Suppression of Co(Ⅱ)ion deposition and hazards:Regulation of SEI film composition and structure

Despite the presence of Li F components in the solid electrolyte interphase(SEI)formed on the graphite anode surface by conventional electrolyte,these Li F components primarily exist in an amorphous state,rendering them incapable of effectively inhibiting the exchange reaction between lithium ions and transition metal ions in the electrolyte.Consequently,nearly all lithium ions within the SEI film are replaced by transition metal ions,resulting in an increase in interphacial impedance and a decrease in stability.Herein,we demonstrate that the SEI film,constructed by fluoroethylene carbonate(FEC)additive rich in crystalline Li F,effectively inhibits the undesired Li^(+)/Co^(2+)ion exchange reaction,thereby suppressing the deposition of cobalt compounds and metallic cobalt.Furthermore,the deposited cobalt compounds exhibit enhanced structural stability and reduced catalytic activity with minimal impact on the interphacial stability of the graphite anode.Our findings reveal the crucial influence of SEI film composition and structure on the deposition and hazards associated with transition metal ions,providing valuable guidance for designing next-generation electrolytes.

Dependence of lithium metal battery performances on inherent separator porous structure regulation

Boosting of rechargeable lithium metal batteries(LMBs) holds challenges because of lithium dendrites germination and high-reactive surface feature.Separators may experience structure-determined chemical deterioration and worsen Li plating-stripping behaviors when smoothly shifting from lithium-ion batteries(LIBs) to LMBs.This study precisely regulations the crystal structure of β-polypropylene and separator porous construction to investigate the intrinsic porous structure and mechanical properties determined electrochemical performances and cycling durability of LMBs.Crystal structure characterizations,porous structure analyses,and electrochemical cycling tests uncover appropriate annealing thermal stimulation concentrates β-lamellae thickness and enhances lamellae thermal stability by rearranging molecular chain in inferior β-lamellae,maximally homogenizing biaxial tensile deformation and resultant porous constructions.These even pores with high connectivity lower ion migration barriers,alleviate heterogeneous Li^(+) flux dispersion,stabilize reversible Li plating-stripping behaviors,and hinder coursing and branching of Li dendrites,endowing steady cell cycling durability,especially at higher currents due to the highlighted uncontrollable cumulation of dead Li,which offers new insights for the current pursuit of high-power density battery and fast charging technology.The suggested separator structure-chemical nature functions in ensuring cyclic cell stability and builds reliable relationships between separator structure design and practical LMBs applications.

Atomically Dispersed Ruthenium Catalysts with Open Hollow Structure for Lithium-Oxygen Batteries

Lithium–oxygen battery with ultrahigh theoretical energy density is considered a highly competitive next-generation energy storage device,but its practical application is severely hindered by issues such as difficult decomposition of discharge products at present.Here,we have developed N-doped carbon anchored atomically dispersed Ru sites cathode catalyst with open hollow structure(h-RuNC)for Lithium–oxygen battery.On one hand,the abundance of atomically dispersed Ru sites can effectively catalyze the formation and decomposition of discharge products,thereby greatly enhancing the redox kinetics.On the other hand,the open hollow structure not only enhances the mass activity of atomically dispersed Ru sites but also improves the diffusion efficiency of catalytic molecules.Therefore,the excellent activity from atomically dispersed Ru sites and the enhanced diffusion from open hollow structure respectively improve the redox kinetics and cycling stability,ultimately achieving a high-performance lithium–oxygen battery.

Lithium intercalation/de-intercalation behavior of a composite Sn/C thin film fabricated by magnetron sputtering

A tin film of 320 nm in thickness on Cu foil and its composite film with graphite of-50 nm in thickness on it were fabricated by magnetron sputtering. The surface morphology, composition, surface distributions of alloy elements, and lithium intercalation/de-intercalation behaviors of the fabricated films were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, electron probe microanalyzer （EPMA）, X-ray photoelectron spectroscopy （XPS）, inductively coupled plasma atomic emission spectrometry （ICP）, cyclic voltammetry （CV）, and galvanostatic charge/discharge （GC） measurements. It is found that the lithium intercalation/de-intercalation behavior of the Sn film can be significantly improved by its composite with graphite. With cycling, the discharge capacity of the Sn film without composite changes from 570 mAh/g of the 2nd cycle to 270 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 90% and 95%. Nevertheless, the discharge capacity of the composite Sn/C film changes from 575 mAh/g of the 2nd cycle to 515 mAh/g of the 20th cycle, and its efficiency for the discharge and charge is between 95% and 100%. The performance improvement of tin by its composite with graphite is ascribed to the retardation of the bulk tin cracking from volume change during lithium intercalation and de-intercalation, which leads to the pulverization of tin.

