Fast ion conducting lithium glasses—Review

For the last few years fast ion conducting lithium glasses are being studied due to their potential use in advanced electrochemical devices. A number of glass systems containing oxides, sulphides and other lithium compounds prepared by both conventional cooling and rapid quenching techniques have been reported. In this paper we review the transport properties of lithium ion conducting glasses. The special features of the ionic conduction process have been highlighted and some experimental techniques to study transport properties have been described. Some of the common observations of the properties have been discussed and finally some important problems for future development have been pointed out.     

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.     

Highly efficient terahertz pulse generation by optical rectification in stoichiometric and cryo-cooled congruent lithium niobate

We report, and review in detail, experiments resulting in a record 3.7% optical-to-terahertz (THz) conversion efficiency by optical rectification (OR) in cryogenically cooled congruent lithium niobate (cLN) using a near-optimal 680 fs pump pulse at 1030 nm. In addition, we report a record conversion efficiency of 1.7% at room temperature using stoichiometric lithium niobate (sLN) which results in 21.8 μJ of THz energy from a 1.2 mJ optical pulse. Electro-optical sampling measurements reveal the THz pulses to be single-cycle and centered at 0.45?THz. The experimentally measured efficiency, THz waveform, and THz spectrum are in good agreement with theoretical calculations. Finally, spatial beam profile measurements are also provided. To our knowledge, these results represent an order of magnitude improvement in efficiency of THz generation by OR in lithium niobate over previous results.     

Inside Front Cover: Photonic Crystal Structures as a Basis for a Three‐Dimensionally Interpenetrating Electrochemical‐Cell System (Adv. Mater. 13/2006)

The inside cover shows an SEM image of a 3D‐interpenetrating electrochemical cell with submicrometer features, as reported by Stein and coworkers on p. 1750. The pores of an inverse‐opal carbon electrode are coated with a conformal layer of a polymer separator and infiltrated with vanadia to form the opposite electrode after lithiation. The idealized scheme illustrates lithium‐ion transport between the electrodes through the polymer membrane.     

Creating Lithium‐Ion Electrolytes with Biomimetic Ionic Channels in Metal–Organic Frameworks

Solid‐state electrolytes are the key to the development of lithium‐based batteries with dramatically improved energy density and safety. Inspired by ionic channels in biological systems, a novel class of pseudo solid‐state electrolytes with biomimetic ionic channels is reported herein. This is achieved by complexing the anions of an electrolyte to the open metal sites of metal–organic frameworks (MOFs), which transforms the MOF scaffolds into ionic‐channel analogs with lithium‐ion conduction and low activation energy. This work suggests the emergence of a new class of pseudo solid‐state lithium‐ion conducting electrolytes.     

Polymer electrolytes for lithium-ion batteries

The motivation for lithium battery development and a discussion of ion conducting polymers as separators begin this review, which includes a short history of polymer electrolyte research, a summary of the major parameters that determine lithium ion transport in polymer matrices, and consequences for solid polymer electrolyte development. Two major strategies for the application of ion conducting polymers as separators in lithium batteries are identified: One is the development of highly conductive materials via the crosslinking of mobile chains to form networks, which are then swollen by lithium salt solutions ("gel electrolytes"). The other is the construction of solid polymer electrolytes (SPEs) with supramolecular architectures, which intrinsically give rise to much enhanced mechanical strength. These materials as yet exhibit relatively common conductivity levels but may be applied as very thin films. Molecular composites based on poly(p-phenylene)- (PPP)-reinforced SPEs are a striking example of this direction. Neither strategy has as yet led to a "breakthrough" with respect to technical application, at least not for electrically powered vehicles. Before being used as separators, the gel electrolytes must be strengthened, while the molecularly reinforced solid polymer electrolytes must demonstrate improved conductivity.     

