用于全固态锂电池的有机-无机复合电解质

固态电解质被认为是解决传统液态锂金属电池安全隐患和循环性能的关键材料，但仍然存在离子电导率低，界面兼容性差等问题.设计兼顾力学性能、离子电导率和电化学窗口的有机-无机复合型固态电解质材料是发展全固态锂电池的明智选择.近年来，基于无机填料与聚合物电解质的有机-无机复合电解质备受关注.设计与优化复合电解质结构对提高复合电解质综合性能具有重要意义.本文详细梳理了有机-无机复合固态电解质在全固态锂电池中展现的多方面优势，从满足不同性能需求的复合电解质结构设计角度出发，综述了有机-无机复合电解质在锂离子传导、锂枝晶的抑制、界面稳定性和相容性等方面的研究进展，并对有机-无机复合电解质的未来发展趋势和方向进行了展望.     

Lithium-ion transport in inorganic solid state electrolyte

An overview of ion transport in lithium-ion inorganic solid state electrolytes is presented, aimed at exploring and designing better electrolyte materials. Ionic conductivity is one of the most important indices of the performance of inorganic solid state electrolytes. The general definition of solid state electrolytes is presented in terms of their role in a working cell(to convey ions while isolate electrons), and the history of solid electrolyte development is briefly summarized. Ways of using the available theoretical models and experimental methods to characterize lithium-ion transport in solid state electrolytes are systematically introduced. Then the various factors that affect ionic conductivity are itemized, including mainly structural disorder, composite materials and interface effects between a solid electrolyte and an electrode. Finally, strategies for future material systems, for synthesis and characterization methods, and for theory and calculation are proposed, aiming to help accelerate the design and development of new solid electrolytes.     

Forming solid electrolyte interphase in situ in an ionic conducting Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3-polypropylene(PP) based separator for Li-ion batteries

A new concept of forming solid electrolyte interphases(SEI) in situ in an ionic conducting Li_(1.5)Al_(0.5)Ge_(1.5)(PO_4)_3-polypropylene(LAGP-PP) based separator during charging and discharging is proposed and demonstrated. This unique structure shows a high ionic conductivity, low interface resistance with electrode, and can suppress the growth of lithium dendrite. The features of forming the SEI in situ are investigated by scanning electron microscopy(SEM) and x-ray photoelectron spectroscopy(XPS). The results confirm that SEI films mainly consist of lithium fluoride and carbonates with various alkyl contents. The cell assembled by using the LAGP-coated separator demonstrates a good cycling performance even at high charging rates, and the lithium dendrites were not observed on the lithium metal electrode. Therefore, the SEI-LAGP-PP separator can be used as a promising flexible solid electrolyte for solid state lithium batteries.     

Concentrated dual-salt electrolytes for improving the cycling stability of lithium metal anodes

Lithium(Li) metal is an ideal anode material for rechargeable Li batteries, due to its high theoretical specific capacity(3860 mAh/g), low density(0.534 g/cm~3), and low negative electrochemical potential(-3.040 V vs. standard hydrogen electrode). In this work, the concentrated electrolytes with dual salts, composed of Li[N(SO_2F)_2](Li FSI) and Li[N(SO_2CF_3)_2](Li TFSI) were studied. In this dual-salt system, the capacity retention can even be maintained at 95.7%after 100 cycles in Li|Li FePO_4 cells. A Li|Li cell can be cycled at 0.5 mA/cm~2 for more than 600 h, and a Li|Cu cell can be cycled at 0.5 m A/cm~2 for more than 200 cycles with a high average Coulombi efficiency of 99%. These results show that the concentrated dual-salt electrolytes exhibit superior electrochemical performance and would be a promising candidate for application in rechargeable Li batteries.     

Sub-10 nm V2O5 Crystals on Carbon Nanosheets for Advanced All-Solid-State Lithium Metal Batteries

V₂O₅, as a lithium-free cathode material, has inherent defects such as sluggish kinetics and volume change and, at the same time, requires a lithium metal anode that tends to form dendrites in liquid electrolytes. Both the lithium dendrite and the flammable electrolyte solvent bring longtime safety issues. This work introduces nonflammable inorganic–organic composite solid electrolyte to inhibit the growth of the lithium dendrite and suppress the instability caused by V₂O₅ nanometerization. However, the long-term cycling and rate performances are still insufficient even when reducing V₂O₅ size to about 50 nm. As an improvement, sub-10 nm V₂O₅/C nanosheets are designed and prepared using corn stalks as precursors through simple impregnation and calcination process. The V₂O₅/C offers a much better electrode/electrolyte contact and interface stability than bulk V₂O₅ and commercial V₂O₅ in the inorganic–organic composite solid electrolyte. The discharge capacity is 228 mAh g⁻¹ at 0.1 C after 50 cycles and ≈110 mAh g⁻¹ at 2.0 C.     

