₁₂(LLZTO). The anode can be perfectly bound to the surface of LLZTO solid electrolyte, and the anode/electrolyte interfacial resistance was reduced from 2319 to 33.75 Ω·cm². The Li-(ZnO)_0.15|LLZTO|Li-(ZnO)_0.15 symmetric battery exhibits a stable Li striping/plating process during charge-discharging at a constant current density of 0.1 mA·cm^-2 for 100 h at room temperature. Moreover, a Li-(ZnO)_0.15|LLZTO-SPE|LFP full battery, comprised of a polyethylene oxide-based solid polymer electrolyte (SPE) film as an interlayer between LiFePO₄ (LFP) cathode and LLZTO solid electrolyte, presents an excellent performance at 60 ℃. The discharge capacity of the full battery reaches 140 mA·h·g^-1 at 0.1 C and the capacity attenuation is less than 3% after 50 cycles.     

固态金属锂电池研究进展：外部压力和内部应力的影响

固态锂金属电池具有理论能量密度高、安全性高等优势,是极有前景的下一代储能系统。然而,固体电极与固体电解质之间有限的固–固接触严重阻碍了界面离子的传输。因此,增加外部压力是增加固–固接触及延长电池循环寿命的重要途径。同时,在充放电过程中,电极体积变化产生的内应力也将影响电池界面特性。通过介绍两种基本物理接触模型,结合硫化物、氧化物、聚合物电解质以及金属锂的物理性质,综述了外压和内部应力对电解质、电极及电池的影响。最后,对外压力与内应力在全固态金属锂电池中的作用进行了总结和展望。     

Interfacial reactions at electrode/electrolyte boundary in all solid-state lithium battery using inorganic solid electrolyte, thio-LISICON

Electrode/electrolyte interface was studied for all solid-state batteries using inorganic solid electrolyte with the crystalline thio-LISICON and glassy Li-Si-P-S-O systems. The formation of the interfacial phase depends on the electrolyte. The thio-LISICON (Li_3.25Ge_0.25P_0.75S₄) and the Li-Al negative electrode provided the best electrode/electrolyte interface for fast charge-discharge characteristics, while the SEI phase formed at the Li-Al/Li₃PO₄-Li₂S-SiS₂ glass boundary caused high interfacial resistance. The formation of the SEI phase is general behavior at the electrode/electrolyte interface of solid-state batteries, and the fast electrochemical reaction is attained as a result of optimization of the electrode/electrolyte combination.     

Stable interfaces constructed by concentrated ether electrolytes to render robust lithium metal batteries

Lithium metal batteries (LMBs) are highly considered as promising candidates for next-generation energy storage systems.However,routine electrolytes cannot tolerate the high potential at cathodes and low potential at anodes simultaneously,leading to severe interfacial reactions.Herein,a highly concentrated electrolyte (HCE) region trapped in porous carbon coating layer is adopted to form a stable and highly conductive solid electrolyte interphase (SEI) on Li metal surface.The protected Li metal anode can poten-tially match the high-voltage cathode in ester electrolytes.Synergistically,this ingenious design promises high-voltage-resistant interfaces at cathodes and stable SEI with abundance of inorganic components at anodes simultaneously in high-voltage LMBs.The feasibility of this interface-regulation strategy is demonstrated in Li | LiFePO4 batteries,realizing a lifespan twice as long as the routine cells,with a huge capacity retention enhancement from 46.4％ to 88.7％ after 100 cycles.This contribution proof-of-concepts the emerging principles on the formation and regulation of stable electrode/electrolyte inter-faces in the cathode and anode simultaneously towards the next-generation high-energy-density batteries.     

基于铝合金/铝化合物的锂金属负极的研究进展

介绍了近年来基于铝合金/铝化合物的锂金属负极的研究进展,总结了使用铝合金或铝化合物对锂金属负极进行修饰或作为负极材料的典型工作,展望了基于铝合金/4吕化合物的锂金属负极的研究方向.     