High-performance all-solid-state polymer electrolyte with fast conductivity pathway formed by hierarchical structure polyamide 6 nanofiber for lithium metal battery

The utilization of all-solid-state electrolytes is considered to be an effective way to enhance the safety performance of lithium metal batteries.However,the low ionic conductivity and poor interface compatibility greatly restrict the development of all-solid-state battery.In this study,a composite electrolyte combining the electrospun polyamide 6(PA6)nanofiber membrane with hierarchical structure and the polyethylene oxide(PEO)polymer is investigated.The introduction of PA6 nanofiber membrane can effectively reduce the crystallinity of the polymer,so that the ionic conductivity of the electrolyte can be enhanced.Moreover,it is found that the presence of finely branched fibers in the hierarchical structure PA6 membrane allows the polar functional groups(C=O and N-H bonds)to be fully exposed,which provides sufficient functional sites for lithium ion transport and helps to regulate the uniform deposition of lithium metal.Moreover,the hierarchical structure can enhance the mechanical strength(9.2 MPa)of the electrolyte,thereby effectively improving the safety and cycle stability of the battery.The prepared Li/Li symmetric battery can be stably cycled for 1500 h under 0.3 mA cm^(-2) and 60℃.This study demonstrates that the prepared electrolyte has excellent application prospects in the next generation all-solid-state lithium metal batteries.

Preparation of Sn nano-film by direct current magnetron sputtering and its performance as anode of lithium ion battery

Sn thin film on Cu foil substrate as the anode of lithium ion battery was prepared by direct current magnetron sputtering(DCMS). The surface morphology,composition and thickness and the electrochemical behaviors of the prepared Sn thin film were characterized by scanning electron microscopy(SEM),X-ray diffraction(XRD),inductively coupled plasma atomic emission spectrometry(ICP),cyclic voltammetry(CV) and galvanostatic charge/ discharge(GC) measurements. It is found that the Sn film is consists of pure Sn with an average particle diameter of 100 nm. The thickness of the film is about 320 nm. The initial lithium insertion capacity of the Sn film is 771 mA·h/g. The reversible capacity of the film is 570 mA·h/g and kept at 270 mA·h/g after 20 cycles.

Challenges in the Development of Film-Forming Additives for Lithium Ion Battery: A Review

Electrolytes additives are ubiquitous and indispensable in all electrochemical devices. In this sense, the principle and the classification of film-forming additives for lithium ion secondary batteries are described. The film formation mechanism and research progress of the pyrazole derivatives, organic halogenide, esters and derivatives, boron compounds and inorganic compounds are introduced. Emphasis is focused on the principles and film-forming mechanisms of each additive. The development of film-forming additives is forecasted and prospected.

Thin-film lithium-ion battery derived from Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3 sintered pellet

Thin-film lithium-ion battery of LiMn2O4/Li1.3Al0.3Ti1.7(PO4)3/LiMn2O4 was fabricated using Li1.3Al0.3Ti1.7(PO4)3 sintered pellet as both substrate and electrolyte. Li1.3Al0.3Ti1.7(PO4)3 sintered pellet was prepared by sol-gel technique, and the thin-film battery was heat-treated by rapid thermal annealing. Phase identification, morphology and electrochemical properties of the components and thin-film battery were investigated by X-ray diffractometry, scanning electron microscopy, electrochemical impedance spectroscopy and galvanostatic charge-discharge experiments. The results show that Li1.3Al0.3Ti1.7(PO4)3 possesses a electrochemical window of 2.4 V and an ionic conductivity of 1.2 ×10-4 S/cm. With Li1.3Al0.3Ti1.7(PO4)3 sintered pellet as both substrate and solid electrolyte, the fabricated thin-film battery with an open circuit voltage of 1.2V can be easily cycled.

Laminar Composite Solid Electrolyte with Poly(Ethylene Oxide)-Threaded Metal-Organic Framework Nanosheets for High-Performance All-Solid-State Lithium Battery

Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.

First-principles study of interphase Ni_3Sn in Sn-Ni alloy for anode of lithium ion battery

This paper investigates the mechanism of Li insertion into interphase Ni3Sn in Ni-Sn alloy for the anode of lithium ion battery by means of the first-principles plane-wave pseudopotential. Compared with other phases, it is found that the Ni3Sn has larger relative expansion ratio and lower electrochemical potential, with its specific plateaus voltage around 0.3 eV when lithium atoms are filled in all octahedral interstitial sites, and the relative expansion ratio increasing dramatically when the lithiated phase transits from octahedral interstitial sites to tetrahedral interstitial sites. So this phase is a devastating phase for whole alloy electrode materials.