Thermal transport in lithium-ion battery: A micro perspective for thermal management

In recent years, lithium ion (Li-ion) batteries have served as significant power sources in portable electronic devices and electric vehicles because of their high energy density and rate capability. There are growing concerns towards the safety of Li-ion batteries, in which thermal conductivities of anodes, cathodes, electrolytes and separator play key roles for determining the thermal energy transport in Li-ion battery. In this review, we summarize the state-of-the-art studies on the thermal conductivities of commonly used anodes, cathodes, electrolytes and separator in Li-ion batteries, including both theoretical and experimental reports. First, the thermal conductivities of anodes and cathodes are discussed, and the effects of delithiation degree and temperature of materials are also discussed. Then, we review the thermal conductivities of commonly used electrolytes, especially on solid electrolytes. Finally, the basic concept of interfacial thermal conductance and simulation methods are presented, as well as the interfacial thermal conductance between separator and cathodes. This perspective review would provide atomic perspective knowledge to understand thermal transport in Li-ion battery, which will be beneficial to the thermal management and temperature control in electrochemical energy storage devices.     

Scientific and technological challenges toward application of lithium–sulfur batteries

Recent progress in improving Li–S batteries' cathodes, anodes, and electrolytes via different approaches is summarized. The poor conductivity of sulfur cathodes, the dissolution of polysulfide intermediates, and the high reactivity of metal Li anodes currently motivate a great deal of research. Urgent challenges concerning Li anodes are also emphasized.     

Solid polymer electrolytes based on poly(lithium carboxylate) salts

The ionic conductivity, lithium ion transference number, electrochemical stability, and thermal property of solid polymer electrolytes composed of poly(ethylene oxide) (PEO) and poly(lithium carboxylate)s, (poly(lithium acrylate) (Poly(Li-A)) or poly(lithium fumarate) (Poly(Li-F)), with and without BF₃·OEt₂ were investigated. The ionic conductivities of all solid polymer electrolytes were enhanced by one to two orders of magnitude with addition of BF₃·OEt₂ because the dissociation of lithium ion and carboxylate anion was promoted by the complexation with BF₃. The lithium ion transference number in the solid polymer electrolytes based on poly(lithium carboxylate)s showed relatively high values of 0.41–0.70, due to the suppression of the transport of counter anion by the use of a polymeric anion. The solid polymer electrolytes with addition of BF₃·OEt₂ showed good electrochemical stability.     

纳米颗粒的表面效应和电极颗粒间挤压作用对锂离子电池电压迟滞的影响

硅作为锂离子电池电极材料之一,其应力效应尤为突出,进而将影响电池性能.本文建立了电化学反应-扩散-应力全耦合模型,并研究了恒压充放电条件下扩散诱导应力、表面效应和颗粒间挤压作用对电压迟滞的影响.结果发现,应力及其导致的电压迟滞程度与颗粒尺寸相关.在大颗粒(颗粒半径r 100 nm)中,扩散诱导应力是导致电势迟滞效应的主要因素,这将导致电池能量耗散.对于纳米级小颗粒(r 100 nm)而言,表面效应占据主导,表面效应虽然能缓解电压迟滞,同时却会使驱动电化学反应部分的过电势回线下移,造成锂化容量衰减.本文综合考虑了扩散诱导应力和表面效应,得出:半径为10 nm的颗粒将会使电极具备较好的综合性能.此外,对于硅电极而言,颗粒间挤压作用会使应力回线向压应力状态演化,进而导致锂化容量的衰减.计算结果表明,在电极设计中,对孔隙率设定下限值有助于提升电极性能.     

Impedance characteristics of three-phase electrodes on solid electrolytes

Previously obtained theoretical expressions for the impedance associated with the diffusion of neutral species through a permeable electrode and along the electrode/electrolyte interface are discussed as they apply to gas electrodes on solid electrolytes. A new result, describing diffusion under circular electrode contacts, is obtained. Representative impedance-plane, admittance-plane and Bode-type plots are given for each theoretical model. The effects of rate-controlling adsorption-desorption exchange with the gas phase are considered, as is the applicability of the idealized theoretical models to irregular electrodes.     

