全固态锂离子电池关键材料研究进展

全固态锂离子电池采用固态电解质替代传统有机液态电解液,有望从根本上解决电池安全性问题,是电动汽车和规模化储能理想的化学电源。为了实现大容量化和长寿命,从而推进全固态锂离子电池的实用化,电池关键材料的开发和性能的优化刻不容缓,主要包括制备高室温电导率和电化学稳定性的固态电解质以及适用于全固态锂离子电池的高能量电极材料、改善电极/固态电解质界面相容性。本文以全固态锂离子电池关键材料为出发点,综述了不同类型的固态电解质和正负极材料性能特征以及电极/电解质界面性能的调控和优化方法等,阐述了未来全固态锂离子电池关键材料的发展方向以及界面问题的解决思路,为探索全固态锂离子电池产业化前景奠定基础。     

薄膜锂离子电池负极材料的研究进展

全固态薄膜锂离子电池是锂离子电池的最新研究领域,其能量密度高、厚度薄、循环寿命长、可靠度高。薄膜化的负极材料是锂离子电池的重要组成部分,负极薄膜材料制备方法的研究取得了较大的进展,未来研究重点是低成本、低能耗、高综合电化学性能的负极薄膜材料以及可批量生产的薄膜制备技术。对薄膜化的硅负极材料、金属或合金薄膜材料、氧化物薄膜材料和复合薄膜材料近几年来的研究状况进行了综述,并对其发展前景进行了展望。     

锂离子电池纳米硅碳负极材料研究进展

高能量密度锂离子二次电池对于缓解能源和环境危机具有重要意义.硅基材料理论比容量远超石墨,是目前公认的下一代锂离子电池负极材料.中国科学院物理研究所自1999年在国际上首次报道纳米化对于硅负极性能提升的重要作用以来,持续对纳米硅基材料的基础科学问题以及产业化应用进行了大量探索,主要包括纳米硅基负极材料的脱嵌锂机理、结构及...     

从正极材料看锂离子电池在储能领域的应用

针对锂离子电池在电力储能中的应用,从电化学性能、安全性能以及价格等方面比较了岩盐结构LiCoO₂、尖晶石型LiMn2O4和橄榄石型LiFePO4 3类主要的锂离子电池正极材料,论述了它们各自的优点和不足之处。对不同正极材料的锂离子电池在储能领域存在的问题进行了分析,对各自的应用前景进行了展望,认为LiMn2O4和LiFePO4分别适用于功率型应用和容量型应用。     

铌元素在锂离子电池中的应用

锂离子电池因其能量密度高、环境污染小等优点得到了广泛应用,但其仍然存在不容忽视的问题,电极材料结构劣化导致的电化学性能下降及热稳定性差等问题仍然比较严重,因此电极材料改性仍然是目前锂离子电池的研究重点.基于铌具有其自身独特的优势,将铌引入锂离子电池作为正极掺杂材料,可以提高电子导电性、提高稳定性、扩展Li+嵌入/脱出通...     

锂离子电池补锂技术

锂离子电池在化成过程中,负极SEI膜的形成会消耗大量活性锂,特别是在添加部分高容量硅基负极材料的情况下,导致电池首周库仑效率和电池容量低.补充活性锂是解决这一问题的有效手段,目前已报道的补充活性锂的途径很多,主要是负极补锂和正极极补锂两大类.负极补锂包括金属锂物理混合锂化,如在负极中添加金属锂粉或在极片表面辊压金属锂箔...     

木质素作为锂离子电池电极材料的研究进展

木质素是地球上储量充足的芳香族高聚物,结构中富含羟基、羧基、醚基等多种官能团.这些官能团的存在允许选择性的修饰这种复杂的化合物.木质素是制浆造纸工业的副产品,成本便宜、来源广泛,通过简单温和的化学活化制备的多孔木质素基碳已成为环境净化、电催化和储能领域的研究热点,尤其是作为锂离子电池的负极材料.本文简要介绍了锂离子电池...     