Lithium intercalation mechanism for β-SnSb in Sn-Sb thin films

Based on the first-principles plane wave pseudo-potential method, the electronic structure and electrochemical performance of LixSn4Sb4 （x=2, 4, 6, and 8） and LixSn12-xSb4 （x=9, 10, 11, and 12） phases were calculated. A Sn-Sb thin film on a Cu foil was also prepared by radio frequency magnetron sputtering. The surface morphology, composition, and lithium intercalation/extraction behavior of the fabricated film were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD） and cyclic voltammetry （CV）. Lithium atoms can easily insert into and extract out of the β-SnSb cell due to the low lithium intercalation formation energy. It is found that lithium atoms first occupy the interstitial sites, and then Sn atoms at the lattice positions are replaced by excessive lithium. The dissociative Sn atoms continue to produce different Li-Sn phases, which will affect the electrode stability and lead to the undesirable effect due to their large volume expansion ratio. The calculated lithium intercalation potential is stable at about 0.7 V, which is consistent with the experimental result.

Characterization and Electrochemical Properties of LiMn_2O_4 Thin Films Prepared by Solution Deposition

LiMn2O4 thin films were prepared by solution deposition using lithium acetate and manganese acetate us raw materials. The phase constitution and surface morphalogy were observed by X-ray diffraction and scanning electron microscopy. The electrochemical properties of the thin films were studied by cycilc voltammetry, charge- discharge experiments and impedance spectroscopy in 1 mol· L^-1 LiPF6 / EC- DMC solution using lithium metal as both the counter and reference electrodes. The films prepared by this method are of spinel phase. The lattice parameter increases with the annealing temperature aud annealing time. The film annealed at 750 ℃ for 30 minutes has the highest capacity of 34.5 μAh ·cm^- 2·μm^-1 , and its capacity loss per cycle is 0. 05% afrer being cycled 100 times.

Electrode structure enabling dendrite inhibition for high cycle stability quasi-solid-state lithium metal batteries

Lithium(Li)metal batteries(LMBs)are widely regarded as the ultimate choice for the next generation of high-energy–density batteries.However,the uncontrollable growth of Li dendrites formed by inhomogeneous deposition seriously hinders its commercialization.Although many studies have achieved significant results in inhibiting the formation of Li dendrites,it is still impossible to eradicate them completely.Therefore,regulating the deposition behavior,such as the growth direction of unevenly deposited Li,is preferable to unilaterally suppressing them in some cases.Here we report a structured anode that can confine the deposited Li within holes and tune it to become vertical-up/horizontal-centripetal mixed growth mode by optimizing the electric field/Li^(+)concentration gradient.The Li^(+) adsorbed by the poly(amic acid)(PAA)insulating layer coated on the anode surface can form the Li^(+)concentration gradient pointing to the center of the hole.Combined with the special electric field formed by the hole structure,it is favorable for the Li^(+)to move into the vertically arrayed holes and simultaneously deposit on the bottom and walls.Furthermore,both in-situ and ex-situ observations confirm that the growth mode is changed and the Li deposition morphology is denser,which can greatly delay capacity fading and prolong cycle life in both liquid and quasi-solid-state LMBs.All the results show that the novel anode provides a new perspective for deep research into solid-state LMBs.

Inverse-opal structured TiO_(2) regulating electrodeposition behavior to enable stable lithium metal electrodes

Lithium metal anode is almost the ultimate choice for high-energy density rechargeable batteries, but its uneven electrochemical dissolution-deposition characteristics lead to poor cycle stability and lithium dendrites safety problems. The fundamental solution to the problems is to interfere electrodeposition process of lithium metal so that it can be carried out reversibly and stably. In this work, an inverse-opal structured TiO2membrane with a thickness of only ~1 μm is designed to regulate the electrodeposition behavior of lithium metal, in which the ordered channels homogenize mass transfer process, the anatase TiO_(2)walls of the ion channels reduce desolvation barrier of solvated lithium-ions, and the spherical cavities with a diameter of ~300 nm confine migration of the adsorbed lithium atoms during electrocrystallization to diminish overpotential of lithium. These systematic effects cover and essentially change the whole process of electrodeposition of lithium metal and eliminate the possibility of lithium dendrite formation. The as-obtained lithium metal electrode delivers a Coulombic efficiency of 99.86% in the 100th cycle, and maintains a low deposition overpotential of 0.01 V for 800 h.

