Effect of electrochemical processing of a γ-butyrolactone-based electrolyte on the cyclability of lithium electrodes

Effect of a preliminary electrolysis of electrolyte on the lithium electrode cyclability in a 1 M LiC1O₄ solution in γ-butyrolactone is studied. On its repeated cycling in the same electrolyte, the lithium electrode’s efficiency decreases and the overvoltage of cathodic and anodic processes considerably increases. Soluble products of electrochemical destruction of the electrolytic system accumulate in solution during the lithium electrode cycling, the products being prone to polymerization. In the presence of these products, the lithium passivation rate increases and the cycling efficiency decreases significantly. It is concluded that the soluble products of the destruction are oligomers formed during electrochemical polymerization of γ-butyrolactone     

三元锂离子动力电池衰减机理

失效分析是通过剖析电池循环过程中复杂的物理和化学变化引起的失效现象,优化材料制备和电池制作工艺,提升电池性能的有效途径。 通过对3.0～4.2 V电压范围1C循环1000周镍钴锰酸锂(NCM,LiNi_0.5Co_0.2Mn_0.3O₂)三元锂离子动力电池拆解分析后发现,正极容量损失约为2.73%,负极容量损失约为2.4%。 对比正负极片循环前后X射线衍射和场发射扫描电子显微镜分析发现,正极容量损失主要由正极颗粒破碎和结构转变引起的,负极衰减主要由循环过程中Li⁺持续脱嵌导致石墨层状结构损伤引起的。 正极过渡金属阳离子溶解并沉积在负极,催化电解液/电极界面副反应,导致负极过度成膜,活性锂损失,影响电极过程动力学也是电池失效的原因之一。     

Ferroelectric Metal–Organic Framework as a Host Material for Sulfur to Alleviate the Shuttle Effect of Lithium–Sulfur Battery

Ferroelectricity has an excellent reversible polarization conversion behavior under an external electric field. Herein, we propose an interesting strategy to alleviate the shuttle effect of lithium–sulfur battery by utilizing ferroelectric metal–organic framework (FMOF) as a host material for the first time. Compared to other MOF with same structure but without ferroelectricity and commercial carbon black, the cathode based on FMOF exhibits a low capacity decay and high cycling stability. These results demonstrate that the polarization switching behaviors of FMOF under the discharge voltage of lithium–sulfur battery can effectively trap polysulfides by polar–polar interactions, decrease polysulfides shuttle and improve the electrochemical performance of lithium–sulfur battery.     

Irreversible capacity of the amorphous silicon thin-film electrodes

Irreversible processes accompanying the lithium incorporation into amorphous thin-film silicon are investigated. It is shown that the irreversible processes occurred during the cathodic polarization result in the formation of passive film at the silicon surface. The passive film at silicon is close, in its composition, to the passive film at carbonaceous materials. However, unlike the carbonaceous electrodes, no effect of electrolyte composition on the irreversible capacity of the silicon electrodes is observed.     

Mechanism of Lithium Storage in MoS2 and the Feasibility of Using Li2S/Mo Nanocomposites as Cathode Materials for Lithium–Sulfur Batteries

The most-popular strategy to improve the cycling stability and rate performance of the sulfur electrode in lithium–sulfur (Li–S) batteries is to astrict the sulfur in a conducting medium by using complicated chemical/physical processing. Lithium sulfide (Li₂S) has been proposed as an alternative electrode material to sulfur. However, for its application, it must meet challenges such as high instability in air together with all of the drawbacks of a sulfur–containing electrode. Herein, we report the feasibility of using Li₂S, which was obtained by electrochemical conversion of commercial molybdenum disulfide (MoS₂) into Li₂S and metallic molybdenium (Mo) at low voltages, as a high-performance active material in Li–S batteries. Metallic Mo prevented the dissolution of lithium polysulfides into the electrolyte and enhanced the conductivity of the sulfide electrode. Therefore, the in situ electrochemically prepared Li₂S/Mo composite exhibited both high cycling stability and high sulfur utilization.     

Electrochemical noise of a lithium electrode in organic electrolytes: A study by a correlation function method

Fluctuations of the potential of a lithium electrode in conditions of galvanostatic polarization in aprotic organic electrolytes are studied by a method of correlation functions. Computer-aided removal of heavy interference in the form of slow variation of the electrode potential proved to be possible to perform with use made of fifth-power polynomials. The time coordinate of the first zero in the correlation function weakly depends on the electrolyte type and lies within the limits 1.5–3 s. At the same time, the electrolyte type affects the dispersion of the electrode potential fluctuations in a substantial manner. In so doing, lithium systems that feature a high cycling efficiency possess a lower level of noise.     

Electrochemical insertion of lithium in thin tin films

The behavior of model electrodes made of lithiated thin films of tin during their cycling is studied. The electrodes show high values of useful specific capacity for the extension of several tens of operation cycles. Dependences of the diffusion coefficient for lithium into tin on the initial electrode potential, temperature, and direction of the electrode process are determined by a chronopotentiometric method. The dependences have a complex character, which is connected with the phase composition of the lithium-tin alloy.     