All solid-state nickel/metal hydride battery with a proton-conductive phosphoric acid-doped silica gel electrolyte

All solid-state nickel/metal hydride (Ni/MH) battery was fabricated by using a proton-conductive phosphoric acid-doped silica gel as an electrolyte. The H₃PO₄-doped silica gel was dried in vacuum at various temperatures for 1 h before fabricating the battery in order to reduce the possibility of corrosion by water on the surface and in the micropores of the gel. The influence of drying temperature on the crystallinity, water content and conductivity of the gel was investigated. The conductivity depended on the drying temperature of the gel. The fabricated all solid-state Ni/MH battery was able to operate several tens of charge-discharge cycles at relatively high current density although the utilization of the battery was low.     

An ambient-temperature superionic conductive,electrochemically stable,plastic cross-linked polymer electrolyte for lithium metal battery

A plastic cross-linked polymer is prepared using acrylonitrile as a monomer and poly(ethylene glycol diacrylate) as a linking agent. A phase diagram-guide rational design is introduced to fabricate the polymer composite electrolyte in the case of succinonitrile complexed with lithium bis-trifluoromethanesulfonimide. The plastic cross-linked polymer-based electrolyte films with ambient-temperature superionic conductivity (2.33 mS cm⁻¹) and a wide electrochemical window (0–5.6 V vs. Li/Li⁺) have been demonstrated. The charging and discharging experiments of the plastic polymer composite electrolyte-based lithium batteries show that the plastic polymer electrolyte can cycle normally and safely at a current density of 0.5 mA cm⁻². These batteries exhibit excellent average coulombic efficiency of 98.5% in the first 150 cycles. The initial capacity at 25°C is 127.5 mAh g⁻¹ (0.2 C), which is close to the value achieved by liquid-electrolyte-based cells under similar conditions. The capacity retention is 91% after 150 cycles.     

锂离子电池硅负极表面改性的研究进展

硅由于具有高的理论比容量、低的脱嵌锂电位、储量丰富等优势已成为当前高能量密度锂离子电池重要开发的高性能负极材料，但硅负极较大的体膨胀效应和较低的电导率等问题限制硅负极在商业中进一步的应用。针对硅负极材料发展所面临的问题，本文着重从硅的表面改性包括表面包覆、表面功能化、人造固相电解质膜等技术展开综述，分析了这些改性策略及电化学性能改进机理，并对硅表面改性技术进一步发展做了简单展望，旨在开发出高能量密度动力锂电池用关键硅负极材料。     

Safety evaluation of rechargeable cells with lithium metal anodes and amorphous V2O5 cathodes

Rechargeable cells with lithium metal anodes have a very large theoretical energy density and are a promising cell system. However, rechargeable lithium metal cells are not yet currently commercially available. One of the biggest problems with the cells is the poor safety aspect resulting from the high chemical reactivity of lithium. We have been studying a cell system consisting of an amorphous (a-)V2O5P2O5 (95:5 in molar ratio) cathode, a lithium (Li) metal anode and an organic electrolyte in fabricating an AA-size prototype. In this paper, we report recent progress on our rechargeable lithium metal cell focusing on its safety.     

Fabrication of all-solid-state battery using Li5La3Ta2O12 ceramic electrolyte

The chemical and electrochemical properties of Li₅La₃Ta₂O₁₂ (LLTa) solid electrolyte were extensively investigated to determine its compatibility with an all-solid-state battery. A well-sintered LLTa pellet with a garnet-like structure was obtained after sintering at 1200 °C for 24 h. Li ion conductivity of the LLTa pellet was estimated to be 1.3×10⁻⁴ S cm⁻¹. The LLTa pellet was stable when in contact with lithium metal. This indicates that Li metal anode, which is the best anode material, can be applied with the LLTa system. A full cell composed of LiCoO₂/LLTa/Li configuration was constructed, and its electrochemical properties were tested. In the resulting cyclic voltammogram, a clear redox couple of LiCoO₂ was observed, implying that the all-solid-state battery with the Li metal anode was successfully operated at room temperature. The redox peaks of the battery were still observed even after one year of storage in an Ar-filled glove-box. It can be concluded that the LLTa electrolyte is a promising candidate for the all-solid-state battery because of its relatively high Li ion conductivity and good stability when in contact with Li metal anode and LiCoO₂ cathode.