三元NCM锂离子电池高电压电解质的研究进展

层状三元材料LiNixCoyMn1-x-yO2(以下简称NCM)具有较高的比容量和工作电压平台及良好的倍率性能,在电动汽车领域占据重要地位.为满足电动汽车续航里程的需求,提高工作电压被视为提升三元锂离子电池能量密度的一种有效手段.然而现存电解液电化学窗口窄,无法实现高电压下的稳定循环.本综述对高工作电压下的NCM电池电...     

Fabrication of all-solid-state lithium battery with lithium metal anode using Al2O3-added Li7La3Zr2O12 solid electrolyte

Li₇La₃Zr₂O₁₂ (LLZ) solid electrolyte is one of the promising electrolytes for all-solid-state battery due to its high Li ion conductivity and stability against Li metal anode. However, high calcination temperature for LLZ preparation promotes formation of La₂Zr₂O₇ impurity phase. In this paper, an effect of Al₂O₃ addition as sintering additive on LLZ solid electrolyte preparation and electrochemical properties of Al₂O₃-added LLZ were examined. By the Al₂O₃ addition, sintered LLZ pellet could be obtained after 1000 °C calcination, which is 230 °C lower than that without Al₂O₃ addition. Chemical and electrochemical properties of the Al₂O₃-added LLZ, such as stability against Li metal and ion conductivity, were comparable with the LLZ without Al₂O₃ addition, i.e. σ_bulk and σ_total were 2.4 × 10⁻⁴ and 1.4 × 10⁻⁴ S cm⁻¹ at 30 °C, respectively. All-solid-state battery with Li/Al₂O₃-added LLZ/LiCoO₂ configuration was fabricated and its electrochemical properties were tested. In cyclic voltammogram, clear redox peaks were observed, indicating that the all-solid-state battery with Li metal anode was successfully operated. The redox peaks were still observed even after one year storage of the all-solid-state battery in the Ar-filled globe-box. It can be inferred that the Al₂O₃-added LLZ electrolyte would be a promising candidate for all-solid-state battery because of facile preparation by the Al₂O₃ addition, relatively high Li ion conductivity, and good stability against Li metal and LiCoO₂ cathode.     

Characterization of low-flammability electrolytes for lithium-ion batteries

In an effort to develop low-flammability electrolytes for a new generation of Li-ion batteries, we have evaluated physical and electrochemical properties of electrolytes with two novel phosphazene additives. We have studied performance quantities including conductivity, viscosity, flash point, and electrochemical window of electrolytes as well as formation of solid electrolyte interphase (SEI) films. In the course of study, the necessity for a simple method of SEI characterization was realized. Therefore, a new method and new criteria were developed and validated on 10 variations of electrolyte/electrode substrates. Based on the summation of determined physical and electrochemical properties of phosphazene-based electrolytes, one structure of phosphazene compound was found better than the other. This capability helps to direct our further synthetic work in phosphazene chemistry.     

Formation of the high lithium ion conducting phase from mechanically milled amorphous Li2S-P2S5 system

The fast ionic conducting structure similar to thio-Lithium Super Ionic Conductor (LISICON) phase is synthesized in the Li₂S-P₂S₅ system. The Li₂S-P₂S₅ glass-ceramics with the composition of xLi₂S·(100−x)P₂S₅ (75 ≤ x ≤ 80) are prepared by the heat-treatment of mechanically milled amorphous sulfide powders. In the binary Li₂S-P₂S₅ system, 78.3Li₂S·21.7P₂S₅ glass ceramic prepared by mechanical milling and subsequent heat-treatment at 260 °C for 3 h shows the highest conductivity of 6.3 × 10⁻⁴ S cm⁻¹ at room temperature and the lowest activation energy for conduction of 30.5 kJ mol⁻¹. The enhancement of conductivity with increasing x up to 78.3 is probably caused by the introduction of interstitial lithium ions at the Li sites which affects the Li ion distribution. The prepared electrolyte exhibits the lithium ion transport number of almost unity and voltage stability of 5 V vs. Li at room temperature.     