全固态锂离子电池中金属锂负极界面优化改性研究

以共聚物PEDOT-co-PEG作为锂金属阳极的表面改性层,采用磷酸铁锂复合阳极和“石榴石型”物质以及聚合氧乙烷聚合物组成的固体电解质制备了全固态锂离子电池。采用SEM分析了锂金属充电-放电反复操作后的形态学改变;采用电化学组抗谱试验研究了改性后的锂金属以及复合固体电解质接触面的稳定性并对全固态锂离子电池的充电-放电性能和界面稳定性进行了研究。结果表明,未改性的锂金属在固态电池充电-放电过程中会生成锂枝晶,从而导致全固态锂离子电池的高电流密度容量快速衰变;“石榴石型”物质以及聚合氧乙烷聚合物组成的固体电解质与改性后的金属锂具有良好的接触面,从而扼制锂枝晶的形成,提高全固态锂离子电池的机械性能;在PEDOT-co-PEG共聚物改性锂金属后,全固态锂离子电池的平稳性显著提高,且容量减弱放缓。     

Lithium solid electrolytes and their applications

The preparation, characterisation and applications of two systems of lithium ion conductors, lithium zinc germanate (Lisicon) and lithium germanate vanadate are described. Ionic conductivity studies include ac conductivity, thermopower andnmr which provide complementary information. High pressure studies and fabrication of a solid-state cell are also reported. An erratum to this article is available at .     

Anion‐Sorbent Composite Separators for High‐Rate Lithium‐Ion Batteries

Novel composite separators containing metal–organic‐framework (MOF) particles and poly(vinyl alcohol) are fabricated by the electrospinning process. The MOF particles containing opened metal sites can spontaneously adsorb anions while allowing effective transport of lithium ions in the electrolyte, leading to dramatically improved lithium‐ion transference number t_Li⁺ (up to 0.79) and lithium‐ion conductivity. Meanwhile, the incorporation of the MOF particles alleviates the decomposition of the electrolyte, enhances the electrode reaction kinetics, and reduces the interface resistance between the electrolyte and the electrodes. Implementation of such composite separators in conventional lithium‐ion batteries leads to significantly improved rate capability and cycling durability, offering a new prospective toward high‐performance lithium‐ion batteries.     

Atomic Interlamellar Ion Path in High Sulfur Content Lithium‐Montmorillonite Host Enables High‐Rate and Stable Lithium–Sulfur Battery

Fast lithium ion transport with a high current density is critical for thick sulfur cathodes, stemming mainly from the difficulties in creating effective lithium ion pathways in high sulfur content electrodes. To develop a high‐rate cathode for lithium–sulfur (Li–S) batteries, extenuation of the lithium ion diffusion barrier in thick electrodes is potentially straightforward. Here, a phyllosilicate material with a large interlamellar distance is demonstrated in high‐rate cathodes as high sulfur loading. The interlayer space (≈1.396 nm) incorporated into a low lithium ion diffusion barrier (0.155 eV) significantly facilitates lithium ion diffusion within the entire sulfur cathode, and gives rise to remarkable nearly sulfur loading‐independent cell performances. When combined with 80% sulfur contents, the electrodes achieve a high capacity of 865 mAh g^?1 at 1 mA cm^?2 and a retention of 345 mAh g^?1 at a high discharging/charging rate of 15 mA cm^?2, with a sulfur loading up to 4 mg. This strategy represents a major advance in high‐rate Li–S batteries via the construction of fast ions transfer paths toward real‐life applications, and contributes to the research community for the fundamental mechanism study of loading‐independent electrode systems.     

Hierarchical Interconnected Expanded Graphitic Ribbons Embedded with Amorphous Carbon: An Advanced Carbon Nanostructure for Superior Lithium and Sodium Storage

Carbon materials have attracted considerable attention as anodes for lithium‐ion and sodium‐ion batteries due to their low cost and environmental friendliness. This work reports an advanced carbon nanostructure that takes advantage of the chelation effect of glucose and metal ions, which ensures the uniform dispersion of metal in the precursor. Thus, an effective catalytic conversion from sp³ to sp² carbon occurs, enabling simultaneously formation of pores with catalyzed graphitic structures. Due to the low carbonization temperature and short carbonization time as well as the different catalytic degree of various metals, a series of expanded graphitic layers from 0.34 to 0.44 nm with defects and amorphous carbon structure are obtained. The structure not only offers accessible graphitic spacings for reversible lithium/sodium ion insertion, but also provides abundant active sites for lithium/sodium ion adsorption in the defects and amorphous structure. Moreover, the hierarchical interconnected porous structure combining graphitic ribbons is beneficial for fast electronic/ionic transport and favorable electrolyte permeation. More importantly, such advanced carbon materials prove their feasibility for balancing the pore structure and degree of graphitization. When serving as the electrode material for lithium‐ion and sodium‐ion batteries, excellent electrochemical performance along with fast kinetics and long cycle life is achieved.     