Ferrocene‐Promoted Long‐Cycle Lithium–Sulfur Batteries

Confining lithium polysulfide intermediates is one of the most effective ways to alleviate the capacity fade of sulfur‐cathode materials in lithium–sulfur (Li–S) batteries. To develop long‐cycle Li–S batteries, there is an urgent need for material structures with effective polysulfide binding capability and well‐defined surface sites; thereby improving cycling stability and allowing study of molecular‐level interactions. This challenge was addressed by introducing an organometallic molecular compound, ferrocene, as a new polysulfide‐confining agent. With ferrocene molecules covalently anchored on graphene oxide, sulfur electrode materials with capacity decay as low as 0.014 % per cycle were realized, among the best of cycling stabilities reported to date. With combined spectroscopic studies and theoretical calculations, it was determined that effective polysulfide binding originates from favorable cation–π interactions between Li⁺ of lithium polysulfides and the negatively charged cyclopentadienyl ligands of ferrocene.     

The development of lithium ion secondary batteries

Lithium ion secondary batteries (LIBs) were successfully developed as battery systems with high volumetric and gravimetric energy densities, which were inherited from lithium secondary batteries (LSBs) with metallic lithium anodes. LSBs have several drawbacks, however, including poor cyclability and quick-charge rejection. The cell reaction in LIB is merely a topochemical one, namely the migration of lithium ions between positive and negative electroces. No chemical changes were observed in the two electrodes or in the electrolytes. This results in little chemical transformation of the active electrode materials and electrolytes, and thus, LIBs can overcome the weaknesses of LSBs; for example, LIBs show excellent cyclability and quick-charge acceptance. Many difficulties, however, were encountered during the course of development, including capacity fade during cycling and safety issues. This article is the story of the development of LIBs and it describes how the difficulties were surmounted.     

锂电池电极过程的原位电化学原子力显微镜研究进展

随着人类对能源的使用与存储需求不断增加,高能量密度和高安全性能的二次锂电池体系正在被不断地开发与完善.深入理解充放电过程中锂电池内部电极/电解质界面的电化学过程以及微观反应机理,有利于指导电池材料的优化设计.原位电化学原子力显微镜将原子力显微镜的高分辨表界面分析优势与电化学反应装置相结合,能够在电池运行条件下实现对电极/电解质界面的原位可视化研究,并进一步从纳米尺度上揭示界面结构的演化规律与动力学过程.本文总结了原位电化学原子力显微镜在锂电池电极过程中的最新研究进展,主要包括基于转化型反应的正极过程、固体电解质中间相的动态演化以及固态电池界面演化与失效分析.     

Electrochemical investigation of lithium intercalation into graphite from molten lithium chloride

Lithium reduction at a graphite electrode in molten lithium chloride was studied at temperatures from 650 to 900 °C using cyclic voltammetry and chronoamperometry. It was found that, during cathodic polarization, lithium intercalation into graphite occurred before deposition of metallic lithium started. This process was confirmed to be rate-controlled by the diffusion of lithium in the graphite. When the cathodic polarization potential was more negative than that for metallic lithium deposition, exfoliation of graphite particles from the electrode surface was observed. This was caused by fast and excessive accumulation of lithium intercalated into the graphite, which produced mechanical stress too high for the graphite matrix to accommodate. The erosion process was abated once the graphite surface was covered by a continuous layer of liquid lithium. These results are of relevance to the mechanism of carbon nanotube and nanoparticle formation by electrochemical synthesis in molten lithium chloride.     

Cycling a Sulfur Electrode: Effect of Physicochemical Properties of Electrolyte Systems

A sulfur electrode is cycled in mixtures of 3-methoxysulfolane and sulfolane with linear ethers (glyme, diglyme, tetraglyme) and lithium trifluoromethane sulfonate (lithium triphlate) as the supporting electrolyte. The decrease in the electrode capacity, observed with an increase in the number ethylene oxide links in glyme molecules and in the number of donor centers in sulfone molecules, is attributed to changes in the form taken by lithium polysulfides in solutions and the increase in the electrolyte viscosity.     

Impedance spectroscopy studies of changes in the properties of lithium-sulfur cells in the course of cycling

Changes in the properties of lithium-sulfur cells during cycling were studied by impedance spectroscopy. The electric conductivity of the electrolyte changed during the charging and discharging of the lithium-sulfur cells as a result of the dissolution of lithium polysulfides formed in electrochemical reactions. The maximum resistance of the electrolyte and the surface layers on the sulfur and lithium electrodes was achieved in the region of the transition between the low- and high-voltage areas on the charge and discharge curves of the cells. This region corresponded to the highest concentration of lithium polysulfides in the electrolyte. For nearly charged or discharged lithium-sulfur cells, the impedance spectra contained linear segments which could be attributed to diffusion limitations at low frequencies. An analysis of the results of impedance studies suggested that the electrochemical processes in lithium-sulfur cells were controlled by diffusion in the surface layer on the sulfur electrode at high degrees of charge or discharge and by the transport properties of the electrolytic system at moderate degrees of charging.     