基于Sn-MOF组装的C/SnS/MoS_(2)纳米管及其锂离子电池性能研究

二硫化钼(MoS_(2))以高理论容量(662 mAhg^(-1))和较大层间距(0.62 nm)一直是锂离子电池负极材料的研究热点。然而,由于MoS_(2)的固有电子/离子导电率差且充放电循环过程中电极材料的体积变化严重,导致MoS_(2)的比容量迅速衰减,阻碍了MoS_(2)材料作为电池电极。在这项工作中,设计并合成了一种新型的C/SnS/MoS_(2)纳米管。具体来说,将Sn以Sn-MOF的形态包覆在一维的MoO3纳米带上,然后硫化得到保留了表面纳米片结构的C/SnS/MoS_(2)纳米管。这种制备方法不仅保留了表面的纳米片结构,也在表面留下来一层薄薄的非晶碳。得益于优越的结构设计,且SnS与MoS_(2)存在着协同作用,这不仅提高了导电性,并且也提升了电池循环的稳定性。做为电极材料时,复合材料能够在0.1 Ag^(-1)电流密度下80次循环后还保持着1110.2 mAhg^(-1)的放电比容量,在2 Ag^(-1)大电流密度下860次循环后保持801.7 mAhg^(-1)的放电比容量。

Preparation and electrochemical properties of LiFePO_4/C composite with network structure for lithium ion batteries

The bare LiFePO4 and LiFePO4/C composites with network structure were prepared by solid-state reaction. The crystalline structures, morphologies and specific surface areas of the materials were investigated by X-ray diffractometry(XRD), scanning electron microscopy(SEM) and multi-point brunauer emmett and teller(BET) method. The results show that the LiFePO4/C composite with the best network structure is obtained by adding 10% phenolic resin carbon. Its electronic conductivity increases to 2.86×10-2 S/cm. It possesses the highest specific surface area of 115.65 m2/g, which exhibits the highest discharge specific capacity of 164.33 mA·h/g at C/10 rate and 149.12 mA·h/g at 1 C rate. The discharge capacity is completely recovered when C/10 rate is applied again.

Large-scale fabrication of re duce d graphene oxide-sulfur composite films for flexible lithium-sulfur batteries

The rapid development of flexible electronic devices requires the design of flexible energy-storage devices. Lithium-sulfur(Li-S) batteries are attracting much interest due to their high energy density. Therefore, flexible Li-S batteries with high areal capacity are desired. Herein, we fabricated freestanding reduced graphene oxide-sulfur(RGO@S) composite films with a cross-linked structure using a blade coating technique, followed by a subsequent chemical reduction. The porous cross-linked structure endows the composite films with excellent electrochemical performance. The batteries based on RGO@S composite films could exhibit a high discharge capacity of 1381 m Ah/g at 0.1 C and excellent cycle stability. Furthermore, the freestanding composite film possesses excellent conductivity and high mechanical strength. Therefore, they can be used as the cathodes of flexible Li-S batteries. As a proof of concept, soft-packaged Li-S batteries were assembled and remained stable electrochemical performance under different bending states.

Effects of Al,F dual substitutions on the structure and electrochemical properties of lithium manganese oxide

Spinel LiMn2O4 and F, Al-doped spinel LiAl0.05Mn1.95O3.58F0.02 have been synthesized by a soft chemistry method using adipic acid as the chelating agent. The synthesized spine/materials were characterized by differential thermal analysis （DTA） and thermogravimetery （TG）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, cyclic voltammetry （CV）, and chargedischarge testing. The results indicate that all the samples have high phase purity, and fluorine is important in controlling the morphology; the doped aluminum enhances the stability of spinel LiMn2O4. The charge-discharge tests indicate that LiAl0.05Mn1.95O4 has high capacity retention, which is 92.60% of the initial after 50 cycles. It is found that the novel compound LiAl0.05Mn1.95O3.98F0.02 with smaller particles can offer much higher capacity, whose initial discharge capacity is 126.5 mAh·g^-1. The cyclic voltammetric experiments disclose the enhanced reversibility of the F, Al^3＋-modified spinel as compared with the undoped spinel.

Promising Electrode and Electrolyte Materials for High-Energy-Density Thin-Film Lithium Batteries

All-solid-state thin-film lithium batteries(TFLBs)are the ideal wireless power sources for on-chip micro/nanodevices due to the significant advantages of safety,portability,and integration.As the bottleneck for increasing the energy density of TFLBs,the key components of cathode,electrolyte,and anode are still underway to be improved.In this review,a brief history of TFLBs is first outlined by presenting several TFLB configurations.Based on the state-of-the-art materials developed for lithium-ion batteries(LIBs),the challenges and related strategies for the application of those potential electrode and electrolyte materials in TFLBs are discussed.Given the advanced manufacture and characterization techniques,the recent advances of TFLBs are reviewed for pursuing the high-energy-density and long-termdurability demands,which could guide the development of future TFLBs and analogous all-solid-state lithium batteries.