可用于锂离子电池的新型锂盐:LiODFB

介绍一种新型的可用于锂离子电池的锂盐:LiODFB(lithium oxalyldifluoroborate).LiODFB独特的化学结构,使其结合了双乙二酸硼酸锂(LiBOB)及四氟硼酸锂(LiBF4)的优势.与LiBOB相比,LiODFB在碳酸酯中的溶解性和溶剂的黏度有了明显改善,从而使锂离子电池具有更好的低温性能和倍率放电性能.而与LiBF4相比,LiODFB能促进稳定固态电解液界面(solid electrolyte interface,SEI)的形成,改善了锂离子电池的高温性能.该种新型锂盐还具有以下优点:与金属锂的化学稳定性好,在高电位下能够很好地使铝箔得到钝化和提高锂离子电池安全性能及抗过充的能力.这些性能使得LiODFB成为一种极有可能替代LiPF6的新型锂盐.     

Formation Energies of the Lithium Intercalations in MoS2

First-principles calculations have been performed to study the lithium intercalations in MoS2. The formation energies, changes of volumes, electronic structures and charge densities of the lithium intercalations in MoS2 are presented. Our calculations show that during lithium intercalations in MoS2, the lithium intercalation formation energies per lithium atom are between 2.5 eV to 3.0 eV. The volume expansions of MoS2 due to lithium intercalations are relatively small     

Flexible Aqueous Li‐Ion Battery with High Energy and Power Densities

A flexible and wearable aqueous symmetrical lithium‐ion battery is developed using a single LiVPO₄F material as both cathode and anode in a “water‐in‐salt” gel polymer electrolyte. The symmetric lithium‐ion chemistry exhibits high energy and power density and long cycle life, due to the formation of a robust solid electrolyte interphase consisting of Li₂CO₃‐LiF, which enables fast Li‐ion transport. Energy densities of 141 Wh kg^?1, power densities of 20 600 W kg^?1, and output voltage of 2.4 V can be delivered during >4000 cycles, which is far superior to reported aqueous energy storage devices at the same power level. Moreover, the full cell shows unprecedented tolerance to mechanical stress such as bending and cutting, where it not only does not catastrophically fail, as most nonaqueous cells would, but also maintains cell performance and continues to operate in ambient environment, a unique feature apparently derived from the high stability of the “water‐in‐salt” gel polymer electrolyte.     

Reversible nanopore formation in Ge nanowires during lithiation-delithiation cycling: an in situ transmission electron microscopy study

Retaining the high energy density of rechargeable lithium ion batteries depends critically on the cycle stability of microstructures in electrode materials. We report the reversible formation of nanoporosity in individual germanium nanowires during lithiation-delithiation cycling by in situ transmission electron microscopy. Upon lithium insertion, the initial crystalline Ge underwent a two-step phase transformation process: forming the intermediate amorphous Li(x)Ge and final crystalline Li(15)Ge(4) phases. Nanopores developed only during delithiation, involving the aggregation of vacancies produced by lithium extraction, similar to the formation of porous metals in dealloying. A delithiation front was observed to separate a dense nanowire segment of crystalline Li(15)Ge(4) with a porous spongelike segment composed of interconnected ligaments of amorphous Ge. This front sweeps along the wire with a logarithmic time law. Intriguingly, the porous nanowires exhibited fast lithiation/delithiation rates and excellent mechanical robustness, attributed to the high rate of lithium diffusion and the porous network structure for facile stress relaxation, respectively. These results suggest that Ge, which can develop a reversible nanoporous network structure, is a promising anode material for lithium ion batteries with superior energy capacity, rate performance, and cycle stability.     