Reaction of SbPO4 with lithium in non-aqueous electrochemical cells: preliminary study and evaluation of its electrochemical performance in anodes for lithium ion batteries

SbPO₄, a phosphate with a layered structure, was tested as an electrode material for lithium cells spanning the 3.0-0.0 V range. Two main electrochemical processes were detected as extensive plateaus at ca. 1.6 and 0.7 V in galvanostatic measurements. The first process was found to be irreversible, thus excluding a potential intercalation-like mechanism for the reaction and being better interpreted as a decomposition reaction leading to the formation of elemental Sb. This precludes the use of this compound as a cathodic material for lithium cells. By contrast, the process at 0.7 V is reversible and can be ascribed to the formation of lithium-antimony alloys. The best electrochemical response was obtained by cycling the cell at a C/20 discharge rate over the voltage range 1.25-0.25 V. Under these conditions, the cell delivers an average capacity of 165 Ah/kg—a value greater than those reported for other phosphates—upon successive cycling.     

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Here, we use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach enabled us to obtain a uniform and thin (around tens of nanometers) sulfur coating on graphene oxide sheets by a simple chemical reaction-deposition strategy and a subsequent low-temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides enabled us to demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mA h g(-1), and stable cycling for more than 50 deep cycles at 0.1C (1C = 1675 mA g(-1)).     

Cycling a Sulfur Electrode in Electrolytes Based on Sulfolane and Linear Ethers (Glymes) in an LiCF3SO3 Solution

The cycling of a sulfur electrode is studied in sulfolane mixtures with linear ethers (1,2-dimethoxyethane, diglyme, tetraglyme) in an LiCF₃SO₃ solution. The results confirm the assumption made previously that different forms of existence of lithium polysulfides in an electrolytic solution affect their electrochemical activity and the decrease in the sulfur electrode capacity during its cycling.     

Reasons for the effect of the amount of electrolyte on the performance of lithium–sulfur cells

As is known, the depth of the electrochemical reduction of sulfur and lithium polysulfides, the reduction rate, and the cycle life of lithium–sulfur cells decrease with the electrolyte content. The present paper studies the reasons for the effect of the amount of electrolyte on the depth of sulfur reduction and the cycle life of lithium–sulfur cells. The main reason for the effect of the amount of electrolyte on the depth of the electrochemical reduction of sulfur was shown to be the generation of solvate complexes of lithium polysulfides. The minimum amount of electrolyte required for complete reduction of sulfur during the discharge of lithium–sulfur cells is determined by the composition of the generated solvate complexes of lithium polysulfides. The solvate numbers of the lithium ion in the solvate complexes of lithium polysulfides generted in sulfolane electrolyte systems were evaluated from the experimental data. An analysis of the results shows that the minimum solvate number of lithium ions in the solvate complexes of lithium polysulfides with sulfolane is 1.     

Carbon Nanofibers Decorated with Molybdenum Disulfide Nanosheets: Synergistic Lithium Storage and Enhanced Electrochemical Performance

Traditional lithium‐ion batteries that are based on layered Li intercalation electrode materials are limited by the intrinsically low theoretical capacities of both electrodes and cannot meet the increasing demand for energy. A facile route for the synthesis of a new type of composite nanofibers, namely carbon nanofibers decorated with molybdenum disulfide sheets (CNFs@MoS₂), is now reported. A synergistic effect was observed for the two‐component anode, triggering new electrochemical processes for lithium storage, with a persistent oxidation from Mo (or MoS₂) to MoS₃ in the repeated charge processes, leading to an ascending capacity upon cycling. The composite exhibits unprecedented electrochemical behavior with high specific capacity, good cycling stability, and superior high‐rate capability, suggesting its potential application in high‐energy lithium‐ion batteries.     

Elimination of irreversible capacity of amorphous silicon: direct contact of the silicon and lithium metal

A method of elimination of the amorphous silicon irreversible capacity is suggested, which is based on the direct contact of the silicon and lithium metal under electrolyte. It is shown that this contact yields a solid-electrolyte film over the electrode surface even prior to its initial cathodic polarization, which results in the elimination of the irreversible capacity of amorphous silicon.     

Cycling a Sulfur Electrode in Mixed Electrolytes Based on Sulfolane: Effect of Ethers

The cycling of a sulfur electrode is studied in 1 M LiCF₃SO₃ solutions in sulfolane mixtures with ethers 1,2-dimethoxyethane, dioxolane, and tetrahydrofuran. The results suggest that the electrochemical behavior of sulfur is defined by the forms of existence of lithium polysulfides in the electrolyte.