Charge/discharge behavior of plasma-fluorinated natural graphites in propylene carbonate-containing solvent

Plasma-fluorination of natural graphite samples with average particle sizes of 5 μm, 10 μm and 15 μm (NG5μm, NG10μm and NG15μm) was performed using CF₄ and charge/discharge characteristics of surface-fluorinated samples were investigated in 1 mol dm⁻³ LiClO₄–ethylene carbonate (EC)/diethyl carbonate (DEC)/propylene carbonate (PC) (1:1:1, v/v/v). Fluorine contents obtained by elemental analysis were in the range of 0.3–0.6 at.% and surface fluorine concentrations determined by X-ray photoelectron microscopy (XPS) were 14.8–17.3 at.%. Plasma-fluorination increased surface disorder of natural graphite samples though reduced surface areas due to its surface etching effect. Electrochemical decomposition of PC was highly reduced on surface-fluorinated NG10μm and NG15μm with high disorder. First coulombic efficiencies of plasma-fluorinated NG10μm and NG15μm increased by 9.7 and 19.3% at 150 mA g⁻¹, respectively.     

Lithium ion secondary batteries; past 10 years and the future

Technologies of lithium ion secondary batteries (LIB) were pioneered by Sony. Since the introduction of LIB on the market first in the world in 1991, the LIB has been applied to consumer products as diverse as cellular phones, video cameras, notebook computers, portable minidisk players and others. Years of assiduous efforts and researches to improve LIB performances enabled LIB to play a leading role in the portable secondary battery market. In this article, the past 10 years’ technological achievement is traced and future possibilities are discussed.     

Surface structure and electrochemical characteristics of plasma-fluorinated petroleum cokes for lithium ion battery

Plasma-fluorination of petroleum coke and those heat-treated at 1860, 2300 and 2800 °C (abbreviated to PC, PC1860, PC2300 and PC2800) was conducted for 15, 30 and 60 min using CF₄ gas at 90 °C. Fluorine contents obtained by elemental analysis were negligible except PC fluorinated for 60 min (0.7 at.%). Fluorine concentration on the surface decreased with increasing heat-treatment temperature of petroleum coke, i.e. from PC to PC2800 when plasma-fluorination was made for 30 and 60 min. Transmission electron microscopic observation revealed that the closed edges of PC2800 were destroyed and opened by plasma-treatment. Plasma-fluorination increased surface disorder of heat-treated petroleum cokes, however, slightly reduced surface areas. These surface structure changes increased first coulombic efficiencies of PC2300 and PC2800 by 6–8 and 8–10% at both 60 and 150 mA g⁻¹, respectively.     

Electrochemical properties of Li1.4Al0.4Ti1.6(PO4)3 synthesized by a co-precipitation method

Sub-micron Li_1.4Al_0.4Ti_1.6(PO₄)₃ (LATP) ceramic powder is synthesized by a co-precipitation method which can be applied for mass production. A pure Nasicon phase is confirmed by X-ray diffraction analysis and the primary particle size of the product is 200-500 nm. The sinterability of LATP is investigated and the relative density of 97% reached at a sintering temperature as low as 900 °C for 6 h. The bulk lithium ionic conductivity of the sintered pellet is 2.19 × 10⁻³ S cm⁻¹, and a total conductivity of 1.83 × 10⁻⁴ S cm⁻¹ is obtained.     

Solid solution lithium alloy cermet anodes

Lithium–magnesium solid solution alloys with compositions between Li_0.6Mg_0.4 and Li_0.8Mg_0.2 were prepared by melting the component metals in argon. Experiments carried out in a transparent cell confirmed the suppression of dendrite formation on the alloy surface. Diffusion kinetics within the bulk alloy limit the practical current density, particularly during discharging. Heating mixtures of lithium nitride and magnesium provides a convenient method of preparing ceramic–metal composites (“cermets”) containing the solid solution alloy and inert magnesium nitride. The cermets can be formed into a desired shape before or after reaction and may offer a route to higher surface area metallic anodes with improved rate capability.