Liquid-phase synthesis of Li2S and Li3PS4 with lithium-based organic solutions

Sulfide solid electrolytes are widely regarded as one of the most promising technical routes to realize all-solid-state batteries (ASSBs) due to their high ionic conductivity and favorable deformability. However, the relatively high price of the crucial starting material, Li₂S, results in high costs of sulfide solid electrolytes, limiting their practical application in ASSBs. To solve this problem, we develop a new synthesis route of Li₂S via liquid-phase synthesis method, employing lithium and biphenyl in 1, 2-dimethoxyethane (DME) ether solvent to form a lithium solution as the lithium precursor. Because of the comparatively strong reducibility of the lithium solution, its reaction with sulfur proceeds effectively even at room temperature. This new synthesis route of Li₂S starts with cheap precursors of lithium, sulfur, biphenyl and DME solvent, and the only remaining byproduct (DME solution of biphenyl) after the collection of Li₂S product can be recycled and reused. Besides, the reaction can proceed effectively at room temperature with mild condition, reducing energy cost to a great extent. The as-synthesized Li₂S owns uniform and extremely small particle size, proved to be feasible in synthesizing sulfide solid electrolytes (such as the solid-state synthesis of Li₆PS₅Cl). Spontaneously, this lithium solution can be directly employed in the synthesis of Li₃PS₄ solid electrolytes via liquid-phase synthesis method, in which the centrifugation and heat treatment processes of Li₂S are not necessary, providing simplified production process. The as-synthesized Li₃PS₄ exhibits typical Li⁺ conductivity of 1.85×10^-4 S·cm^-1 at 30 ℃.     

Size effects in lithium ion batteries

Size-related properties of novel lithium battery materials, arising from kinetics, thermodynamics, and newly discovered lithium storage mechanisms, are reviewed. Complementary experimental and computational investigations of the use of the size effects to modify electrodes and electrolytes for lithium ion batteries are enumerated and discussed together.Size differences in the materials in lithium ion batteries lead to a variety of exciting phenomena. Smaller-particle materials with highly connective interfaces and reduced diffusion paths exhibit higher rate performance than the corresponding bulk materials. The thermodynamics is also changed by the higher surface energy of smaller particles, affecting, for example,secondary surface reactions, lattice parameter, voltage, and the phase transformation mechanism. Newly discovered lithium storage mechanisms that result in superior storage capacity are also briefly highlighted.     

Some innovative technologies using solid electrolytes in measuring gas compositions

Solid electrolytes have received considerable scientific attention and assumed important technological significance in recent years, due to potential practical applications in fuel cells, batteries, electrochromics, process control, sensors and environmental protection. Use of solid electrolytes for developing electrochemical gas sensors is a well established field with successful commercial applications related mainly to oxygen measurements. Discovery of new solid electrolytes have led to new areas of development and applications such as hydrogen monitoring. Applicability of solid electrolytes have also been extended to species which are not ionically mobile in the electrolyte by use of auxiliary phases. More recently, significant progress in sensing of molecular species such as CO₂, SO₂, SO₃, NO, NO₂, HCl, H₂O and HF have been achieved by interfacing 2 or more electrolytes in electrochemical chains and/or by using auxiliary phases, semi-permeable coatings or in-situ catalysts to promote the desired electrode reactions. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997     

Nanoparticles Engineering for Lithium‐Ion Batteries

Lithium‐ion batteries (LIBs) have been extensively investigated due to the ever‐increasing demand for new electrode materials for electric vehicles (EVs) and clean energy storage. A wide variety of nano/microstructured LIBs electrode materials are hitherto created via self‐assembly, ranging from 0D nanospheres; 1D nanorods, nanowires, or nanobelts; and 2D nanofilms to 3D nanorod array films. Nanoparticles can be utilized to build up integrated architectures. Understanding of nanoparticles’ self‐assembly may provide information about their organization into large aggregates through low‐cost, high‐efficiency, and large‐scale synthesis. Here, the focus is on the recent advances in preparing hierarchically nano/microstructured electrode materials via self‐assembly. The hierarchical electrode materials are assembled from single component, binary to multicomponent building blocks via different driving forces including diverse chemical bonds and non‐covalent interactions. It is expected that nanoparticle engineering by high‐efficient self‐assembly process will impact the development of high‐performance electrode materials and high‐performance LIBs or other rechargeable batteries.     

RETRACTED ARTICLE: Polymer electrolytes: characteristics and peculiarities

Polymer electrolytes are an important component of many electrochemical devices. This paper reviews state-of-the-art of the electrochemical and physical properties of polymer electrolytes. This review mainly encompasses the properties of different salts, solvents, and polymer hosts, which are encaged in liquid electrolytes. The additions of filler in polymer electrolytes result in composite polymer electrolytes, having high mechanical integrity and ionic conductivity, that are ideal electrolyte for these applications. The next generation state-of-the-art room-temperature ionic liquids based electrolytes, which are far superior to corresponding nonionic solvent-based electrolytes, are also discussed. An erratum to this article can be found at     

Electrochromic & magnetic properties of electrode materials for lithium ion batteries

Progress in electrochromic lithium ion batteries(LIBs) is reviewed, highlighting advances and possible research directions. Methods for using the LIB electrode materials' magnetic properties are also described, using several examples.Li_4Ti_5O_(12)(LTO) film is discussed as an electrochromic material and insertion compound. The opto-electrical properties of the LTO film have been characterized by electrical measurements and UV–Vis spectra. A prototype bi-functional electrochromic LIB, incorporating LTO as both electrochromic layer and anode, has also been characterized by charge–discharge measurements and UV–Vis transmittance. The results show that the bi-functional electrochromic LIB prototype works well. Magnetic measurement has proven to be a powerful tool to evaluate the quality of electrode materials. We introduce briefly the magnetism of solids in general, and then discuss the magnetic characteristics of layered oxides, spinel oxides, olivine phosphate Li Fe PO_4, and Nasicon-type Li_3Fe_2(PO_4)_3. We also discuss what kind of impurities can be detected, which will guide us to fabricate high quality films and high performance devices.     