A Universal Strategy for Hollow Metal Oxide Nanoparticles Encapsulated into B/N Co‐Doped Graphitic Nanotubes as High‐Performance Lithium‐Ion Battery Anodes

Yolk–shell nanostructures have received great attention for boosting the performance of lithium‐ion batteries because of their obvious advantages in solving the problems associated with large volume change, low conductivity, and short diffusion path for Li⁺ ion transport. A universal strategy for making hollow transition metal oxide (TMO) nanoparticles (NPs) encapsulated into B, N co‐doped graphitic nanotubes (TMO@BNG (TMO = CoO, Ni₂O₃, Mn₃O₄) through combining pyrolysis with an oxidation method is reported herein. The as‐made TMO@BNG exhibits the TMO‐dependent lithium‐ion storage ability, in which CoO@BNG nanotubes exhibit highest lithium‐ion storage capacity of 1554 mA h g^?1 at the current density of 96 mA g^?1, good rate ability (410 mA h g^?1 at 1.75 A g^?1), and high stability (almost 96% storage capacity retention after 480 cycles). The present work highlights the importance of introducing hollow TMO NPs with thin wall into BNG with large surface area for boosting LIBs in the terms of storage capacity, rate capability, and cycling stability.     

二维晶体材料MXene的电化学应用研究进展

MXene是一种类石墨烯结构的新型二维过渡金属碳化物或碳氮化物,通过氟盐和盐酸或氢氟酸刻蚀前驱体MAX相中的活泼金属元素得到,其化学通式为Mn+1XnT(n=1,2,3…),T表示表面所附着的官能团(-H、-F或-OH)。得益于其表面的官能团,MXene在储能方面应用较为广泛。通过表面改性、离子插层,增加MXene晶面间距,提高离子传输效率,以优化MXene在电化学方面的应用。综述了以Ti3C2为代表的MXene的制备方法、理论研究以及在锂离子电池、锂硫电池、超级电容器等方面的应用研究进展,展望了MXene在电化学领域的应用前景和未来的研究方向。     

Ultrathin graphite foam: a three-dimensional conductive network for battery electrodes

We report the use of free-standing, lightweight, and highly conductive ultrathin graphite foam (UGF), loaded with lithium iron phosphate (LFP), as a cathode in a lithium ion battery. At a high charge/discharge current density of 1280 mA g(-1), the specific capacity of the LFP loaded on UGF was 70 mAh g(-1), while LFP loaded on Al foil failed. Accounting for the total mass of the electrode, the maximum specific capacity of the UGF/LFP cathode was 23% higher than that of the Al/LFP cathode and 170% higher than that of the Ni-foam/LFP cathode. Using UGF, both a higher rate capability and specific capacity can be achieved simultaneously, owing to its conductive (～1.3 × 10(5) S m(-1) at room temperature) and three-dimensional lightweight (～9.5 mg cm(-3)) graphitic structure. Meanwhile, UGF presents excellent electrochemical stability comparing to that of Al and Ni foils, which are generally used as conductive substrates in lithium ion batteries. Moreover, preparation of the UGF electrode was facile, cost-effective, and compatible with various electrochemically active materials.     

Pulse voltammetric and ac impedance spectroscopic studies on lithium ion transfer at an electrolyte/Li4/3Ti5/3O4 electrode interface

Pulse voltammetry and ac impedance spectroscopy were used to study the lithium ion kinetics at a lithium ion insertion electrode consisting of Li4/3Ti5/3O4 thin films in an organic electrolyte. In the cyclic voltammogram, two redox peaks appeared at around 1.56 V vs Li/Li+ due to the insertion and extraction of lithium ion at the electrode. Differential pulse voltammetry gave a large reduction current at approximately 1.56 V during a cathodic scan due to lithium ion insertion into the electrode. From the peak current and potential, the charge-transfer resistance was evaluated by quantitative analysis using approximate equations for irreversible reactions. In the Nyquist plot, one semicircle was observed at 1.56 V, which was assigned to the charge-transfer resistance due to lithium ion transfer at the electrode/electrolyte interface. The value of the charge-transfer resistance at 1.56 V was almost identical to that evaluated by differential pulse voltammetry with an identical characteristic relaxation time. This result shows that both dc differential pulse voltammetry and ac impedance spectroscopy are useful for elucidating the phase transfer kinetics of lithium ion at insertion electrodes.