储氢材料与金属氢化物-镍电池

储氢合金是金属氢化物-镍电池的关键材料，文中简要评述了稀土镍系合金、Laves相系合金、镁基合金、钒基固溶体和纳米管材料作为储氢电极材料的研究进展与目前存在问题，并简要介绍了动力金属氢化物-镍电池的开发动态。     

Ge Nanoparticles Encapsulated in Interconnected Hollow Carbon Boxes as Anodes for Sodium Ion and Lithium Ion Batteries with Enhanced Electrochemical Performance

A carbothermal reaction route to Ge nanoparticle homogeneously encapsulated hollow carbon boxes from NH₄H₃Ge₂O₆/resorcinol formaldehyde precursors is designed, using NH₄H₃Ge₂O₆ as a Ge precursor from commercial GeO₂ and NH₄OH. The Ge/C hybrid anode for sodium ion battery displays a higher Na⁺ storage capacity of 346 mA h g^?1 after 500 cycles at a current density of 100 mA h g^?1, almost approaching the theoretical capacity of Ge. Furthermore, Ge/C anode shows significantly improved electrochemical performance for Li⁺ storage, showing a higher initial Coulombic efficiency of 85.1% and a superior reversible capacity of 1336 mA h g^?1 at a high current density of 200 mA g^?1 after 150 cycles. An excellent rate capability with a capacity of 825 mA h g^?1 at a current density of 4.0 A g^?1 can be obtained based on Ge/C anodes. The enhanced electrochemical performance can be attributed to the unique microstructures of Ge/C hybrid anode. The internal void space of hollow carbon boxes can accommodate the volume expansion of Ge during lithiation or sodiation process, thus preserving the structural integrity of electrode material. The interconnected carbon shell can increase the electronic conductivity of the electrode, resulting in the high rate capability and cycling stability.     

Laser‐induced phase changes in olivine FePO4: a warning on characterizing LiFePO4‐based cathodes with Raman spectroscopy

Raman spectroscopy is an excellent technique for probing lithium intercalation reactions of many diverse lithium ion battery electrode materials. The technique is especially useful for probing LiFePO₄‐based cathodes because the intramolecular vibrational modes of the PO₄³⁻ anions yield intense bands in the Raman spectrum, which are sensitive to the presence of Li⁺ ions. However, the high power lasers typically used in Raman spectroscopy can induce phase transitions in solid‐state materials. These phase transitions may appear as changes in the spectroscopic data and could lead to erroneous conclusions concerning the delithiation mechanism of LiFePO₄. Therefore, we examine the effect of exposing olivine FePO₄ to a range of power settings of a 532‐nm laser. Laser power settings higher than 1.3 W/mm² are sufficient to destroy the FePO₄ crystal structure and result in the formation of disordered FePO₄. After the laser is turned off, the amorphous FePO₄ compound crystallizes in the electrochemically inactive α‐FePO₄ phase. The present experimental results strongly suggest that the power setting of the excitation laser should be carefully controlled when using Raman spectroscopy to characterize fundamental lithium ion intercalation processes of olivine materials. In addition, Raman spectra of the amorphous intermediate might provide insight into the α‐FePO₄ to olivine FePO₄ phase transition that is known to occur at temperatures higher than 450 °C. Copyright © 2008 John Wiley & Sons, Ltd.     

表面效应对锂离子电池正极材料LiMn2O4性能的影响

应用基于自旋极化和广义梯度近似(generalized gradient approximation,GGA)的密度泛函理论计算,研究了锂离子电池正极材料LiMn₂O₄ (001)表面原子和电子结构.发现表面和亚表面附近的原子在垂直于(001)面的方向上具有非常大的弛豫,这对LiMn₂O₄材料在锂离子电池中应用时发现的表面Mn的溶解现象有很大关联.由于表面效应,在LiMn₂O₄ (001) 表面只有三价Mn³⁺离子存在,而这些三价锰离子非常活跃,在该材料电极/电解液界面很容易发生歧化反应,从而加速了Mn的溶解.其他计算结果也和实验观察相符合. 关键词： 锂二次电池 表面弛豫 从头算